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.     

N-doped mesoporous alumina for adsorption of carbon dioxide

N-doped mesoporous alumina has been synthesized using chitosan as the biopolymer template. The adsorbent has been thoroughly investigated for the adsorption of CO₂ from a simulated flue gas stream (15% CO₂ balanced with N₂) and compared with commercially available mesoporous alumina procured from SASOL, Germany. CO₂ adsorption was studied under different conditions of pre-treatment and adsorption temperature, inlet CO₂ concentration and in the presence of oxygen and moisture. The adsorption capacity was determined to be 29.4 mg CO₂/g of adsorbent at 55℃. This value was observed to be 4 times higher in comparison to that of commercial mesoporous alumina at a temperature of 55℃. Basicity of alumina surface coupled with the presence of nitrogen in template in synthesized sample is responsible for this enhanced CO₂ adsorption. Adsorption capacity for CO₂ was retained in the presence of oxygen; however moisture had a deteriorating effect on the adsorption capacity reducing it to nearly half the value.     

以粉煤灰为原料制备低温CO2吸附剂的工艺参数优化

利用高铝粉煤灰预脱硅液作为载体原料,通过使用胺基化合物对载体改性制备低温CO_2吸附剂.应用6 sigma中的工具,对制备工艺进行优化,得到理想的吸附剂,并对吸附剂样品进行表征.结果表明制备的CO_2吸附剂表现出良好的CO_2吸附性能.此类CO_2吸附剂具有吸附容量高(160 mg·g~(-1))、吸附速率快、对设备腐蚀低、成本低廉等特点,是一种极具工业应用潜力的CO_2吸附剂.     

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.     

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.     

CO2 capture performance of bi-functional activated bleaching earth modified with basic-alcoholic solution and functionalization with monoethanolamine: isotherms, kinetics and thermodynamics

CO_2 capture performance of bifunctional activated bleaching earth(ABE) was investigated at atmospheric pressure. The sorbents were characterized by means of X-ray diffraction(XRD), Brunauer–Emmett–Teller(BET), Caron-Hydrogen-Nitrogen analysis(CHN), Fourier transform infrared(FT-IR) and thermal gravimetric analysis(TGA). The CO_2 capacity was enhanced via basic-modification and monoethanolamine(MEA) loading of the ABE sorbent to obtain a bifunctional surface property. Here, basic-modified calcined ABE with a 30 wt.%MEA loading(SAB-30) showed the highest CO_2 capture capacity, but this was decreased with excess MEA loading( 30 wt.%). At a 10%(V/V) initial CO_2 concentration feed, the maximum capacity of SAB-30 increased from 2.71 mmol/g at 30℃(without adding moisture to the feed) to 3.3 mmol/g at 50℃ when adding 10%(V/V) moisture to the feed. Increasing the moisture concentration further reduced the maximum CO_2 capacity due to the blocking effect of the excess moisture on the sorbent surface. However, SAB-30 could completely capture CO_2 even in a 100%(V/V) initial CO_2 concentration feed. A maximum CO_2 capacity of5.7 mmol/g for SAB-30 was achieved at 30℃. Varying the ratio of sorbent weight to total flow rate of the gas stream had no discernible effect on the equilibrium CO_2 capture capacity. Avrami's equation and Toth's isotherm model provided a good fitting for the data and suggested the presence of more than one reaction pathway in the CO_2 capture process and the heterogeneous adsorption surface of SAB-30. Thermodynamics studies revealed that CO_2 capture on the bifunctional SAB-30 is feasible, spontaneous and exothermic in nature.     

Capture of carbon dioxide from flue gas on TEPA-grafted metal-organic framework Mg2(dobdc)

Carbon dioxide （CO2） adsorption on a standard metal-organic framework Mg2（dobdc） （Mg/DOBDC or Mg-MOF-74） and a tetraethylenepentamine （TEPA） modified Mgz（dobdc） （TEPA-Mg/DOBDC） were investigated and compared. The structural information, surface chemistry and thermal behavior of the adsorbent samples were characterized by X-ray powder diffraction （XRD）, infrared spectroscopy （IR）, thermogravimetric analysis （TGA） and nitrogen adsorption-desorption isotherm analysis. CO2 adsorption capacity was measured by dynamic adsorption experiments with N2-CO2 mixed gases at 60℃. Results showed that the CO2 adsorption capacity of Mg/DOBDC was significantly improved after amine modification, with an increase from 2.67 to 6.06 mmol CO2/g adsorbent. Moreover, CO2 adsorption on the TEPA-Mg/DOBDC adsorbent was promoted by water vapor, and the adsorption capacity was enhanced to 8.31 mmol CO2/g absorbent. The adsorption capacity of the TEPA-Mg/DOBDC adsorbent dropped only 3% after 5 consecutive adsorption]desorption cycles. Therefore, this kind of adsorbent can be considered as a promising material for the capture of CO2 from flue gas.     

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 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.     

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.     

介孔炭干凝胶对孔雀石绿的吸附性能研究

以间苯二酚和甲醛为原料,采用溶胶-凝胶法,通过调整碱性催化剂碳酸钠用量,制备了一系列介孔丰富的炭干凝胶吸附剂.主要考察了介孔炭干凝胶对染料孔雀石绿的吸附性能,并进行了孔结构、表面形貌和官能团的分析.结果表明,催化剂用量不同的介孔炭干凝胶具有不同的粒径和孔径,当间苯二酚与碳酸钠的物质的量比为1000∶1时,制得的吸附剂比表面积和介孔最丰富,且其对孔雀石绿的吸附量最大.同时,介孔炭干凝胶的用量、吸附时间和温度对吸附容量均有一定的影响,吸附过程符合伪二阶动力学模型和Langmuir等温模型,最大吸附量为208.33 mg·g~(-1);吸附过程是自发的吸热反应.介孔炭干凝胶对孔雀石绿的主要吸附机理是染料分子与羟基和羧基等官能团之间存在静电作用、氢键作用及范德华力作用.     

钙基CO2吸收剂的锆改性研究

实验采用共沉淀法以Ca(Ac)2·H2O作为CaO前驱体,经NH3·H2O沉淀、静置、醇洗、烘干制备锆改性钙基高温二氧化碳吸收剂,并考察锆添加量、反应温度及时间、CO2分压等因素列其吸收性能的影响.经锆改性后,吸收剂中掺杂ZrO2形成了良好的介孔结构,可维持较高的碳酸化转化率,提高吸收剂的循环热稳定性.测试结果表明,当...     

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.     

Efficient nitrogen doped porous carbonaceous CO2 adsorbents based on lotus leaf

In this work, the waste biomass lotus leaf was converted into N-doped porous carbonaceous CO₂ adsorbents. The synthesis process includes carbonization of lotus leaf, melamine post-treatment and KOH activation. For the resultant sorbents, high nitrogen content can be contained due to the melamine modification and advanced porous structure were formed by KOH etching. These samples were carefully characterized by different techniques and their CO₂ adsorption properties were investigated in detail. These sorbents hold good CO₂ adsorption abilities, up to 3.87 and 5.89 mmol/g at 25 and 0°C under 1 bar, respectively. By thorough investigation, the combined interplay of N content and narrow microporous volume was found to be responsible for the CO₂ uptake for this series of sorbents. Together with the high CO₂ adsorption abilities, these carbons also display excellent reversibility, high CO₂/N₂ selectivity, applicable heat of adsorption, fast CO₂ adsorption kinetics and good dynamic CO₂ adsorption capacity. This study reveals a universal method of obtaining N-doped porous carbonaceous sorbents from leaves. The low cost of raw materials accompanied by easy synthesis procedure disclose the enormous potential of leaves-based carbons in CO₂ capture as well as many other applications.     

再生条件对钾基CO_2吸附剂吸附性能的影响

通过固定床实验研究了再生条件对钾基CO2吸附剂吸附性能的影响。深入分析了再生温度和气氛对吸附穿透时间和饱和吸附量的影响。研究发现,当再生温度为200℃,N2气氛下再生时效果最佳,在此条件下再生后钾基CO2吸附剂循环性能良好,10次循环后仍然能有很好的吸附效果;再生气氛中有H2O或CO2时会影响再生反应的进行,不利于吸附剂的再生。     

Carbon dioxide adsorption behaviors of aluminum-pillared montmorillonite-supported alkaline earth metals

The Al-pillared montmorillonite-supported alkaline earth metal 5M/Al-PILC (PILC = pillared clay, M = Mg, Ca, Sr, and Ba) and xMg/Al-PILC (x = 1, 3, 5, and 7 wt.%) samples were prepared using an impregnation method. Physical properties of the materials were determined by means of X-ray diffraction (XRD) and N₂ adsorption-desorption, and their CO₂ adsorption behaviors were investigated using the thermogravimetric analyzer (TG), CO₂ temperature-programmed desorption (CO₂-TPD), and in situ diffuse reflectance infrared transform spectroscopy (in situ-DRIFTS) techniques. It is shown that 5Mg/Al-PILC possessed the highest CO₂ adsorption capacity (2.559 mmol/g). The characterization results indicate that Al-pillaring increased the specific surface area of montmorillonite, which was beneficial for the adsorption of CO₂. The CO₂ adsorption process on the sample was mainly chemical adsorption, and alkalinity was the main factor influencing its adsorption capacity. The alkalinity of the sample was enhanced by loading an appropriate amount of alkaline earth metal, and the adsorbed CO₂ was present in the form of bicarbonate and carbonate. In addition, the 5Mg/Al-PILC sample exhibited an excellent regeneration efficiency. We believe that the outcome of this research would provide a good option for developing highly effective CO₂ adsorption materials.     

钙法解吸并固定乙醇胺富液中CO2

针对醇胺类吸收剂富液中CO_2的解吸及后续处置所存在的不足,提出一种新型解吸方案——钙法.通过CO_2负荷试验和Ca(OH)_2投加量试验确定了该法理想处理负荷为0.84 mol·L-1,理想投加比例为C∶Ca=1∶1(摩尔比),此条件下反应15 min和30 min的解吸率达到52.17%和55.02%,这表明钙法矿化解吸乙醇胺富液中CO_2是可行的.在此基础上,进一步研究了pH、温度和搅拌强度对CO_2解吸固定效果的影响.试验结果表明,CO_2解吸率随着pH和搅拌强度的增加而增大,但当pH和搅拌强度增大到一定程度后,解吸率增长放缓甚至出现下降.较高的解吸温度尽管解吸率更大,但高温条件下无法达到矿化固定CO_2的目的.CO_2二次吸收负荷试验表明经钙法解吸后的MEA再生液具有良好的可重复使用性.     

Enhanced CO2 adsorptive performance of PEI/SBA-15 adsorbent using phosphate ester based surfactants as additives

In this study,a series of polyetherimide/SBA-15: 2-D hexagonal P6 mm,Santa Barbara USA(PEI/SBA-15) adsorbents modified by phosphoric ester based surfactants(including tri(2-ethylhexyl)phosphate(TEP),bis(2-ethylhexyl) phosphate(BEP) and trimethyl phosphonoacetate(TMPA))were prepared for CO_2 adsorption.Experimental results indicated that the addition of TEP and BEP had positive effects on CO_2 adsorption capacity over PEI/SBA-15.In particular,the CO_2 adsorption amount could be improved by around 20% for 45PEI–5TEP/SBA-15 compared to the additive-free adsorbent.This could be attributed to the decrease of CO_2 diffusion resistance in the PEI bulk network due to the interactions between TEP and loaded PEI molecules,which was further confirmed by adsorption kinetics results.In addition,it was also found that the cyclic performance of the TEP-modified adsorbent was better than the surfactant-free one.This could be due to two main reasons,based on the results of in situ DRIFT and TG-DSC tests.First and more importantly,adsorbed CO_2 species could be desorbed more rapidly over TEP-modified adsorbent during the thermal desorption process.Furthermore,the enhanced thermal stability after TEP addition ensured lower degradation of amine groups during adsorption/desorption cycles.     

脉冲电晕法藕合Ca(OH)2固体吸收处理四氯乙烯废气研究

采用线-筒式脉冲电晕反应器对四氯乙烯去除效果进行了研究.结果表明,四氯乙烯去除率随电压的增大而增大.在氮气中加入氧气,四氯乙烯降解效果低于纯氮气下的降解效果.四氯乙烯在氮气下的主要气相产物为Cl_2和少量的CCl_4.当氧气加入后,四氯乙烯主要降解为CO_2、CO、COCl_2、O_3和C_2Cl_4O.为了去除有害中间产物,在反应器中加入Ca(OH)_2固体吸收剂,这明显提高了有害中间产物的去除,存在水汽及含Ca(OH)_2固体吸收剂时并未检测到COCl_2、O_3和有害中间产物C_2Cl_4O,但水汽不利于四氯乙烯去除.     

西维因在活性炭及草木灰上的吸附及解吸特性

在详细表征活性炭(AC)、草木灰(PA)和沉积物(S)表面性质及化学组成的基础上,研究他们对农药西维因的吸附等温线及吸附和解吸动力学特征.结果表明,化学组成类似,孔隙结构不同的碳吸附剂所遵循的吸附机理不同.介孔分布较多的AC吸附机理复杂,介孔分布较少的PA以线性分配作用为主,AC对西维因的吸附量远大于PA,表面积标化饱和吸附量显示,表面积是影响吸附量的关键因素.AC对西维因的解吸量远小于吸附量,与PA的解吸量相当,PA的解吸量与吸附量相近,且解吸动力学数据均能用准一级动力学方程拟合,说明以分配作用黏附于碳吸附剂上的西维因可能又以分配的形式解吸.沉积物(S)中掺混AC和PA后,对西维因的吸附量增加,解吸量降低,证明AC和PA均具有应用于污染沉积物治理的潜力,但复杂的沉积物体系使得吸附并非简单的叠加.