棉秆基活性炭的制备及其对2,4-二硝基苯酚的吸附

以棉秆为原料,以KOH为活化剂,制备了高比表面棉秆基生物质活性炭。分析了制得的活性炭的元素组成、表面官能团、吸附能力等物化性能,探讨了浸渍比,活化温度,活化时间等工艺参数对制备活性炭得率、表面官能团、碘值、亚甲基蓝值等性能的影响,并通过静态吸附实验比较了不同条件下制备活性炭对2,4-二硝基苯酚的吸附性能,探讨了典型炭样品对2,4-二硝基苯酚的等温吸附特性。结果表明,KOH活化棉秆基生物质活性炭的表面物化性质随浸渍比、活化温度等工艺参数变化而变化,活化适宜条件为浸渍比1：3、活化温度800℃、活化时间90 min,在此条件下制得的炭样的碘值为1 251 mg/g,亚甲基蓝吸附值为478 mg/g,分别是国家一级品标准的1.25倍与3.54倍;对2,4-二硝基苯酚的Langmuir最大吸附量为747 mg/g,与Freundlich模型相比,Langmuir模型能较好地描述2,4-二硝基苯酚在炭样上的吸附行为,表明制备活性炭样品表面吸附位的能量分布较为均一。     

2,4-dichlorophenoxyacetic acid (2,4-D) micropollutant herbicide removing from water using granular and powdered activated carbons: a comparison applied for water treatment and health safety

Abstract

Activated carbons are well-known porous materials as an effective adsorbent used for the removal of emerging contaminants, such as herbicides, which are increasingly present in water bodies. Most water treatment plants, specially in Brazil, are unable to completely remove such contaminants by the conventional process and advanced treatment using activated carbons is required. The aim of this paper was to verify the influence of the activated carbons granulometry and specific surface area on the 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide removal efficiency using distilled-deionized water and filtered water collected from a conventional Water Treatment Plant. Commercial activated carbons samples used in this work were obtained from two different manufacturers. Activated carbons were analyzed by the specific surface area, pore size and volume distribution, nuclear magnetic resonance, infrared and x-ray spectroscopy, moisture, volatile matter and ash contents. Batch adsorption isotherms experiments were used and performed by Langmuir and Freundlich models. Granular and powdered activated carbons removed over 99% of 2,4-D in distilled water and near to 99% using filtered water. The activated carbons evaluated in this work presented high performance and played a key role in water treatment by removing 2,4-D herbicide, ensuring the protection of human health and the ecosystem.     

化学改性活性炭对水中阿特拉津的吸附去除

以5 mol/L HNO3,40%NaOH及5%H2O2对活性炭进行化学改性,采用序批式实验研究了活性炭改性前后对阿特拉津(AT)的吸附平衡特性,并以Langmuir和Freundlich模型对吸附等温线进行了拟合。结合活性炭改性前后孔结构和表面化学的变化特征,探讨了不同改性方法对AT吸附去除的影响效应。结果表明:活性炭经5 mol/L HNO3改性后对AT的吸附性能显著降低;而5%H2O2和40%NaOH改性炭对AT的吸附能力较原炭明显增强,且40%NaOH改性炭的吸附能力大于5%H2O2改性炭。原炭及改性炭对AT的吸附等温线均符合Langmuir模型。HNO3改性炭对AT吸附的降低主要是由于表面酸性基团的增加引起的;H2O2改性炭对AT吸附能力的提高主要是由于比表面积的增大引起的;而NaOH改性炭对AT吸附能力的提高是由比表面积增大和表面碱性基团增加共同作用的结果。几种改性炭和原炭对AT去除率的大小顺序依次为:NaOH改性炭>H2O2改性炭>原炭>HNO3改性炭。     

微波活化中孔酸性生物质炭对亚甲基蓝的吸附行为与机理

以甘蔗渣为原料,采用微波辅助磷酸活化法制备了同时富含中孔结构和含氧酸官能团的生物质炭,以氮气吸附、红外光谱FT-IR等技术对炭样品表面物化性质进行了表征,通过静态实验法测定了生物质炭对水中亚甲基蓝的吸附特性,分析了溶液pH、初始浓度、温度对吸附的影响,研究了不同pH下蔗渣生物质炭对亚甲基蓝的吸附行为,并从热力学及动力学角度探讨了生物质炭对亚甲基蓝的吸附机理。结果表明,不同制备参数下生物质炭的得率均大于39.2%,但表面物化性质因参数变化有较大差异。在浸渍比1∶1,烘干时间10 h,活化功率900 W,活化时间22 min的条件下,制得的生物质炭的比表面积为1 021 m2/g,亚甲基蓝值超过国家一级品标准1.70倍,表面富含微中孔结构和羟基、羰基、羧基等酸性官能团,中孔约占总孔的40%。静态吸附实验表明,溶液初始浓度对吸附有较大的影响,吸附量随初始浓度的增加,pH的升高及温度的上升而增大,Freundlich方程、Redlich-Peterson方程与Temkin方程能较好地描述等温吸附行为;吸附动力学结果表明,数据符合Elovich方程,吸附行为更倾向于化学吸附;热力学研究表明,吸附吉布斯自由能(ΔG0)0,吸附标准焓变(ΔH0)70 kJ/mol,说明该吸附为自发的吸热反应,且化学反应在吸附过程中发挥了重要作用。     

改性核桃果皮基活性炭对Cu2+的吸附

以核桃外果皮制备活性炭及改性活性炭,对制得的活性炭进行表征,研究了5种活性炭对重金属Cu2+的吸附性能。研究表明,以氯化锌为活化剂制得的活性炭,其碘吸附值及表面酸性基团含量均高于磷酸活化制备的活性炭,改性后的活性炭吸附性能明显增强,碘吸附值最高达到678.53 mg·g-1,对Cu2+的最高去除率达到91.43%。吸附量和Cu2+去除率随时间、温度和pH的升高而增大,5种活性炭投加量增加,导致吸附量减小,但Cu2+去除率增大,吸附平衡时间为3 h。5种活性炭对Cu2+的吸附均符合准二级动力学模型。磷酸和氯化锌活化的活性炭吸附等温线符合Tempkin模型,而3种改性活性炭的吸附等温线则较好地符合Langmuir模型。     

Kinetics of benzene adsorption onto activated carbon

An activated carbon bed adsorption process is influenced by the adsorbents' characteristics, volatile organic compound (VOC) characteristics, and process conditions. In the literatures, the adsorption processes of the adsorbents and VOCs were usually considered to be in equilibrium. In this study, the VOC adsorption processes by activated carbon were considered to be a kinetic process, i.e. they are not in equilibrium. Then, isothermal adsorption curves and a small column experiment were simulated.     

活性染料K-2BP、KN-B和KN-R在椰壳活性炭上的脱色性能

开展椰壳活性炭对活性染料K-2BP、KN-B和KN-R的吸附脱色研究。发现K-2BP、KN-B和KN-R在该型活性炭上的吸附脱色率均随初始pH值的降低、温度的升高、染料初始浓度的降低、活性炭用量的增加以及NaCl盐度的增加而增加。在pH=7和T=25℃下,K-2BP、KN-B和KN-R在活性炭上的等温吸附规律符合Langmuir模型方程,最大饱和吸附量Qmax分别为263.15、256.41和250 mg/g,吸附自由能△G298 K分别为-10.632、-3.783和-2.805 kJ/mol;该条件下K-2BP、KN-B和KN-R的动力学吸附规律均符合准一级动力学吸附方程。等温吸附研究和吸附动力学研究均表明,相同条件下3种活性染料在该型活性炭上的吸附效果由高到低的顺序为:K-2BP>KN-B>KN-R。     

Reductive transformation of 2,4-dichlorophenoxyacetic acid by nanoscale and microscale Fe3O4 particles

Reductive transformation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nanoscale and microscale Fe₃O₄ was investigated and compared. Disappearance of the parent species and formation of reaction intermediates and products were kinetically analyzed. Results suggest that the transformation of 2,4-D followed a primary pathway of its complete reduction to phenol and a secondary pathway of sequential reductive hydrogenolysis to 2,4-dichlorophenol (2,4-DCP), chlorophenol (2-CP, 4-CP) and phenol. About 65% of 2,4-D with initial concentration of 50 μ M was transformed within 48 h in the presence of 300 mg L^?1 nanoscale Fe₃O₄, and the reaction rates increased with increasing dosage of nanoscale Fe₃O₄. The decomposition of 2,4-D proceeded rapidly at optimum pH 3.0. Chloride was identified as a reduction product for 2,4-D in the magnetite–water system. Reductive transformation of 2,4-D by microscale Fe₃O₄ was slower than that by nanoscale Fe₃O₄. The reactions apparently followed pseudo-first-order kinetics with respect to the 2,4-D transformation. The degradation rate of 2,4-D decreased with the increase of initial 2,4-D concentration. In addition, anions had a significant adverse impact on the degradation efficiency of 2,4-D.     

Adsorption of acid dye onto activated carbons prepared from agricultural waste bagasse by ZnCl2 activation

A series of activated carbons were prepared from agricultural waste sugarcane bagasse by chemical activation with zinc chloride (ZnCl2) as an activating agent at 500 degrees C and 0.5 h soaking time. The Langmuir surface area and total pore volume were used to estimate the average pore diameter of the carbon products. The values of the surface area and pore volume increased linearly with increase in the impregnation ratio (IR) up to 100 wt%. The adsorption capacities of the derived adsorbents for Acid Orange 10 were measured at 20 degrees C and 40 degrees C to gain further insights into the acidic surface oxides of the adsorbent from the results of Fourier transform infrared (FTIR) spectroscopy analysis and pH measurement. Adsorption isotherms of the acid dye on adsorbents prepared were determined and correlated with common isotherm equations. It was found that the Langmuir model appears to fit the isotherm data better than the Freundlich model. The physical properties of these adsorbents were consistent with the parameters obtained from the isotherm equations.     

粉末活性炭对三烯丙基异氰脲酸酯的吸附性能

用静态吸附法考察粉末活性炭对水中三烯丙基异氰脲酸酯（CAIC）的吸附行为,采用单因素分析法对活性炭吸附化工废水中TAIC的工艺条件进行研究。实验结果表明,在TAIC模拟废水中,其TAIC初始浓度为800 mg/L,pH为7,在温度为298 K、转速为150 r/min的条件下,当活性炭的投加量达到4.4 g/L,吸附反应时间为50 min时,TAIC的去除效率最高为96.17%;对于实际废水,其TAIC初始浓度为1 500 mg/L,溶液pH为3,在温度为298 K、转速为150 r/min的条件下,当活性炭投加量达到10 g/L,吸附反应时间为2 h时,TAIC的去除效率最高为46.8%。这也是由于实际废水组分复杂,其他有机物存在一定的吸附竞争机制。     

粉末活性炭对三烯丙基异氰脲酸酯的吸附性能简

用静态吸附法考察粉末活性炭对水中三烯丙基异氰脲酸酯（CAIC）的吸附行为,采用单因素分析法对活性炭吸附化工废水中TAIC的工艺条件进行研究。实验结果表明,在TAIC模拟废水中,其TAIC初始浓度为800 mg/L,pH为7,在温度为298 K、转速为150 r/min的条件下,当活性炭的投加量达到4.4 g/L,吸附反应时间为50 min时,TAIC的去除效率最高为96.17%;对于实际废水,其TAIC初始浓度为1 500 mg/L,溶液pH为3,在温度为298 K、转速为150 r/min的条件下,当活性炭投加量达到10 g/L,吸附反应时间为2 h时,TAIC的去除效率最高为46.8%。这也是由于实际废水组分复杂,其他有机物存在一定的吸附竞争机制。     

活性炭对水中微量酰胺咪嗪吸附规律

选择3种商品活性炭(煤质炭MAC、杏壳炭XAC、椰壳炭YAC),从其对水中微量药物酰胺咪嗪(carbamaz-epine,CBZ)的吸附平衡、吸附等温式、吸附动力学和热力学等方面详细考察了不同种类活性炭对CBZ的吸附去除规律。实验结果表明,3种活性炭与CBZ接触反应10 h后均达到吸附平衡,对CBZ的平衡吸附量在8.3 mg/g左右;比较了Lang-muir和Freundlich两种吸附等温式,发现Langmuir方程更适合描述3种活性炭对CBZ的吸附过程;计算表明3种活性炭的吸附过程均符合拟二级动力学方程,Weber-Morris方程的模拟结果则说明膜扩散和内扩散共同限制了3种活性炭对CBZ的吸附速率;3种活性炭的Ea值分别为29.87 kJ/mol(MAC)、36.02 kJ/mol(XAC)和38.86 kJ/mol(YAC),表明3种活性炭吸附CBZ时同时发生了物理吸附和化学吸附作用,且以化学吸附为主;20～40℃时3种活性炭的△G均为负值,说明3种活性炭对CBZ的吸附反应可以自发进行;MAC、XAC、YAC的△H值分别为-3.10、-3.05和-3.02 kJ/mol,负值表明吸附过程放热,上述△H值较小则说明温度对CBZ的吸附影响不大;3种活性炭吸附CBZ过程的△S值为0.94 J/(mol.K)(MAC)、2.24 J/(mol.K)(XAC)和2.97 J/(mol.K)(YAC),说明吸附过程熵值增加,在外界条件不改变的情况下该吸附过程不可逆,同时可以看出在3种活性炭中,CBZ分子更倾向于吸附在YAC上。     

磷酸微波活化多孔生物质炭对亚甲基蓝的吸附特性

以甘蔗渣为原料,采用微波辅助H3PO4活化法制备富含含氧酸官能团的中孔生物质炭。通过扫描电子显微镜SEM、傅立叶变换红外光谱FT-IR等技术对生物质炭物理化学性质进行表征,并通过静态实验法,探讨炭样对亚甲基蓝的吸附行为及热力学性质。结果表明,H3PO4活化制备蔗渣生物质炭的适宜条件为浸渍比1：1,烘干时间10h,活化功率900W,活化时间22min,在此条件下制得的生物质炭得率为39．2％,碘值为817mg／g,亚甲基蓝值为229mg／g,为国家一级品标准的1．7倍。红外光谱分析表明,炭样表面以羟基、羰基、羧基等酸性官能团为主。静态吸附实验表明,Freundlich方程与Redlich—Peterson方程能较好地描述等温吸附行为,表现为优惠吸附。热力学研究表明,吸附吉布斯自由能（△G0）〈0,说明吸附反应是自发过程,而吸附标准焓变（△H0）〉70KJ／mol,表明亚甲基蓝在制备炭样上的吸附是吸热反应,升温有利于吸附,且化学反应在吸附过程中发挥了重要作用。     

3种表面修饰活性炭对水体中磷的吸附

为克服活性炭磷吸附能力有限的问题,使用ZnCl2、十六烷基三甲基氯化铵（CTAC）和Fe/Al（氢）氧化物纳米颗粒分别研究了物理结构法、表面活性剂法和载体法3 种表面修饰方法对活性炭磷吸附能力的影响。实验发现,载体法为3 种方法中最好的修饰方法。对载体法制备吸附剂的材料用量的比较发现,在Fe（III）和Al（III）摩尔比为9 ：1 的条件下,把1.5 g活性炭加入到总浓度为1 mol·L-1的200 mL Fe(III)和Al(III)混合溶液中,形成的纳米Fe/Al（氢）氧化物能够较好地利用活性炭表面,该复合材料1.5AC-Fe/Al在磷平衡浓度约为50 mg·L-1时吸附量达到29.3mg·g-1。该材料表征结果表明,纳米Fe/Al（氢）氧化物颗粒被成功负载在活性炭表面。在酸性条件下,复合材料表面的—H+和—OH2+所引起的静电吸附和配位交换是促进吸附带负电磷酸根离子的原因。     

Effects of 2,4-dichlorophenoxyacetic acid formulation on medulla spinalis of Poecilia reticulata: A histopathological study

This study investigated the possible effects of a commonly used foliar herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) formulation on medulla spinalis of lebistes. Fish were exposed to 2,4-D (15, 30, 45 mg L⁻¹), behavioral changes were monitored. Fish were fixed, histopathological examination was carried out on sections taken from the upper parts of the fish body. Histopathology showed increase in neuronal loss, swelling indicating formation of intracellular edema, vacuolization noticed as the formation of vacuoles within or adjacent to cells, deformation in the Nissl granules, pyknosis and gliosis in medulla spinalis. Behavioral changes were decreased general activity, grouping, shortness in breath, sudden rotations and jumping, loss of equilibrium and colour. In conclusion, this commercial formulation of 2,4-D is considerably neurotoxic to lebistes. Fish constitute the last link in the chain of the feeding cycle in aquatic eco-system, number of studies investigating acute and chronic neurotoxicity of various herbicides in fish should be increased.     

Adsorptive removal of an acid dye by lignocellulosic waste biomass activated carbon: equilibrium and kinetic studies

Chemically prepared activated carbon material derived from palm flower was used as adsorbent for removal of Amido Black dye in aqueous solution. Batch adsorption studies were performed for the removal of Amido Black 10B (AB10B), a di-azo acid dye from aqueous solutions by varying the parameters like initial solution pH, adsorbent dosage, initial dye concentration and temperature with three different particle sizes such as 100 μm, 600 μm and 1000 μm. The zero point charge was pH 2.5 and the maximum adsorption occurred at the pH 2.3. Experimental data were analyzed by model equations such as Langmuir, Freundlich and Temkin isotherms and it was found that the Freundlich isotherm model best fitted the adsorption data and the Freundlich constants varied from (K_F) 1.214, 1.077 and 0.884 for the three mesh sizes. Thermodynamic parameters such as ΔG, ΔH and ΔS were also calculated for the adsorption processes and found that the adsorption process is feasible and it was the endothermic reaction. Adsorption kinetics was determined using pseudo first-order, pseudo second-order rate equations and also Elovich model and intraparticle diffusion models. The results clearly showed that the adsorption of AB10B onto lignocellulosic waste biomass from palm flower (LCBPF) followed pseudo second-order model, and the pseudo second-order rate constants varied from 0.059 to 0.006 (g mg⁻¹ min) by varying initial adsorbate concentration from 25 mg L⁻¹ to 100 mg L⁻¹. Analysis of the adsorption data confirmed that the adsorption process not only followed intraparticle diffusion but also by the film diffusion mechanism.     

Utilization of Arachis hypogaea hull,an agricultural waste for the production of activated carbons to remove phenol from aqueous solutions

Arachis hypogaea hulls, an agricultural waste, were used to prepare activated carbon by chemical activation with zinc chloride under four different activation atmospheres. The most important parameter in chemical activation was found to be the chemical ratio (activating agent/precursor). Carbonization temperature and time are the other two important variables, which had significant effect on the pore structure of carbon. The maximum Brunquer-Emmett-Teller (BET) surface area and micropore volume of the activated carbon was found to be 418 m²/g and 0.28 cm³/g, respectively. The activated carbon developed shows substantial capability to adsorb phenol from aqueous solutions. The kinetic data were fitted to the models of intraparticle diffusion, pseudo-second-order, and Lagergren, and followed more closely the pseudo-second-order chemisorption model. The isotherm equilibrium data were well fitted by the Langmuir and Freundlich models. Solution pH has significant effect on adsorption and the maximum uptake of phenol was reported at pH 3.5.     

粉末活性炭对水溶液中邻苯二甲酸二(2-乙基己基)酯的吸附

采用静态吸附法研究了邻苯二甲酸二(2-乙基己基)酯(DEHP)在粉末活性炭上的吸附性能,探讨了粉末活性炭对DEHP的吸附等温线、吸附动力学和吸附热力学特征。结果表明,粉末活性炭对DEHP吸附等温线符合Langmuir吸附等温式;分别采用拟一级反应、拟二级反应和颗粒内扩散反应模型对吸附动力学过程进行了拟合,实验数据遵循颗粒内扩散模型;在20、30、40和50℃下,对应的吉布斯自由能(ΔG0)分別为-2.014、-1.441、-0.868和-0.296 kJ/mol,表明该反应自发进行;焓变(ΔH0)<0,证实该反应为放热反应;熵变(ΔS0)<0,说明该吸附反应是熵值减小的过程;吸附活化能Ea=7.234 kJ/mol和粘附概率S*=0.036分别介于5～40 kJ/mol和0～1范围内,表明该吸附过程主要为物理吸附;活性炭吸附前后红外谱图分析,也验证物理吸附为PAC吸附DEHP之主要机制。     

四环素在活性炭上的吸附行为及机理

考察了活性炭和四环素的相关性质,并通过静态吸附实验探讨了2种活性炭对四环素的吸附和脱附行为,以及pH值、离子强度等水化学条件对活性炭吸附四环素的影响。结果表明,四环素在活性炭上的吸附基本不受离子强度影响;但随着pH值上升,其吸附量下降。四环素在活性炭上吸附的驱动力可能为两者所含官能团间的氢键作用。     

酸碱改性活性炭吸附微污染水源水中的Ni2+

通过HNO3-KOH对活性炭进行改性,采用扫面电镜（SEM）、比表面积分析（BET）、红外光谱分析（FT-IR）和Boehm滴定法对改性前后的活性炭进行表征,研究了改性前后的活性炭在不同条件下对微污染水源水中Ni2+的吸附能力和动力学。结果表明：改性活性炭表面含氧酸性官能团数量增加,比表面积和总孔容均略有降低,孔径变化不明显。在Ni2+浓度为0.4 mg·L-1,改性活性炭投加量5.0 g·L-1,温度30 ℃时,反应1 h去除率可达95.55%,剩余Ni2+浓度为0.017 8 mg·L-1,达到《生活饮用水卫生标准》（GB5749-2006）中的要求。相同条件下,改性前活性炭对Ni2+的去除率仅为74.45%,剩余Ni2+浓度达不到标准要求。活性炭对Ni2+的等温吸附更符合Langmuir方程,吸附动力学数据符合准二级动力学方程。