负载型钾基吸附剂的CO2吸附机理及失效特性

为获得不同载体钾基吸附剂对CO_2的吸附机理,对3种载体(循环流化床锅炉飞灰、活性炭和氧化铝)和3种K_2CO_3理论负载量(10%、30%和50%)改性条件下的吸附剂进行了研究,获得了反应温度(50、60、70、80和90℃)及CO_2浓度(5%、7.5%、10%、12.5%和15%)对吸附剂CO_2吸附性能的影响,同时利用比表面积及孔隙度分析仪和X射线衍射仪研究了负载和反应前后吸附剂的微观特性,结合其反应动力学过程,探明其影响机理。结果表明:3种吸附剂的最佳理论负载量为30%,且70℃的反应温度和12.5%的CO_2浓度为最佳反应工况;K_2CO_3/AC吸附剂的实际负载量和CO_2吸附性能最优,而K_2CO_3/Al_2O_3吸附剂则最差;吸附剂的碳酸化反应过程中,相比比孔容积,比表面积发挥更重要的作用;随着反应温度的升高,内扩散阻力显著增强;SO_2和HCl会与K_2CO_3反应生成新的物质导致吸附剂逐渐失效,3种吸附剂中K_2CO_3/AC的循环失效性能最好。     

Mg-Al-Me (Me=La,Ce,Zr)复合氧化物制备及其除氟性能

采用双滴共沉淀-煅烧法制备Mg-Al-Me(Me=La,Ce,Zr)金属复合氧化物吸附剂,通过扫描电子显微镜(SEM)和X射线衍射(XRD)对制备的吸附剂进行表征.采用批实验考察了吸附时间,初始氟浓度和共存离子(Cl~-、NO_3~-、SO_4~(2-)、CO_3~(2-)、HCO_3~-、PO_4~(3-))对氟吸附性能的影响.结果表明,3种吸附剂对氟吸附过程可用准二级动力学模型描述.3种吸附剂对氟吸附速率主要受液膜扩散速率、颗粒内扩散速率和吸附反应速率共同控制.等温吸附结果显示Mg-Al-La对氟吸附能力最大,MgAl-Ce次之,Mg-Al-Zr最小,3种材料对氟吸附规律均符合Langmuir等温吸附方程,其最大饱和吸附量分别为54.22、51.65、50.89 mg·g-1.共存离子对3种材料吸氟存在不同程度的竞争,其影响次序是Cl~-NO_3~-SO_4~(2-)CO_3~(2-)≈HCO_3~-PO_4~(3-).     

改性磁性纳米颗粒固定内生菌Bacillus nealsonii吸附废水中Cd2+的特性研究

从重金属超累积植物龙葵体内提取内生菌Bacillus nealsonii,采用二氧化硅改性纳米Fe_3O_4颗粒与海藻酸钠将其包埋交联进行固定化,制得一种新型球状生物吸附剂,并应用于废水中Cd~(2+)的吸附处理.同时,通过正交实验研究了该球状生物吸附剂的最佳制备条件和吸附处理条件,并采用扫描电镜等表征手段与构建吸附动力学考察了其吸附特征.结果表明,球状生物吸附剂的最佳制备条件为:改性纳米Fe3O4颗粒质量分数为0.1%,海藻酸钠质量分数为8.0%,菌液接种量为0.4%,交联时间为2 h;其最佳吸附处理条件为p H=6、吸附时间12 h、吸附剂用量(干重)2.5 g·L-1,在Cd~(2+)初始浓度为50 mg·L-1时的吸附率可达96%以上.研究发现,球状生物吸附剂的内外部结构孔隙率较大,有利于促进Cd~(2+)的吸附.该吸附过程遵循准二级反应动力学,以化学吸附为主,符合Freundlich等温吸附模型,最大单分子吸附量可达13.02 mg·g-1.解吸实验结果表明,该吸附剂具有较好的可重复利用性.     

浸渍法制备负载化离子液体吸附剂及其表征

采用浸渍法制备了负载化离子液体吸附剂[Bmim]BF_4@SBA-15,N_2吸附、SEM及TG表征发现:离子液体主要负载于SBA-15载体孔道内,少量附着于载体外表面。为优化制备条件,重点考察了共溶剂、反应时间、离子液体和载体的质量比等因素对负载量的影响。实验结果表明:当丙酮为共溶剂、离子液体与载体质量比为6∶1、浸渍时间为9 h时,离子液体负载量可达66.8%。在此基础上,对负载化离子液体进行CO_2吸附性能测试,发现随离子液体负载量增加,CO_2吸附量先增大后减小。当负载量为34.9%时,CO_2吸附量可达40.3 mg/g。     

纳米Fe3O4负载的浮游球衣菌去除Cr(Ⅵ)的研究

以纳米Fe₃O₄负载浮游球衣菌（Sphaerotilus natans）为复合生物吸附剂,考察了其对Cr(Ⅵ)的吸附性能,并对生物吸附机理进行了初步研究.结果表明,pH值是影响复合生物吸附剂吸附Cr(Ⅵ)的主要因素,吸附的最佳pH为2～3;用此复合生物吸附剂对Cr(Ⅵ)进行吸附,其单位吸附量为0.0217 mmol/g.用HCl对其进行再生,再生率在90％以上;—CONH₂和—NH—是菌体吸附Cr(Ⅵ)的主要活性基团,静电吸引是复合生物吸附剂吸附Cr(Ⅵ)的主要机理之一.     

EDTA-nSiO2纳米颗粒对Cd2+的吸附

nSiO_2纳米颗粒是一种广泛应用的工程纳米材料,为增加其对水溶液中Cd~(2+)的吸附性能,采用接枝改性的方法制备出乙二胺四乙酸(EDTA)改性nSiO_2纳米颗粒(EDTA-nSiO_2),并用透射电镜、氮气吸附-解吸、红外光谱和差热分析等手段对其进行了结构表征,同时以其为吸附剂,通过批处理实验法探讨了体系pH、吸附时间、温度、离子强度等因素对Cd~(2+)吸附的影响,并结合X射线能谱(XPS)分析对其吸附机制进行了分析.结果表明,以EDTA为改性剂,可以成功制备出稳定性良好的EDTA-nSiO_2纳米颗粒,其对Cd~(2+)的吸附受体系p H控制;nSiO_2对Cd~(2+)的吸附量较小,EDTA改性可增加nSiO_2对Cd~(2+)的吸附作用,随着p H的升高,Cd~(2+)的吸附效果逐渐增强,在p H大于4.0后逐渐趋于稳定.EDTA-nSiO_2对Cd~(2+)的吸附速率较快,可在1 h内达到吸附平衡.EDTA-nSiO_2对Cd~(2+)的吸附为吸热的自发过程,吸附等温线可用Langmuir模型描述.NaCl浓度增加会导致Cd~(2+)的吸附量下降,当体系Na Cl浓度从0增加到100 mmol·L~(-1),Cd~(2+)的最大吸附量从0.433 mmol·g-1降低至0.294mmol·g-1.0.1 mol·L~(-1)HCl是较为合适的吸附剂再生液,Cd~(2+)洗脱率约94.36%.结合pH、温度、离子强度、再生和XPS分析结果,可以推测出EDTA-nSiO_2对Cd~(2+)的吸附是包含有简单的物理吸附和离子交换过程,并以化学络合为主的吸附过程.EDTA-nSiO_2是一种对水体Cd~(2+)具有较好吸附能力的工程纳米材料吸附剂.     

磁性吸附材料CuFe2O4吸附砷的性能

根据Cu(Ⅱ)和Fe(Ⅲ)都对砷有较强的亲和性,制备了同时含有Cu(Ⅱ)和Fe(Ⅲ)的、可用磁分离方法进行分离回收的磁性吸附材料CuFe₂O₄,并对其进行了表征及吸附砷的性能研究.结果表明,该吸附剂对砷的吸附能力与溶液pH有关,在弱酸性及中性条件下,吸附砷的能力最强,而对As(V)的吸附能力比对As(Ⅲ)更强些,在平衡浓度为10μg/L时,其吸附容量可达10mg/g左右,可以很容易地将水中浓度为1～20mg/L的As(V)降到10μg/L以下.实验考察了几种无机阴离子对吸附砷的影响,表明较高浓度(砷浓度的20倍)的硫酸盐对As(Ⅲ)和As(V)的吸附均有一定影响,盐酸盐及磷酸盐则影响不明显;负载的As(V)可较容易地用0.1mol/L NaOH洗脱下来,使吸附剂再生,而As(Ⅲ)则难以洗脱,这与2种价态砷的吸附机理不同有关.     

纳米Fe3O4负载的浮游球衣菌去除重金属离子的工艺研究

以纳米Fe₃O₄负载浮游球衣菌（Sphaerotilus natans）制备复合生物吸附剂,对此吸附剂进行表征并考察了其吸附水中重金属离子的性能.红外光谱分析表明,此复合生物吸附剂表面的主要活性基团为酰胺基（—CONH—）和羟基（—OH）.吸附性能研究表明,菌含量和流量是影响复合生物吸附剂吸附重金属离子的主要因素,在Cu²⁺初始浓度c₀<20 mg/L,菌含量1.5 g/L（菌/ Fe₃O₄＝3∶2）,流量0.96 L/h 时吸附剂对Cu²⁺的吸附效果最好;用稀盐酸对复合生物吸附剂进行再生,吸附剂可重复使用10次以上,再生液可重复使用3次; 吸附选择性为：Pb²⁺ > Cu²⁺ > Zn²⁺>Cd²⁺.     

人造沸石的载铁改性及除去水中氟的性能

以人造沸石为载体,采用盐酸浸泡活化和氯化铁溶液浸泡改性的方法制备除氟吸附剂,用模拟高氟水样进行静态吸附及动态过柱实验.动力学研究结果表明:吸附剂吸附速度快,40 min接近吸附平衡,吸附速率可用拟二级动力学方程描述.吸附等温线符合Langmuir方程,饱和吸附量为9.83 mg/g,吸附平衡常数为0.030 2 L/m...     

活性炭负载DBU流化床吸附CO_2反应条件研究

采用浸渍法将DBU负载到活性炭上制成吸附剂。通过扫描电镜、N_2吸附分析仪、热重分析仪对吸附剂进行表征测定,并在流化床上进行正交实验,研究不同反应条件对活性炭负载DBU吸附CO_2的影响。结果表明:影响活性炭负载DBU流化床吸附CO_2的主要因素是CO_2浓度,其次是DBU负载率和吸附剂质量;最佳反应条件是DBU负载率7.4%,气流量0.8 L/min,水蒸气预处理时间5 min,CO_2浓度10%,吸附剂质量10 g,再生温度为100℃。     

树脂基固态胺吸附剂室温下对低浓度CO2的吸附性能研究

以大孔甲基丙烯酸酯吸附树脂为载体,聚乙烯亚胺(PEI)为有机胺,采用液相浸渍法制备出固态胺吸附剂,并研究了其在室温下对低浓度CO2的吸附行为.同时,利用氮气吸附、热重分析和扫描电镜表征了材料的物理化学性质,并采用热重法和固定床吸附法考察了材料的CO2吸附性能.结果表明,大孔树脂担载50%PEI(质量分数)时吸附性能最佳,对纯CO2的最大吸附量为175 mg·g-1;CO2的吸附行为由扩散动力学与吸附热力学共同决定,低温有利于提高吸附容量;吸附剂对400 ppm~15%浓度的CO2都具有优异的动态吸附性能,其中对400 ppm CO2的吸附量达到86 mg·g-1,对15%CO2的吸附量达到150 mg·g-1;湿度对吸附起促进作用,相对湿度为10%时,对400 ppm CO2的吸附量提高至139mg·g-1;吸附剂具有优异的循环性能,具有直接空气捕集CO2的潜力.     

粉煤灰用于碳捕集、利用及封存的研究进展

总结了国内外粉煤灰用于CO₂捕集、利用和封存的不同技术研究进展,同时对今后的研究和机遇进行了展望.粉煤灰自身可通过直接干式、半干式、湿式和间接方法对CO₂进行矿化捕集封存,在CO₂矿化的同时降低粉煤灰自身重金属的浸出,并且矿化后的粉煤灰因有效降低游离CaO和MgO的含量而更适合于制作混凝土添加剂.粉煤灰也可制成活性炭、沸石和多孔二氧化硅等产品,并对CO₂进行物理吸附捕集,制成产品的类型主要取决于粉煤灰自身的成分组成和理化性质.在CO₂利用方面,粉煤灰除了可拓展建材的利用途径外,还可制作CO₂多种化学工艺所需催化剂或催化剂载体,以及制作新型材料拟薄水铝石等.我国“双碳”目标的提出及燃煤电厂粉煤灰自身的理化特性为粉煤灰提供了一条新的综合利用途径.     

Adsorption of carbon dioxide on amine-modified TiO2 nanotubes

TiO2 nanotubes (TiNT) were prepared by a hydrothermal treatment and modified by three kinds of amines,namely ethylenediamine,polyetherimide and tetraethylenepentamine (TEPA),to study their CO2 adsorption properties from gas streams.The resultant samples were characterized by X-ray diffraction,transmission electron microscopy,and infrared spectroscopy,as well as low temperature N 2 adsorption.CO2 capture was investigated in a dynamic packed column at 30℃.TEPA-modified TiO2 nanotubes showed the highest adsorption capacity of 167.64 mg/g because it had the highest amino-group content among the three amines.CO2 fixation on TiNT impregnated by TEPA was investigated at 30,50,and 70℃,and the adsorption capacity increased slightly with temperature.Following the adsorption step,the sorbents were regenerated by temperature programmed desorption,and the TiNT-TEPA sample,as CO2 sorbent,was found to be readily regenerated and energy-efficient.The cycle test also revealed that the TiNT-TEPA adsorbent is fairly stable,with only a 5% drop in the adsorption capacity after 10 adsorption/desorption cycles.In addition,the CO2 adsorption behavior was investigated with the deactivation model,and which showed an excellent prediction for the TiNT-TEPA breakthrough curves.     

Sorbents with high efficiency for CO2 capture based on amines-supported carbon for biogas upgrading

Sorbents for CO_2 capture have been prepared by wet impregnation of a commercial active carbon(Ketjen-black, Akzo Nobel) with two CO_2-philic compounds, polyethylenimine(PEI)and tetraethylenepentamine(TEPA), respectively. The effects of amine amount(from 10 to70 wt.%), CO_2 concentration in the feed, sorption temperature and gas hourly space velocity on the CO_2 capture performance have been investigated. The sorption capacity has been evaluated using the breakthrough method, with a fixed bed reactor equipped with on line gas chromatograph. The samples have been characterized by N_2 adsorption–desorption,scanning electron microscopy and energy dispersive X-ray(SEM/EDX). A promising CO_2 sorption capacity of 6.90 mmol/gsorbenthas been obtained with 70 wt.% of supported TEPA at 70℃ under a stream containing 80 vol% of CO_2. Sorption tests, carried out with simulated biogas compositions(CH_4/CO_2mixtures), have revealed an appreciable CO_2 separation selectivity; stable performance was maintained for 20 adsorption–desorption cycles.     

Influence of SO2 in incineration flue gas on the sequestration of CO2 by municipal solid waste incinerator fly ash

The influence of CO2 content and presence of SO2 on the sequestration of CO2 by municipal solid waste incinerator(MSWI) fly ash was studied by investigating the carbonation reaction of MSWI fly ash with different combinations of simulated flue gas.The reaction between fly ash and 100% CO2 was relatively fast;the uptake of CO2 reached 87g CO2/kg ash,and the sequestered CO2 could be entirely released at high temperatures.When CO2 content was reduced to 12%,the reaction rate decreased;the uptake fell to 41g CO2/kg ash,and 70.7% of the sequestered CO2 could be released.With 12% CO2 in the presence of SO2,the reaction rate significantly decreased;the uptake was just 17g CO2/kg ash,and only 52.9% of the sequestered CO2 could be released.SO2 in the simulated gas restricted the ability of fly ash to sequester CO2 because it blocked the pores of the ash.     

Optimization of CO2 adsorption capacity and cyclical adsorption/desorption on tetraethylenepentamine-supported surface-modified hydrotalcite

The objective of this research was to investigate CO_2adsorption capacity of tetraethylenepentamine-functionalized basic-modified calcined hydrotalcite(TEPA/b-c HT)sorbents at atmospheric pressure formed under varying TEPA loading levels,temperatures,sorbent weight to total gaseous flow rate(W/F)ratios and CO_2concentrations in the influent gas.The TEPA/b-c HT sorbents were characterized by means of X-ray diffraction(XRD),Fourier transform infrared spectrometry(FT–IR),thermal gravimetric analysis(TGA),Brunauer–Emmet–Teller(BET)analysis of nitrogen(N_2)adsorption/desorption and carbon–hydrogen–nitrogen(CHN)elemental analysis.Moreover,a full 2~4factorial design with three central points at a 95%confidence interval was used to screen important factor(s)on the CO_2adsorption capacity.It revealed that85.0%variation in the capacity came from the influence of four main factors and the15.0%one was from their interactions.A face-centered central composite design response surface method(FCCCD–RSM)was then employed to optimize the condition,the maximal capacity of 5.5–6.1 mmol/g was achieved when operating with a TEPA loading level of 39%–49%(W/W),temperature of 76–90°C,W/F ratio of 1.7–2.60(g·sec)/cm~3and CO_2concentration of 27%–41%(V/V).The model fitted sufficiently the experimental data with an error range of±1.5%.From cyclical adsorption/desorption and selectivity at the optimal condition,the 40%TEPA/b-c HT still expressed its effective performance after eight cycles.     

Mesoporous carbon adsorbents from melamine-formaldehyde resin using nanocasting technique for CO2 adsorption

Mesoporous carbon adsorbents, having high nitrogen content, were synthesized via nanocasting technique with melamine–formaldehyde resin as precursor and mesoporous silica as template. A series of adsorbents were prepared by varying the carbonization temperature from 400 to 700°C. Adsorbents were characterized thoroughly by nitrogen sorption, X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), thermogravimetric analysis(TGA), elemental(CHN) analysis, Fourier transform infrared(FTIR) spectroscopy and Boehm titration. Carbonization temperature controlled the properties of the synthesized adsorbents ranging from surface area to their nitrogen content, which play major role in their application as adsorbents for CO_2 capture.The nanostructure of these materials was confirmed by XRD and TEM. Their nitrogen content decreased with an increase in carbonization temperature while other properties like surface area, pore volume, thermal stability and surface basicity increased with the carbonization temperature. These materials were evaluated for CO_2 adsorption by fixed-bed column adsorption experiments. Adsorbent synthesized at 700°C was found to have the highest surface area and surface basicity along with maximum CO_2 adsorption capacity among the synthesized adsorbents. Breakthrough time and CO_2 equilibrium adsorption capacity were investigated from the breakthrough curves and were found to decrease with increase in adsorption temperature. Adsorption process for carbon adsorbent–CO_2 system was found to be reversible with stable adsorption capacity over four consecutive adsorption–desorption cycles. From three isotherm models used to analyze the equilibrium data, Temkin isotherm model presented a nearly perfect fit implying the heterogeneous adsorbent surface.     

Eutectic mixture promoted CO2 sorption on MgO-TiO2 composite at elevated temperature

The development of carbon dioxide(CO_2) sorbents that can operate at elevated temperatures is significant for the advancement of pre-combustion capture technologies.Recently, promoter-based systems composed of alkali/alkaline earth metal nitrates and/or carbonates have been considered as next-generation solid sorbents due to their improved CO_2 uptake and kinetics. However, obtaining stable MgO sorbents against temperature swing regeneration still remained challenging. Herein, we report MgO-TiO_2 solid sorbents promoted by eutectic mixture(KNO_3 and LiNO_3) for elevated temperature CO_2 sorption. The developed sorbents show improved CO_2 sorption capacity, which may be attributed to the alternative CO_2 sorption pathway provided by the ionization of highly dispersed MgO in the eutectic mixture. The MgO-TiO_2 framework was also shown to assist in retaining the MgO configuration by constraining its interaction with CO_2. Furthermore, it is demonstrated that constructing composite structures is essential to improve the CO_2 sorption characteristics,mainly recyclability, at elevated temperatures. The developed promoter integrated sorbents showed exceptionally high CO_2 sorption capacity of 30 wt.% at an elevated temperature(300°C) with pronounced stability under temperature swing operation.     

Mesoporous carbon adsorbents from melamine–formaldehyde resin using nanocasting technique for CO2 adsorption

Mesoporous carbon adsorbents, having high nitrogen content, were synthesized via nanocasting technique with melamine–formaldehyde resin as precursor and mesoporous silica as template. A series of adsorbents were prepared by varying the carbonization temperature from 400 to 700°C. Adsorbents were characterized thoroughly by nitrogen sorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), elemental (CHN) analysis, Fourier transform infrared (FTIR) spectroscopy and Boehm titration. Carbonization temperature controlled the properties of the synthesized adsorbents ranging from surface area to their nitrogen content, which play major role in their application as adsorbents for CO₂ capture. The nanostructure of these materials was confirmed by XRD and TEM. Their nitrogen content decreased with an increase in carbonization temperature while other properties like surface area, pore volume, thermal stability and surface basicity increased with the carbonization temperature. These materials were evaluated for CO₂ adsorption by fixed-bed column adsorption experiments. Adsorbent synthesized at 700°C was found to have the highest surface area and surface basicity along with maximum CO₂ adsorption capacity among the synthesized adsorbents. Breakthrough time and CO₂ equilibrium adsorption capacity were investigated from the breakthrough curves and were found to decrease with increase in adsorption temperature. Adsorption process for carbon adsorbent–CO₂ system was found to be reversible with stable adsorption capacity over four consecutive adsorption–desorption cycles. From three isotherm models used to analyze the equilibrium data, Temkin isotherm model presented a nearly perfect fit implying the heterogeneous adsorbent surface.     

加速碳酸化技术对城市垃圾焚烧飞灰重金属稳定性影响研究

对南方某城市生活垃圾焚烧厂新鲜焚烧飞灰对CO₂的吸收及其碳酸化的过程进行了研究,实验从水分添加量、CO₂的分压等因素,考察了飞灰中重金属Pb的稳定化效果,并利用X射线衍射实验(XRD)、扫描电镜实验(SEM)对反应机理进行了分析.结果表明,不添加水分时,焚烧飞灰对CO₂的吸收效果较差;当水分添加量大于10％时,焚烧飞灰对CO₂的吸收效果较好.焚烧飞灰对纯CO₂的吸收效果较好,空气中的CO₂含量较低,在反应1 d后吸收效果不是十分明显.XRD实验结果表明,CO₂的吸收会使焚烧飞灰中大量的Ca(OH)₂与CO₂反应转化为CaCO₃,从而降低焚烧飞灰的碱性;部分重金属的氧化物会被碳酸化成生相应的碳酸盐.SEM实验结果表明,经过碳酸化处理后的飞灰颗粒表面生成了片状和圆柱状的晶体物质.