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。     

基于钠基吸附剂的烟气脱碳系统余热利用研究

针对基于钠基固体吸附剂的燃烧后脱碳技术应用于燃煤电厂后综合能耗偏高的问题,本文提出与供热机组结合的碳捕集/供热双机组系统,利用低温热网回水回收系统低品位余热。依据双机组的抽汽混合与否构建了两种系统流程,分析了两种不同方案下的系统性能。研究结果表明,在有效回收脱碳系统碳酸化反应余热后,独立抽汽方案中碳捕集综合能耗从4.05GJ/t CO₂降低至1.26GJ/t CO₂,而混合抽汽方案中碳捕集综合能耗降低至1.13GJ/t CO₂,同时双机组系统的热网供热量较单供热机组分别增加了67.5%和72.8%,经济效益显著。分析了混合抽汽方案的系统中碳捕集综合能耗随相关运行参数变化的规律,发现碳酸化反应温度和热网回水温度因为能够直接影响系统余热利用程度因而更易对碳捕集综合能耗产生影响。     

钙循环捕集CO2后CaO的水合/脱水热化学储热性能

提出了基于CaO的钙循环捕集CO₂与CaO/Ca(OH)₂体系热化学储热耦合新工艺，在双固定床反应器上，研究了循环捕集CO₂中煅烧条件和碳酸化条件对CaO储热性能的影响，探究CaO循环捕集CO₂过程和循环水合/脱水储热过程的相互作用。研究表明，多次循环碳酸化/煅烧捕集CO₂后CaO仍具有较高储热性能，10次循环捕集CO₂后再经10次储热循环，CaO水合转化率可达0.66mol/mol。与苛刻煅烧条件相比，温和煅烧条件下经历多次循环捕集CO₂后CaO的储热性能更高。在碳酸化气氛中加入水蒸气对经历多次循环捕集CO₂后CaO储热性能的影响不大。钙循环捕集CO₂过程和水合/脱水循环储热过程能够相互促进。该工艺有望同时实现CO₂捕集和储热，具有一定的应用前景。     

CO2 capture by double metal modified CaO-based sorbents from pyrolysis gases

High-temperature pyrolysis technology can effectively solve the problem of municipal solid waste pollution. However, the pyrolysis gas contains a large amount of CO₂, which would adversely affect the subsequent utilization. To address this problem, a novel method of co-precipitation modification with Ca, Mg and Zr metals was proposed to improve the CO₂ capture performance. X-ray diffraction (XRD) patterns and energy dispersive X-ray spectroscopy analysis showed that the two inert supports MgO and CaZrO₃ were uniformly distributed in the modified calcium-based sorbents. In addition, the XRD results indicated that CaZrO₃ was produced by the reaction of ZrO₂ and CaO at high temperatures. The effects of doping ratios, adsorption temperature, calcination temperature, CO₂ concentration and calcination atmosphere on the adsorption capacity and cycle stability of the modified calcium-based sorbent were studied. The modified calcium-based sorbent achieved the best CO₂ capture performance when the doping ratio was 10:1:1 with carbonation at 700 ℃ under 20% CO₂/80% N₂ atmosphere and calcination at 900 ℃ under 100% N₂ atmosphere. After ten cycles, the average carbonation conversion rate of Ca-10 sorbent was 72%. Finally, the modified calcium-based sorbents successfully reduced the CO₂ concentration of the pyrolysis gas from 37% to 5%.     

碳酸酐酶和甲酸脱氢酶的稳定性研究进展

化石燃料的大量燃烧使温室气体CO₂的排放量不断增加,对环境造成恶劣影响,将CO₂捕集并转化为高附加值化学品是实现节能减排和变废为宝的一种双赢策略。酶催化CO₂捕集和转化具有高效、高选择性、反应条件温和、环境友好等优点。碳酸酐酶（CA）可大大加速CO₂水合反应,而甲酸脱氢酶（FDH）可催化CO₂还原为甲酸,二者协同可增强CO₂还原动力学。但酶促反应的工业化应用过程中,酶所处环境的温度、酸碱度以及其他离子的种类和浓度等因素均可能导致酶失活,因此,酶的稳定性研究至关重要。本文从热稳定性、酸碱稳定性和离子稳定性的角度,综述了CA和FDH的稳定性研究进展。改善酶稳定性的手段包括使用极端微生物、酶分子设计与改造、固定化等,重点讨论了固定化对酶稳定性的提升效果,为未来的工业化应用提供参考。     

基于热流逸效应的燃煤电厂烟气二氧化碳分离系统

分离捕集CO₂是实现“双碳”目标的重要途径之一。常规的CO₂分离方法普遍能耗较高,若能以余(废)热为动力来分离CO₂则可综合利用能源、降低能耗。本文针对高碳排放但却拥有丰富余(废)热资源的燃煤电厂,提出了一种基于热流逸效应的烟气CO₂分离系统,并建立了相应的分离过程数学模型和系统性能评价指标。分析表明,CO₂的浓度和回收率均随热流逸式气体分离器串联级数的增加而升高,但浓度和回收率达到某一阈值后效果不再明显;典型的1000MW燃煤电厂烟气经该系统中串联的24级分离器处理后,CO₂的物质的量分数最高可达98.89%,回收率达72.53%。此外,该系统可梯级利用烟气的余热,?效率为64.8%,单位能耗为0.047GJ/tCO₂,与传统CO₂分离方法相比具有一定节能潜力。利用热流逸效应分离CO₂符合当下净零碳排放的政策导向,为CO₂的分离捕集提供了新思路。     

基于热重-质谱联用的煤粉富氧燃烧动力学及污染物生成特性

富氧燃烧是最具工业化前景的燃烧中碳捕集技术之一,为更深入掌握煤粉富氧燃烧的着火模式和污染物生成特性,本文构建了热重-质谱联用实验系统,以烟煤和无烟煤标准煤样为对象,针对3个不同的氧气体积分数：21%、30%和50%,研究了O₂/Ar和O₂/CO₂气氛下煤粉的富氧燃烧特性。结果表明,O₂/CO₂气氛下煤粉着火温度和燃尽温度均降低,燃烧速率提高,燃烧时间缩短;两种煤粉在O₂/Ar气氛下的燃烧都属于非均相着火,而富氧燃烧都属于均相着火模式;氧气体积分数在30%以上时,无烟煤O₂/CO₂燃烧的表观活化能明显低于O₂/Ar气氛,在相同工况下烟煤的表观活化能均低于无烟煤;O₂/CO₂气氛促进了CO和挥发分NO的逸出,生成温度均低于O₂/Ar气氛,CO会对NO起到还原作用。     

四乙烯五胺改性多孔二氧化硅制备及CO2吸附性能

以十六烷基三甲基溴化铵（CTAB）为模板剂，原硅酸乙酯（TEOS）为硅源，1,3,5-三异丙基苯（TPB）为扩孔剂，制备不同孔道结构的多孔二氧化硅纳米微球（PSNs），将四乙烯五胺（TEPA）通过物理浸渍法负载到PSNs上，合成TEPA-PSNs吸附剂。利用扫描电镜、透射电镜、红外光谱、N₂吸附-脱附循环实验和热重分析对材料的结构性能和热稳定性能进行表征，成功制备了具有不同孔道结构的胺基化多孔二氧化硅。对吸附剂材料进行CO₂吸脱附实验和动力学研究，结果表明：当TPB含量增多时，吸附剂材料吸附的CO₂量也随之增大，并且TEPA-PSNs-0.5在75℃时吸附量最大，达4.70mmol/g；一阶动力学模型能较好地预测该吸附剂的CO₂吸附过程；经过5次循环，其再生性能仍然高达94.34%。因此，合成的胺基化多孔二氧化硅具有高吸附量和良好稳定性，是用于二氧化碳捕集的潜在材料。     

Review of solvent based carbon-dioxide capture technologies

Currently, a large proportion of global fossil fuel emissions originate from large point sources such as power generation or industrial processes. This trend is expected to continue until the year 2030 and beyond. Carbon capture and storage (CCS), a straightforward and effective carbon reduction approach, will play a significant role in reducing emissions from these sources into the future if atmospheric carbon dioxide (CO₂) emissions are to be stabilized and global warming limited below a threshold of 2 °C. This review provides an update on the status of large scale integrated CCS technologies using solvent absorption for CO₂ capture and provides an insight into the development of new solvents, including advanced amine solvents, amino acid salts, carbonate systems, aqueous ammonia, immiscible liquids and ionic liquids. These proposed new solvents aim to reduce the overall cost CO₂ capture by improving the CO₂ absorption rate, CO₂ capture capacity, thereby reducing equipment size and decreasing the energy required for solvent regeneration.     

空气中直接捕集CO2技术研究进展

减少碳排放并推动碳中和是应对气候变化、促进经济社会绿色转型的重要途径之一,碳中和技术已成为工业界和学术界的关注焦点。目前碳捕集与封存主要对工业固定源排放的CO₂进行处置捕集,而对占CO₂总排放近50%的分布源CO₂关注度不高。直接空气捕集(direct air capture,DAC)技术不仅可对数以百万计的小型化石燃料燃烧装置以及数以亿计的交通工具等分布源排放的CO₂进行捕集处理,还可有效降低大气中CO₂浓度。介绍了DAC的发展历史、研究现状以及发展趋势,综述了已有DAC技术的工艺流程以及反应装置,对DAC现行工艺中涉及的空气捕捉模块、吸收剂或吸附剂再生模块、CO₂储存模块进行了叙述,对比了几种工艺的优缺点以及吸附剂类型和再生方式,指出DAC技术发展的关键在于研发高效低成本的吸收/吸附材料和设备。分析了DAC吸收/吸附材料的作用原理以及吸附效果,碱性溶液原料成本相对低廉,但再生过程中能耗较高。分子筛及金属有机框架吸附剂虽然再生能耗较低,但对空气中CO₂的吸附容量和吸附选择性表现一般。胺类吸附剂具有较好的吸附能力,由于其再生温度较低,可使用工业废热或少量热能为系统供能;使用胺类吸附剂时吸附和解吸在一个单元中逐步发生,具有更高的效率和操作时间,有望降低DAC系统成本。对比了DAC与其他碳捕集技术的成本并进行了技术经济性分析,DAC成本主要包含运营和维护成本(N_Q&M)、吸附剂材料成本(N_S)和工厂设备的净成本(N_bop);指出目前限制DAC工业化应用的主要因素之一在于吸收/吸附材料和相关工艺成本过高,随着阴离子交换树脂等新型吸附剂的出现和工艺的发展,DAC成本逐年下降。全面探究吸收/吸附材料稳定性、动力学、吸附容量、选择性、再生能量损失等综合性能,研发利于快速装载和卸载吸附剂的相关装置,开发成本低廉的工艺系统是目前DAC领域的发展方向和迫切需求。DAC技术将为减少全球碳排放、实现碳中和提供重要技术支撑。     

耦合膜分离的新型CO2低温捕集系统性能优化

CO₂捕集作为温室气体排放控制的有效手段已成为重要研究课题。作为新兴捕集技术之一,低温CO₂捕集因产品纯度高、无附加污染等优势受到关注。然而,该技术能耗和捕集率对于气体中CO₂浓度十分敏感,对于高CO₂浓度气体可获得较高的CO₂捕集率和较低能耗水平。基于此,本文提出了耦合膜分离的新型CO₂低温捕集系统,通过膜材料选择渗透性实现待捕集气体CO₂浓度主动调控,并在最优浓度下进行CO₂低温捕集。首先基于不同传统低温捕集系统特点,对比分析了不同耦合系统模式,从而确定了最优耦合系统结构。针对最优耦合系统进行了运行参数优化,并分别基于实现系统捕集能耗最低与捕集率最高的目标,获得了膜渗透侧CO₂浓度与进气CO₂浓度间的关系式,为该耦合系统中膜组件选型提供指导。研究表明,本文提出的耦合系统捕集能耗为1.92MJ/kgCO₂,相比于传统单一低温系统捕集能耗可降低16.5%。     

基于整体煤气化联合循环的燃烧前CO2捕集工艺及系统分析

CO₂减排作为应对全球变暖的重要手段而逐渐成为国内外研究热点。为研究燃烧前CO₂捕集系统关键技术,以华能（天津）265MW级整体煤气化联合循环发电系统（IGCC）示范电站为依托,从气化装置抽出合成气约10000m³/h（标况下）,进行一氧化碳耐硫变换、甲基二乙醇胺（MDEA）硫碳共脱、PDS硫回收等技术研究,同时完成我国首套工业规模级燃烧前捕集工艺模拟、系统分析及现场测试。研究结果表明：满负荷运行工况下,每年可捕集CO₂ 7.811万吨,系统单位能耗2.35GJ/t（CO₂）,CO₂捕集率≥ 85%;模拟结果与实际运行数据相吻合。其中MDEA工段能耗占捕集能耗的93.3%,热再生部分则占MDEA工段能耗的81.61%;同时分析了捕集系统各工段CO₂损失过程,增加四段变换可使系统能耗基本不变同时捕集率增加至92.29%;考察了CO₂压缩液化工段能耗及成本。本研究结果可为燃烧前CO₂捕集的设计、工业放大及过程优化提供理论支持。     

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。     

ZIF-8浆液中试分离CO2/N2过程模拟及能耗分析

ZIF-8/2-甲基咪唑-乙二醇-水浆液(ZIF-8浆液)可以高效低耗能地分离CO₂。为了进一步评估ZIF-8浆液在填料塔中分离CO₂的塔效率及能耗,使用Peng-Robinson(PR)状态方程,求出CO₂和ZIF-8浆液的二元交互作用参数(k_CO2),将二元交互作用参数和Aspen Plus软件进行关联,对CO₂/N₂多级吸收分离进行过程模拟。计算结果表明在中试填料塔中,ZIF-8浆液仅需要5块理论塔板即可将CO₂浓度由20%(mol)降低至2%(mol)以下,填料塔的塔板效率为25%。对中试分离CO₂/N₂进行能耗计算,结果表明当解吸条件为解吸温度333 K,解吸压力0.8 MPa和空气吹扫流量200 L/h时,CO₂捕集等效功最低可至0.474 GJ/t CO₂。在同样条件下使用ZIF-8浆液和MEA(30%(mass))水溶液进行碳捕集时,CO₂捕集等效功分别为0.507 GJ/t CO₂和0.957 GJ/t CO₂,ZIF-8浆液的CO₂捕集等效功仅为MEA水溶液的53%。     

Recent progress in porous organic polymers and their application for CO2 capture

Carbon capture, storage, and utilization (CCSU) is recognized as an effective method to reduce the excessive emission of CO₂. Absorption by amine aqueous solutions is considered highly efficient for CO₂ capture from the flue gas because of the large CO₂ capture capacity and high selectivity. However, it is often limited by the equipment corrosion and the high desorption energy consumption, and adsorption of CO₂ using solid adsorbents has been receiving more attention in recent years due to its simplicity and high efficiency. More recently, a great number of porous organic polymers (POPs) have been designed and constructed for CO₂ capture, and they are proven promising solid adsorbents for CO₂ capture due to their high Brunauer-Emmett-Teller (BET) surface area (S_BET), adjustable pore size and easy functionalization. In particular, they usually have rigid skeleton, permanent porosity, and good physiochemical stability. In this review, we have a detailed review for the different POPs developed in recent years, not only the design strategy, but also the special structure for CO₂ capture. The outlook of the opportunities and challenges of the POPs is also proposed.     

A large-scale experimental study on CO2 capture utilizing slurry-based ab-adsorption approach

The increasing concentration of CO_2 in atmosphere is deemed the main reason of global warming.Therefore,efficiently capturing CO_2 from various sources with energy conservation is of great significance.Herein,a series of experiments were carried out to successfully test the slurry-based ab-adsorption method for continuously capturing CO_2 in the large-scale cycled separation unit with cost-effect taking into account the scale-up criteria.A bubble column(with height 4900 mm and inner diameter 376 mm) and a desorption tank(with volume 310 L) are the essential components of the separation unit.The novel slurry used in this study was formed with zeolitic imidazolate framework-8 and 2-methylimidazole-water solution.The influence of operation conditions was investigated systematically.The results show that increasing sorption pressure and slurry height level,decreasing gas volume flow and sorption temperature are beneficial for separation processes.The volume fraction of CO_2 in the feed gas was also studied.Although the scale-up effect had been observed and it was found that it exerted a negative effect on CO_2 capture,depending on experimental conditions,CO_2 removal efficiency could still reach 85%-95% and the maximum CO_2 loading in the recycled slurry could be up to0.007 mol·L~(-1)·kPa~(-1).Furthermore,the slurry-based method could be operated well even under very moderate regeneration conditions(333 K and 0.05 MPa),which means that the novel approach shows greater energy conservation than traditional amine absorption methods.     

一种低能耗捕集CO2煤基甲醇和电力联产过程设计

传统的煤制甲醇过程所需合成气的氢碳比为2.1左右,而煤气化粗合成气氢碳比仅为0.7左右,因此需要将部分合成气进行变换来调节氢碳比。然而,变换气与未变换气混合后使得CO₂浓度降低,从而导致CO₂捕集能耗增加。提出了一种低能耗捕集CO₂煤基甲醇和电力联产过程。新联产过程中部分粗合成气首先经过变换,将CO转变为H₂和CO₂,CO₂浓度提高,在此时进行CO₂捕集可实现捕集能耗的降低。经CO₂捕集后,得到富H₂气体,富H₂气体分流后与另一部分煤气化粗合成气混合调节甲醇合成的氢碳比。对新的过程进行了建模、模拟与分析。结果表明相比传统的带CO₂捕集的煤制甲醇和IGCC发电过程,新的联产过程的能量节约率可达到16.5%,CO₂捕集能耗下降30.3%。     

电化学二氧化碳还原制甲酸催化剂的研究进展

随着日益增长的能源需求,人类社会对于传统碳基化石能源过度依赖,不仅加速了地球上有限能源储备的消耗,还导致大气中二氧化碳(CO₂)不断累积。如何对二氧化碳进行可持续的捕获再利用,实现高效的零碳网络循环,已成为人类亟需解决的重大挑战之一。近年来,使用绿色可持续电力的电化学二氧化碳还原反应(CO₂RR)生产增值化学品成为研究热点。本文首先介绍了CO₂RR的基本电化学反应原理;然后总结了电化学还原CO₂制备甲酸/甲酸盐的主要金属基催化剂,着重介绍了Bi、Sn、In三类金属基催化剂的设计调控策略;进一步概括了电化学相关的原位表征手段,分别介绍了原位光谱技术和原位X射线表征技术;最后对电催化二氧化碳还原研究领域的未来发展进行了展望。     

Gas leakage recognition for CO2 geological sequestration based on the time series neural network

The leakage of stored and transported CO₂ is a risk for geological sequestration technology. One of the most challenging problems is to recognize and determine CO₂ leakage signal in the complex atmosphere background. In this work, a time series model was proposed to forecast the atmospheric CO₂ variation and the approximation error of the model was utilized to recognize the leakage. First, the fitting neural network trained with recently past CO₂ data was applied to predict the daily atmospheric CO₂. Further, the recurrent nonlinear autoregressive with exogenous input (NARX) model was adopted to get more accurate prediction. Compared with fitting neural network, the approximation errors of NARX have a clearer baseline, and the abnormal leakage signal can be seized more easily even in small release cases. Hence, the fitting approximation of time series prediction model is a potential excellent method to capture atmospheric abnormal signal for CO₂ storage and transportation technologies.     

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.