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.     

三乙烯四胺改性风化煤对废水中Ni2+的吸附机制

为提高风化煤对Ni2+的吸附性能,以XWC（新疆风化煤）为基体,TETA（三乙烯四胺）为改性剂,采用交联反应联合超声波振荡制备ACA（胺化煤基吸附剂）,利用SEM（扫描电镜）等手段对其进行表征,并考察了体系pH、吸附剂用量、反应时间及溶液初始ρ（Ni2+）对吸附过程的影响,通过吸附动力学和吸附等温模型对吸附机制进行描述.结果表明,TETA中的多乙烯多胺基成功接枝到煤粉表面使风化煤的表面颗粒增多,比表面积由6.875 m2/g减至3.440 m2/g,孔容由0.011 cm3/g减至0.005 cm3/g.在pH为8.0、ACA用量为0.4 g时吸附效果最好.ACA和XWC对Ni2+的吸附过程均符合准二级动力学方程及Langmuir吸附等温模型.拟合得ACA的饱和吸附量为188.68 mg/g,较改性前提高了5.1倍.研究显示,ACA处理ρ（Ni2+）范围为200~1 000 mg/L的废水时,对Ni2+的去除率稳定在95%以上.      

自然型氨基酸及其钾盐的 CO2吸收和再生特性

在CO2吸收过程中,选择具有不挥发和不发生氧化降解特性的氨基酸盐吸收剂有助于降低吸收剂损失和减轻环境污染风险,故本研究以CO2吸收速率和再生速率为指标,对L-精氨酸和精氨酸钾（PA）吸收剂的CO2吸收性能和常压下热再生性能进行了实验分析,并研究了吸收剂质量分数、反应温度及吸收-再生循环次数对CO2吸收特性的影响,同时还与乙醇胺（MEA）、二乙醇胺（DEA）和三乙醇胺（TEA）进行了对比分析.结果表明,在实验的质量分数范围内,PA具有最高的CO2吸收速率和吸收能力,分别为24.5×10-3mol.（L.min）-1和1.99 mol.mol-1,比相同质量分数的MEA高2.1%和290.2%.温度影响结果表明,40℃时PA和MEA的CO2吸收速率均高于其他实验温度.相同再生条件下,PA的贫液CO2负荷要略高于MEA,但PA的再生程度可达72.8%,比MEA高19%.同时,3次＂吸收-再生＂循环之后,10%PA的CO2吸收能力仍可保持在1.03mol.mol-1,比10%MEA高255.2%.实验结果也表明,L-精氨酸具有较强的CO2吸收能力,其CO2吸收速率与同质量分数的DEA可比.     

有机胺对CO2吸收解吸的研究

利用常压搅拌吸收-解吸装置,在不同温度和浓度条件下,对MEA(乙醇胺)、DEA(二乙醇胺)、MDEA(N-甲基二乙醇胺)、TETA(三乙烯四胺)、DETA(二乙烯三胺)5种有机胺吸收解吸CO2进行研究.探讨了反应温度、吸收液浓度、有机胺种类对CO2吸收和解吸过程的影响规律,并利用正交试验法筛选出性能较好的混合胺复配剂.结果表明,当TETA/DEA=5:1,吸收温度为318K,解吸温度为388K时,混合胺具有较优的吸收解吸综合性能.     

碳酸钾-三乙烯四胺复合溶液吸收模拟烟气中CO_2试验研究

本菲尔溶液在工业脱除二氧化碳中已获得较广泛的应用,但存在吸收速率差、再生负荷高等缺点。开发新型复合溶液成为目前研究热点。采用搅拌实验装置,研究不同配比的碳酸钾-TETA复合溶液对烟道气中二氧化碳的吸收和解吸性能,揭示了吸收速率、吸收容量与酸碱度、时间之间的内在联系,并对CO2从复合溶液中初始逸出温度、溶液再生温度、溶液再生率、再生前后溶液pH下降率进行了细致记录分析。实验结果表明:碳酸钾-TETA复合溶液配比为0.6∶0.4时吸收效果最佳,吸收量约为0.914mol/L;同时再生温度最低,为106℃;再生率最高,为96.7%。与相同配比的碳酸钾-MEA(一乙醇胺)、碳酸钾-DEA(二乙醇胺)、碳酸钾-DETA(二乙烯三胺)复合溶液相比具有一定再生优势。实验结果还表明碳酸钾-TETA复合体系之间存在正交互作用。     

二氧化碳捕集技术进展研究

CO2排放主要源于化石燃料燃烧过程,减少化石燃料燃烧过程排放的CO2对于降低大气中CO2浓度具有重要意义.针对燃烧过程排放的CO2,分析了CO2捕集技术的原理、工艺流程、优劣性和适用性,并归纳了CO2捕集技术的研发趋势.结果表明:CO2捕集技术主要包括燃料燃烧前捕集、燃烧后捕集和富氧燃烧.为了有效缓解因CO2排放导致的一系列环境及社会问题,后续需要进一步降低CO2捕集技术的成本以及通过立法以约束企业的CO2排放行为.     

Capture and separation of CO2 from flue gas by coupling free and immobilized amines

A novel system was proposed for the capture and separation of CO2 from flue gas. In this method, a resin was employed to regenerate the amine capturing CO2 from flue gas at room temperature. The feasibility for the resin to regenerate amines such as MEA, MAE, TEA, and ammonia was demonstrated. It was also discovered that the resin could be regenerated by hot water.     

吸收CO2新型混合化学吸收剂的研究

以吸收剂吸收速率和再生程度为指标,在小型实验装置台上研究了3种混合吸收剂不同配比的吸收和再生特性,以确定其吸收剂主体和添加剂的合适配比.结果表明,在甲基二乙醇胺(MDEA)中添加哌嗪(PZ),当混合吸收液CO2负荷为0.2 mol·mol-1时,MDEA∶PZ=1∶0.4(m∶m)混合液CO2吸收速率比MDEA∶PZ=1∶0.2(m∶m)混合液提高了约70%.再生40 min,PZ 相对浓度为0的吸收液再生程度为91.04%,PZ相对浓度为0.2、0.4和0.8时,混合吸收液的再生程度分别降低为83.06%、77.77%和76.67%.综合比较,MDEA∶PZ=1∶0.4(m∶m)是该混合吸收液合适的配比,吸收速率和再生特性都有较好改善.在10%一级胺中添加2%三级胺既能保持高吸收效率,又能略微降低再生能耗.在10%二乙醇胺(DEA)中加入2%2-氨基-2-甲基-1-丙醇(AMP),混合液表现出DEA/AMP混合吸收剂中较好的吸收和再生特性.3种配方中,在一级胺中添加少量三级胺吸收速率最高,二级胺和少量空间位阻胺混合吸收剂的再生性能最好.而综合吸收和再生2个指标,三级胺和中量活化剂的混合液有优势.     

固态胺SO2吸附-解吸循环特性

采用新的固态胺吸附材料研究其对SO₂的吸附性能.针对几种不同种类及孔径的分子筛嫁接胺基合成固态胺吸附材料,研究了其对SO₂吸附规律,特别是研究了固态胺解吸再生的特性.研究结果表明固态胺具有较高的SO₂吸附量,经20次吸附-解吸循环,留在固态胺中的残余量较低.结果还表明,分子筛结构的种类和孔径对固态胺吸附SO₂的效果有重大影响,通常孔径较小的分子筛,吸附效果较差.但分子筛中SiO₂/Al₂O₃的提高可降低解吸后的残余量.研究CO₂,NO_x对固态胺吸附剂的影响规律,结果表明,CO₂对固态胺SO₂吸附基本无影响,NO_x则会干扰SO₂的吸附.通过对解吸残余量化学成分的研究表明,解吸残余量具有与液态胺热稳定物类似的组分.由于固态胺可以有较高的工作温度,因此固态胺将更易于循环再生.     

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。     

不同特性的多孔炭对CO2的吸附研究

分别用苯胺和糠醇为碳源、NaY分子筛为硬模板在碳化温度为700与900℃下合成了多孔炭(MC-AN-700、MC-AN-900、MC-FA-700和MC-FA-900),并对材料进行了结构表征,研究了低浓度CO2在这些材料和商业活性炭(AC)上的动态吸附.结果显示,MC-AN-700的氮和氧的含量均最高,分别为6.59%和8.71%;MC-FA-900的总孔容居于首位,为0.73cm3/g,但微孔体积中,AC的最大,为0.35cm3/g.在常温常压下,初始浓度为10%的 CO2在5种材料上的饱和吸附量的顺序为:MC-AN-700(2.20mmol/g)>MC-AN- 900(1.72mmol/g)>AC(1.59mmol/g)>MC-FA-900(1.45mmol/g)>MC-FA-700(1.09mmol/g),吸附差异受吸附剂的微孔孔容和氮含量共同影响.在2%~10%的范围内,CO2吸附量随初始浓度增加而增加;在20、45和65℃3个温度下,CO2吸附量随温度升高而降低.经4次脱附再生后,MC-AN-700的吸附量仍保持了原有吸附量的91%,高于MC-FA-900(86%)与AC(85%).     

氨基离子液体负载活性炭CO2吸附性能的负协同效应

通过三亚乙基四胺与L-乳酸的酸碱中和反应合成[TETA][L]离子液体,并将不同质量分数的离子液体负载到椰壳活性炭中,利用傅里叶红外光谱仪、X射线衍射仪、全自动比表面和孔径分布分析仪研究[TETA][L]离子液体浸渍对椰壳活性炭微观结构以及CO₂吸附性能的影响。结果表明:离子液体与活性炭之间的相互作用会导致石墨微晶细晶化,对活性炭的结构稳定性有不利影响,而离子液体对椰壳活性炭孔隙结构的"堵塞式"填充,导致复合材料CO₂物理吸附性能显著下降和CO₂化学吸附性能有限增加,这是造成复合材料CO₂总吸收性能显著降低的根本原因,且离子液体在活性炭中呈现了一种由小孔径到大孔径的"阶梯式"填充行为。     

葡萄树基活性炭的制备及其CO2吸附特性

为探讨葡萄树基活性炭在碳捕集与封存领域中的潜力,分别以葡萄树枝和树皮为原料采用CO₂活化法在800℃下制备了葡萄树枝基活性炭和葡萄树皮基活性炭,根据N₂物理吸附法计算了比表面积,用二维非定域密度函数理论（2D-NLDFT）分析了孔径分布特性,并使用热重分析法表征了两种活性炭的热解特性以及30℃的CO₂吸附特性.结果表明:①葡萄树枝基活性炭具有微孔结构,微孔孔径在0.36~1.6 nm之间,孔径为0.66 nm的微孔最多;葡萄树皮基活性炭具有大量微孔和少量中孔,孔径主要集中在0.36~1.9 nm之间.②葡萄树枝基和葡萄树皮基活性炭的CO₂吸附容量分别为1.096和0.247 mmol/g.③两种活性炭的CO₂吸附以物理吸附为主,其CO₂饱和产物在45℃前释放全部CO₂,葡萄树枝基活性炭的CO₂饱和产物较葡萄树皮基活性炭的CO₂饱和产物难于释放CO₂.④两种活性炭吸附CO₂后,在热重特性上出现的微量变化表明活性炭物质结构上的变化.研究显示,葡萄树枝基活性炭是一种良好的CO₂捕集材料,但其CO₂吸附容量比其他同类活性炭低,CO₂吸附量较高的葡萄树基活性炭的制备条件和改性方法需要进一步研究.      

Amine reclaiming technologies in post-combustion carbon dioxide capture

Amine scrubbing is the most developed technology for carbon dioxide(CO2) capture.Degradation of amine solvents due to the presence of high levels of oxygen and other impurities in flue gas causes increasing costs and deterioration in long term performance,and therefore purification of the solvents is needed to overcome these problems. This review presents the reclaiming of amine solvents used for post combustion CO2capture(PCC). Thermal reclaiming, ion exchange, and electrodialysis, although principally developed for sour gas sweetening, have also been tested for CO2 capture from flue gas.The three technologies all have their strengths and weaknesses, and further development is needed to reduce energy usage and costs. An expected future trend for amine reclamation is to focus on process integration of the current reclaiming technologies into the PCC process in order to drive down costs.     

碳基吸附剂对典型有机防晒剂二苯甲酮-3的吸附性能及热力学研究

针对环境水体中药物及个人护理用品(PPCPs)的污染问题,选择在环境水体中存在的有机紫外防晒剂二苯甲酮-3(BP-3)作为典型污染物,以颗粒活性炭(GAC)、粉末活性炭(PAC)和碳纳米管(CNT)作为吸附剂,考察吸附剂对BP-3的吸附性能、吸附特性和吸附热力学.结果表明:吸附性碳材料对BP-3具有良好的吸附性能,3种碳材料的最大吸附容量排列为:PACGACCNT,其中,PAC的单层最大吸附容量为450.36mg·g-1.Freundlich、Redlich-Peterson和Temkin吸附等温线方程能够较好地拟合吸附数据,Langmuir吸附等温线方程对PAC的吸附拟合效果较好,而对粒径较大的吸附剂(GAC、CNT)的拟合效果不理想.PAC、GAC的吸附过程可以采用一级动力学或者二级动力学模型拟合,而CNT适合采用一级动力学模型来描述.吸附热力学分析表明,PAC、GAC和CNT对BP-3的吸附过程都是自发进行的,其中,PAC和GAC的吸附过程是吸热的,升高温度有利于吸附反应的进行;而CNT的吸附过程是放热的.     

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.     

酸-碘改性壳聚糖-膨润土脱除单质汞特性及机理分析

为探明烟气中酸性气体(SO2,NO,HCl)和H2O对酸-碘改性壳聚糖-膨润土吸附剂脱除单质汞(Hg0)的影响和脱除机理,在小型固定床试验台架上开展了Hg0脱除的实验研究.结果表明:由于SO2与Hg0在吸附剂表面活性位上存在竞争吸附,SO2抑制吸附剂对Hg0的脱除.H2O和较高浓度(1000μg/m3)的NO对脱汞具有明显地促进作用.由于低温下HCl与Hg0较高的反应能垒,HCl对脱汞没有影响.与单一烟气成分影响相比,在SO2、NO、HCl和H2O的联合作用下,吸附剂的长时间脱汞性能得到大幅提高.机理分析表明壳聚糖首先被酸中的H+质子化,之后再吸附酸与KI反应生成的I2,进而有效地吸附Hg0.量子化学计算表明壳聚糖在酸性条件下对I2具有良好的吸附特性,改性壳聚糖吸附剂对Hg0具有较好的吸附能力,其吸附能约为127kJ/mol.     

吸附存储-间歇放电法氧化甲苯的反应过程研究

以SBA-15为催化剂,对比连续降解法和吸附存储-间歇放电法净化低浓度甲苯的活性,结果表明吸附存储-间歇放电法下甲苯去除率、碳平衡和CO2选择性更高.运用GC-MS分析了2种降解方式催化剂表面中间产物随时间的变化,苯甲醛进一步氧化分解进而打开苯环,是等离子体催化降解甲苯的控制步骤.对比SBA-15、Mn/SBA-15、Ag/SBA-15、AgMn/SBA-15 4种催化剂在吸附存储-间歇放电法下降解甲苯的活性.结果显示Ag和Mn的引入加速了对2-庚烯醇的氧化催化,AgMn/SBA-15表现出最好的碳平衡、CO2选择性.     

Carbon dioxide capture using polyethylenimine-loaded mesoporous carbons

A high efficiency sorbent for CO2 capture was developed by loading polyethylenimine (PEI) on mesoporous carbons which possessed well-developed mesoporous structures and large pore volume. The physicochemical properties of the sorbent were characterized by N2 adsorption/desorption, scanning electron microscopy (SEM), thermal gravimetric analysis (TG) and Fourier transform infrared spectroscopy (FT-IR) techniques followed by testing for CO2 capture. Factors that affected the sorption capacity of the sorbent were studied. The sorbent exhibited extraordinary capture capacity with CO2 concentration ranging from 5% to 80%. The optimal PEI loading was determined to be 65 wt.% with a CO2 sorption capacity of 4.82 mmol-CO2 /g-sorbent in 15% CO2 /N2 at 75°C, owing to low mass-transfer resistance and a high utilization ratio of the amine compound (63%). Moisture had a promoting effect on the sorption separation of CO2 . In addition, the developed sorbent could be regenerated easily at 100°C, and it exhibited excellent regenerability and stability. These results indicate that this PEI-loaded mesoporous carbon sorbent should have a good potential for CO2 capture in the future.