废茶活性炭脱硫脱硝性能的应用研究

为探讨废茶活性炭对于SO2和NO脱除作用的制约因素,分别考察了材料孔径结构、石墨化程度及表面结构对其脱硫脱硝性能的影响,同时研究了其吸附机制及动力学过程.结果表明,较高的石墨化程度是影响材料脱硫性能的主要因素,微孔径较小且含氮碱性基团较高时有利于SO2的脱除;发达的中孔结构是制约NO脱除效率的关键因素,含氮碱性基团对NO的脱除具有一定的促进作用;烟气中SO2和NO共存时,材料的脱硫脱硝性能均有所降低,氧气和水蒸气的加入能够改善其脱硫脱硝效率;废茶活性炭在无水环境下对于SO2和NO的吸附作用均以物理吸附为主,水蒸气的存在促进了材料对SO2的化学吸附;通过动力学模型的拟合发现,Bangham吸附模型能够很好地描述材料脱硫脱硝的动力学过程,其R2均高于0.989,材料对于SO2和NO的吸附速率常数均随氧气和水蒸气的加入而减小.     

微波辐照技术在活性炭脱硫中的应用

采用微波辐照技术对煤质活性炭进行加热,研究了不同的微波功率、辐照时间和样品粒径等因素对活性炭脱硫性能的影响,找出了合适的处理条件.同时,将改性活性炭和原炭对SO2的吸附和催化性能做了比较,说明了微波辐照活性炭具有比原炭更好的吸附和催化性能.采用氮气吸附仪、pH精密酸度计、XPS、元素分析等测试了改性活性炭和原炭的物理化学性能:活性炭的表面积和孔结构没有显著改变;活性炭的脱硫性能与活性炭的pH值有着一定的关系;具有较低氧含量和较高的氮含量的活性炭具有较好的脱硫活性;CH2　和　CO(烯酮基)官能团含量相对增加有利于SO2的吸附.     

纳米助燃固硫添加剂的催化作用机理

溶胶.凝胶法制备的纳米TiO2作为CaO固硫添加剂,用热分析法对纳米TiO2催化煤燃烧以及催化CaO固硫的过程进行了实验研究.对燃烧后煤灰的孔径分布进行了分析.采用未反应收缩核模型对固硫反应的动力学过程进行表征.研究结果表明,纳米TiO2与CaO共同作用条件下对煤燃烧有明显的促进作用,即燃烧反应活化能E下降,同时纳米TiO2还能增大燃烧后煤灰的孔径,提高固硫率.氧气的存在抑制氧化钙的固硫转化率,纳米TiO2可以消弱氧气的抑制作用.对固硫反应的影响表现为在反应后期(即产物层扩散控制阶段),与固硫转化率和孔径分布的实验结果非常吻合;讨论了纳米TiO2催化燃烧催化固硫的机理,纳米TiO2导致碳晶格的扭曲,增加表面活性部位,加快氧气的吸附速度,使添加剂周围燃烧速度加快,煤灰孔隙增大从而强化燃烧,促进SO2转化成SO3的本征反应,促进二氧化硫向氧化钙内部的扩散从而提高CaO的固硫效果.     

电厂烟气中SO2对活性炭吸附单质铅(Pb0)的影响机理

利用密度泛函理论系统研究了SO_2对活性炭吸附单质铅(Pb~0)的影响,其中,结构优化与频率计算采用B3LYP/def2-SVP级别方法和基组,单点能计算采用B3LYP/def2-TZVP级别方法和基组.同时,利用玻尔兹曼分布函数分析了SO_2与Pb~0在活性炭表面的竞争吸附关系,结果表明,Pb~0在纯净活性炭上的吸附能力大于SO_2.此外,本研究发现,SO_2的预吸附会增强活性炭对Pb~0的吸附效果.通过静电势分布揭开了SO_2促进活性炭吸附Pb~0的深层原因,结果发现,吸附SO_2以后活性炭表面静电势极大值增大,极小值减小,吸附剂吸附能力因此增强.最后,利用电子密度差分图揭示出SO_2改性活性炭在吸附Pb~0时,SO_2对Pb~0吸附的影响可以分为直接影响和间接影响两种.     

Mercury removal from coal combustion flue gas by modified fly ash

Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and other methods were used to characterize the samples. Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption. High specific surface areas and small pore diameters are beneficial to efficient mercury removal. Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency, in particular. The C-M bond, which is formed by the reaction of C and Ti, Si and other elements, may improve mercury oxidation. The samples modified with CuBr2 , CuCl 2 and FeCl3 showed excellent performance for Hg removal, because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+). Cu2+ and Fe3+ can also promote Hg 0 oxidation as catalysts. HCl and O2 promote the adsorption of Hg by modified fly ash, whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites. Fly ash samples modified with CuBr2 , CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.     

Adsorption and desorption of SO2, NO and chlorobenzene on activated carbon

Activated carbon (AC) is very effective for multi-pollutant removal; however, the complicated components in flue gas can influence each other''s adsorption. A series of adsorption experiments for multicomponents, including SO₂, NO, chlorobenzene and H₂O, on AC were performed in a fixed-bed reactor. For single-component adsorption, the adsorption amount for chlorobenzene was larger than for SO₂ and NO on the AC. In the multi-component atmosphere, the adsorption amount decreased by 27.6% for chlorobenzene and decreased by 95.6% for NO, whereas it increased by a factor of two for SO₂, demonstrating that a complex atmosphere is unfavorable for chlorobenzene adsorption and inhibits NO adsorption. In contrast, it is very beneficial for SO₂ adsorption. The temperature-programmed desorption (TPD) results indicated that the binding strength between the gas adsorbates and the AC follows the order of SO₂ > chlorobenzene > NO. The adsorption amount is independent of the binding strength. The presence of H₂O enhanced the component effects, while it weakened the binding force between the gas adsorbates and the AC. AC oxygen functional groups were analyzed using TPD and X-ray photoelectron spectroscopy (XPS) measurements. The results reveal the reason why the chlorobenzene adsorption is less affected by the presence of other components. Lactone groups partly transform into carbonyl and quinone groups after chlorobenzene desorption. The chlorobenzene adsorption increases the number of C = O groups, which explains the positive effect of chlorobenzene on SO₂ adsorption and the strong NO adsorption.     

Regeneration performance and carbon consumption of semi-coke and activated coke for SO2 and NO removal

To decrease the operating cost of flue gas purification technologies based on carbon-based materials, the adsorption and regeneration performance of low-price semi-coke and activated coke were compared for SO₂ and NO removal in a simulated flue gas. The functional groups of the two adsorbents before and after regeneration were characterized by a Fourier transform infrared (FTIR) spectrometer, and were quantitatively assessed using temperature programmed desorption (TPD) coupled with FTIR and acid–base titration. The results show that semi-coke had higher adsorption capacity (16.2% for SO₂ and 38.6% for NO) than activated coke because of its higher content of basic functional groups and lactones. After regeneration, the adsorption performance of semi-coke decreased because the number of active functional groups decreased and the micropores increased. Semi-coke had better regeneration performance than activated coke. Semi-coke had a larger SO₂ recovery of 7.2% and smaller carbon consumption of 12% compared to activated coke. The semi-coke carbon-based adsorbent could be regenerated at lower temperatures to depress the carbon consumption, because the SO₂ recovery was only reduced a small amount.     

秸秆污泥基活性炭的制备及吸附H2S的实验研究

以市政污泥和玉米秸秆的混合物为原材料,KOH为活化剂,制备了秸秆污泥基活性炭(AC).实验考察了秸秆与污泥用量比例,以及活化剂用量对秸秆污泥基活性炭物化特性的影响.结果显示,m(污泥)∶m(秸秆)∶m(KOH)为3∶7∶2的条件下,制备的活性炭C372以微孔为主,微孔率达到0.59,比表面积达到369.271 m2·g-1.该活性炭的穿透硫容与饱和硫容均最高,分别为5.82 mg·g-1(以H2S计)和7.00 mg·g-1(以H2S计),活性炭表面内酯基的存在不利于其对硫化氢的吸附.SEM和BET表征分析显示,随着秸秆在污泥中比例的增加,活性炭比表面积增大,对H2S的吸附量提高.活性炭C372具有较好的再生性能,二次再生后其穿透硫容与饱和硫容均能恢复55%以上.     

消除烟道气中二氧化硫的活性炭催化剂——SO2在催化剂上动态吸附研究

本文考察了流动态体系中,烟气主要组分(O₂和水蒸汽)的含量对SO₂在活性炭上吸附量的影响;研究了SO₂吸附动力学。结果表明,在一定空速和吸附温度下,烟气中O₂和水蒸汽含量分别为5%和8%(Ⅴ%)左右时,SO₂吸附量为最大。SO₂在活性炭上吸附动力学曲线很好地遵循Elovich方程;SO₂吸附活化能E_a⁰为21.939×10³J/mol以及Elovich参数,进而得出吸附活化能E_a,与吸附温度的关系。     

Antimony(V) removal from water by iron-zirconium bimetal oxide: Performance and mechanism

A Fe-Zr binary oxide adsorbent has been successfully synthesized using a co-precipitation method. It showed a better performance for antimonate (Sb(V)) removal than zirconium oxide or amorphous ferric oxide. The experimental results showed that the Fe-Zr adsorbent has a capacity of 51 mg/g at an initial Sb(V) concentration of 10 mg/L at pH 7.0. Sb(V) adsorption on the Fe-Zr bimetal oxide is normally an endothermic reaction. Most of the Sb(V) adsorption took place within 3 hr and followed a pseudo second-order rate law. Co-existing anions such as SO₄^2-, NO₃^- and Cl^- had no considerable effects on the Sb(V) removal; PO₃^4- had an inhibitory effect to some extent at high concentration; while CO_₃^2- and SiO₄^4- showed significant inhibitory effects when they existed in high concentrations. The mechanism of Sb(V) adsorption on the adsorbent was investigated using a combination of zeta potential measurements, XPS, Raman, FT-IR observations and SO₄^2- release determination. The ionic strength dependence and zeta potential measurements indicated that inner-sphere surface complexes were formed after Sb(V) adsorption. Raman and XPS observations demonstrated that both Fe-OH and Zr-OH sites at the surface of the Fe-Zr adsorbent play important roles in the Sb(V) adsorption. FT-IR characterization and SO₄^2- release determination further demonstrated that the exchange of SO₄^2- with Sb(V) also could promote the adsorption process. In conclusion, this adsorbent showed high potential for future application in Sb(V) removal from contaminated water.     

碱改性活性炭表面特征及其吸附甲烷的研究

采用不同浓度的氢氧化钠对椰壳活性炭进行表面改性.BET和SEM分析改性前后活性炭的表面结构,Boehm滴定和SEM/EDS方法测定活性炭表面元素及含氧基团.研究改性活性炭对甲烷的吸附性能和吸附行为.结果表明,经氢氧化钠改性处理后,活性炭孔径变化不明显,表面含氧基团显著减少;当氢氧化钠的浓度>3.3 mol·L-1时,活性炭的比表面积和孔容大于未处理的活性炭,并且随碱的浓度增加而增大.与改性前的活性炭相比,甲烷在碱改性活性炭上的吸附量提高了24%.增加活性炭的比表面积和孔容,减少表面的含氧基团有利于甲烷的吸附.甲烷的吸附行为符合Langmuir等温吸附式,吸附常数为163.7 m3·mg-1.     

SO_2体积分数对ZL50活性炭吸附脱硫行为的影响和动力学分析

通过动态吸附烟气脱硫实验,考察了烟气中不同SO2体积分数对ZL50脱硫脱硝活性炭脱硫行为的影响,并进行了动力学分析.随着烟气中SO2体积分数增大,脱硫率和ZL50脱硫脱硝活性炭的活性度下降;SO2吸附量和吸附速率增大.模拟结果表明,Bangham模型模拟效果最优,SO2的催化氧化反应对化学吸附有重要影响;Lagergren准一级吸附速率常数随SO2进口体积分数的增加而增大,表明SO2的催化氧化反应在吸附前期可能为速控步骤.推导和定义了Lagergren模型和Bangham模型的初始吸附速率;推导了文献上的Ho模型和Elovich模型的初始速率式。定义的Bangham初始吸附速率与初始吸附速率实验值吻合最好;建立的Bangham吸附反应动力学模型能较好地描述SO2动态吸附速率.结果表明,SO2的初始反应速率分级数为1或接近1,而O2和水蒸气的初始速率分级数分别为0.15～0.20和0.45～0.50之间的常数.     

新型铁铜铝三元复合氧化物除磷性能与机制研究

采用共沉淀法制备了一种新型铁铜铝三元复合氧化物吸附剂,系统研究了其对磷的吸附行为,并对吸附磷前后的吸附剂进行了表征.吸附实验结果表明,铁铜铝三元复合氧化物对磷具有优异的吸附去除效能,Freundlich吸附等温线模型能更好地拟合其对磷的吸附,最大吸附量为62.6 mg·g-1(pH=7.0),显著高于多数文献报道的磷吸附剂;吸附速率较快,吸附动力学更符合Elovich模型;溶液pH对磷吸附有一定影响,随着pH的升高,磷吸附量降低,离子强度则影响不大;共存阴离子对磷吸附具有抑制作用,影响的大小顺序为SiO_3~(2-)SO_4~(2-)CO_3~(2-)Cl~-,而共存阳离子Ca2+和Mg2+则对磷吸附略有促进作用.Zeta电位、红外谱图(FTIR)和X射线光电子能谱(XPS)表征分析表明,磷在铁铜铝三元复合氧化物表面发生了特性吸附,磷酸根主要通过取代复合氧化物表面的羟基形成内表面络合物而被吸附去除.溶出实验结果表明,当pH在5.0~8.5范围内,Fe~(3+)、Cu~(2+)、Al~(3+)的溶出量均较低.由此可知,铁铜铝三元复合氧化物是一种具有良好应用前景的除磷吸附剂.     

Pd/activated carbon sorbents for mid-temperature capture of mercury from coal-derived fuel gas

Higher concentrations of Hg can be emitted from coal pyrolysis or gasification than from coal combustion, especially elemental Hg. Highly efficient Hg removal technology from coal-derived fuel gas is thus of great importance. Based on the very excellent Hg removal ability of Pd and the high adsorption abilities of activated carbon（AC） for H2 S and Hg, a series of Pd/AC sorbents was prepared by using pore volume impregnation, and their performance in capturing Hg and H2 S from coal-derived fuel gas was investigated using a laboratory-scale fixed-bed reactor. The effects of loading amount, reaction temperature and reaction atmosphere on Hg removal from coal-derived fuel gas were studied. The sorbents were characterized by N2 adsorption, X-ray diffraction（XRD） and X-ray photoelectron spectroscopy（XPS）. The results indicated that the efficiency of Hg removal increased with the increasing of Pd loading amount, but the effective utilization rate of the active component Pd decreased significantly at the same time. High temperature had a negative influence on the Hg removal. The efficiency of Hg removal in the N2-H2S-H2-CO-Hg atmosphere（simulated coal gas） was higher than that in N2-H2S-Hg and N2-Hg atmospheres, which showed that H2 and CO, with their reducing capacity, could benefit promote the removal of Hg. The XPS results suggested that there were two different ways of capturing Hg over sorbents in N2-H2S-Hg and N2-Hg atmospheres.     

Heterogeneous oxidation of SO2 by O3-aged black carbon and its dithiothreitol oxidative potential

Ozone (O₃) is an important atmospheric oxidant. Black carbon (BC) particles released into the atmosphere undergo an aging process via O₃ oxidation. O₃-aged BC particles may change their uptake ability toward trace reducing gases such as SO₂ in the atmosphere, leading to different environmental and health effects. In this paper, the heterogeneous reaction process between O₃-aged BC and SO₂ was explored via in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Combined with ion chromatography (IC), DRIFTS was used to qualitatively and quantitatively analyze the sulfate product. The results showed that O₃-aged BC had stronger SO₂ oxidation ability than fresh BC, and the reactive species/sites generated on the surface had an important role in the oxidation of SO₂. Relative humidity or 254 nm UV (ultraviolet) light illumination enhanced the oxidation uptake of SO₂ on O₃-aged BC. The oxidation potentials of the BC particles were detected via dithiothreitol (DTT) assay. The DTT activity over BC was decreased in the process of SO₂ reduction, with the consumption of oxidative active sites.     

SO2对MnOx/PG催化剂低温脱硝的影响机理研究

采用等体积浸渍法制备了锰氧化物负载凹凸棒石(MnO_x/PG)低温SCR催化剂,通过SO₂暂态响应、程序升温表面反应(TPSR)等实验技术研究了烟气中SO₂对催化剂SCR脱硝活性的影响行为.采用程序升温脱附(TPD)、BET比表面及孔径分布测定、XPS等表征技术对催化剂硫中毒的机理及化学本质进行了深入分析.结果表明,低温下烟气中SO₂对MnO_x/PG催化剂的SCR脱硝活性存在显著的抑制作用,催化剂中毒主要由烟气中SO₂的催化氧化引起.一方面SO₂氧化为SO₃后与NH₃及H₂O竞争反应形成复杂的硫酸铵盐堵塞催化剂孔道,另一方面与活性组分MnO₂结合形成MnSO₄使得部分活性组分形态发生变迁.其中硫酸铵盐的形成可通过适当的热处理得以去除,而MnSO₄则不可恢复,但催化剂SCR活性却显著增加,表明MnSO₄的形成不是催化剂失活的主要因素.吸附态的硫可显著增加催化剂表面酸性,因此对SCR活性有促进作用.催化剂失活主要机理为:由气相SO₂的连续氧化并与NH₃相结合形成硫酸铵盐,并且在低温下难以分解,以致堵塞催化剂活性中心.     

酸碱改性活性炭及其对甲苯吸附的影响

分别用酸溶液(H_2SO_4、HNO_3、H_3PO_4)和碱溶液(NaOH或NH_3·H_2O)浸渍方法对活性炭进行改性,并对酸改性活性炭进行碱溶液二次改性处理,通过表征改性前后活性炭BET比表面积、孔结构、表面官能团等理化特征和测定其对甲苯蒸气的饱和吸附量,研究了影响活性炭吸附甲苯蒸气的关键因素.结果表明,酸改性使BET比表面积、微孔面积、微孔容积减少、表面酸性官能团增加,而碱改性呈现相反的理化特征变化.活性炭理化特征的变化可能与改性溶液的酸碱性、氧化还原性有关,并且这种相反的变化直接关系到活性炭对甲苯蒸气的吸附.3种酸改性的活性炭对甲苯蒸气饱和吸附量相对于原活性炭减少9.6%~20.0%,而两种碱改性的活性炭则增加29.2%~39.2%.相关性分析显示甲苯吸附量与BET比表面积、微孔面积、微孔容积正相关,而与表面酸性官能团负相关;多元回归分析进一步表明微孔容积和酸性官能团数量是影响活性炭甲苯吸附的关键因素.二次改性活性炭甲苯吸附量与表面含氧酸性官能团拟合结果则表明,—COOH、C＝O和—OH都对活性炭甲苯吸附能力有影响,其中—COOH影响较大.研究结果表明有效提高活性炭对甲苯吸附能力,改性宜以提高活性炭微孔容积和减小活性炭表面酸性官能团数量,特别是—COOH数量为目标导向.     

Removal of tetracycline from water by Fe-Mn binary oxide

Significant concerns have been raised over the presence of antibiotics including tetracyclines in aquatic environments. A series of Fe-Mn binary oxide with different Fe:Mn molar ratios was synthesized by a simultaneous oxidation and coprecipitation process for TC removal. Results showed that Fe-Mn binary oxide had higher removal efficiency than that of hydrous iron oxide and hydrous manganese oxide, and that the oxide with a Fe:Mn molar ratio of 5:1 was the best in removal than other molar ratios. The tetracycline removal was highly pH dependent. The removal of tetracycline decreased with the increase of initial concentration, but the absolute removal quantity was more at high concentration. The presence of cations and anions such as Ca²⁺, Mg²⁺, CO₃^2- and SO₄^2- had no significant effect on the tetracycline removal in our experimental conditions, while SiO₃^2- and PO₄^3- had hindered the adsorption of tetracycline. The mechanism investigation found that tetracycline removal was mainly achieved by the replacement of surface hydroxyl groups by the tetracycline species and formation of surface complexes at the water/oxide interface. This primary study suggests that Fe-Mn binary oxide with a proper Fe:Mn molar ratio will be a very promising material for the removal of tetracycline from aqueous solutions.     

等离子体催化降解甲苯途径的原位红外研究

考察了在常温常压条件下,等离子体分别协同SiO₂、Al₂O₃、NiO/Al₂O₃降解甲苯的性能,并从材料的介电常数、对甲苯的吸附性及臭氧分解能力等角度分析了不同活性表现的原因,同时,采用原位红外技术研究了甲苯降解过程中催化剂表面吸附物种的变化.结果表明,当甲苯浓度为100 ppm,气体流量为100 mL·min^-1时,一定范围内,甲苯降解率随着能量密度、介电常数、吸附性及臭氧分解能力的提高而提高.甲苯在催化剂表面的吸附对其降解途径有十分重要的影响:在放电区域中加入SiO₂,甲苯仍然在气相中完成降解;而存在Al₂O₃ 及NiO/Al₂O₃时,甲苯氧化成苯甲酸的过程主要发生在催化剂表面,是甲苯催化降解的关键步骤,苯甲酸在活性位点的积累将降低催化剂的反应活性.     

污泥生物炭硼掺杂改性及其对水中1,2-二氯乙烷吸附行为和机制

以市政污泥为前驱体，采用硼酸掺杂改性共热解法，制备了污泥生物炭(BC600)和B掺杂污泥生物炭(BBC600),采用SEM、BET、FTIR、Zeta电位和静态接触角等手段对材料进行了结构表征，研究了BC600和BBC600对水中1,2-二氯乙烷(1,2-DCA)的吸附行为、机制和影响因素.结构表征结果表明，B掺杂改性后，生物炭中B元素含量、比表面积和孔容分别提高了76%、48%和30%;B掺杂改性对生物炭表面电荷及亲疏水性影响不大，BC600和BBC600表面均带有负电荷，接触角均<90°,两者均具有较好的亲水性.吸附实验结果表明，BBC600对1,2-DCA的吸附性能优于BC600,缘于BBC600更大的比表面积和强度更高的含氧官能团；准一级动力学方程可以较好描述BC600吸附1,2-DCA过程，准二级动力学方程能较好拟合BBC600吸附1,2-DCA过程，颗粒内扩散不是影响吸附速率的唯一限速步骤；碱性条件下生物炭材料更加分散和稳定，且其含氧官能团去质子化，供电子能力增强，有利于对1,2-DCA的吸附；腐殖酸(HA)对BC600吸附1,2-DCA呈现低浓度促进，高浓度抑制的作...