微孔分子筛的合成及其去除水中氨氮的实验研究

以廉价的天然矿物岩石作为主要原料,采用水热晶化法合成了微孔分子筛。分子筛有效孔径约为0.9 nm,BET比表面积583m2/g,阳离子交换容量(CEC)316 meq/100 g。将其用于水体中氨氮的去除,实验结果表明,分子筛对氨氮的吸附速率较快,吸附时间为20 min时,吸附基本达饱和;分子筛对氨氮的最大吸附量可达11.6 mg/g,其吸附规律很好地符合Fruendlich吸附等温式;在有干扰离子如Ca2+、Mg2+、Al3+和Fe3+等存在的情况下,仍能优先选择吸附NH4+,且吸附率几乎没有变化。动态吸附柱实验的效果好于静态实验,出水12 h内去除率均>85％;饱和了氨氮的分子筛,用氢氧化钠溶液洗脱再生,解吸率达92％,再生后的分子筛与原分子筛相比吸附率几乎没有降低。     

Effective uptake of decontaminating agent (citric acid) from aqueous solution by mesoporous and microporous materials: an adsorption process

The presence of citric acid in decontamination waste can cause complexation of the radioactive cations resulting in interferences in their removal by various treatment processes such as chemical precipitation, ion-exchange, etc., which are employed for the removal of radioactivity and may cause potential danger to the environment. Mesoporous Al-MCM-41 (Si/Al=30, 51, 72 and 97) and Si-MCM-41 molecular sieves were synthesized hydrothermally and characterized by XRD, BET (surface area) and FT-IR to evaluate the removal of citric acid through an adsorption process. Adsorption of citric acid over Al-MCM-41 shows the applicability of Freundlich and Langmuir isotherm and follows first order kinetics. The effects of contact time, concentration of citric acid, adsorbents (various Si/Al ratios of Al-MCM-41, Si-MCM-41, Hbeta zeolite and commercial carbon) and pH have been investigated. It has been found that the amount of citric acid adsorbed per unit gram of catalyst followed the order Al-MCM-41 (Si/Al=30)>Al-MCM-41 (Si/Al=51)>activated charcoal>Al-MCM-41 (Si/Al=72)>Al-MCM-41 (Si/Al=97)>Si-MCM-41>Hbeta zeolite.     

MCM-41介孔分子筛的合成及其对铜离子的吸附性能简

以微硅粉为硅源，CTAB和PEG-6000为模板剂，合成MCM-41介孔分子筛。采用XRD、N₂吸附-脱附曲线、FTIR以及TEM表征了其结构、比表面积、孔径分布及晶体形貌，并且以该样品为吸附剂，对含Cu²⁺的溶液进行了静态吸附实验。结果表明，以微硅粉为硅源成功合成了具有典型六方排列孔道结构的MCM-41，其比表面积为869.5 m²/g，孔容为0.97 cm³/g，平均孔径为3.3 nm；溶液pH为5~6时，MCM-41对Cu²⁺的去除效果最好；MCM-41对Cu²⁺的最大吸附吸附容量36.3 mg/g；MCM-41对Cu²⁺的吸附性能符合Langmuir吸附方程的特征。动力学研究表明，该过程符合准二级动力学模型。     

不同硅铝比的ZSM-5型沸石分子筛吸附水中Cu2＋离子的研究

考察了3种不同硅铝比的ZSM-5沸石分子筛（25H、38H和50H，25、38和50为硅铝比）对水中Cu2＋的吸附过程及其影响因素。结果表明，3种材料均能有效吸附去除水中Cu2＋离子，动力学符合假二阶动力学模型，吸附等温线符合Langmuir吸附等温式。3种材料吸附速率及吸附容量顺序为：25H〉50H〉38H，其中，25H最大吸附容量达到12．83mg／g。投加量由0．8g／L增加至2．0g／L，材料对Cu2＋吸附去除率由87．0％增加至97．5％。考察水中常见阳离子对吸附的干扰作用，结果表明，干扰离子的影响顺序为：Pb2＋〉K＋〉Na＋〉Mg2＋；随着干扰离子浓度的增大，材料对Cu2＋的去除率显著下降。硅铝比及晶粒形貌均对沸石分子筛吸附Cu2＋有较大影响，小的孔径不利于Cu2＋的吸附，低硅铝比有利于Cu2＋在分子筛上的吸附。     

Adsorption properties of regenerative materials for removal of low concentration of toluene

A specific type of material, activated carbon fiber (ACF), was modified by SiO₂, and the final products ACF-x were obtained as ACF-12.5, ACF-20, ACF-40, and ACF-80 according to different dosages of tetraethoxysilane (TEOS). The modified material on the ACF surface had a significant and smooth cover layer with low content of silica from scanning electron microscope (SEM) image. The modified ACF-x showed the stronger hydrophobicity, thermal stability, and adsorption capacity, which had almost no effect in the presence of water vapor and no destruction in multiple cycles. ACF-20 was proven as the most efficient adsorbent in humid conditions. The dual-function system composed of the regenerative adsorbents and the combustion catalyst would be efficient in consecutive toluene adsorption/oxidation cycles, in which the combustion catalyst was prepared by the displacement reaction of H₂PtCl₆ with foam Ni. Therefore, the adsorption/catalytic oxidation could be a promising technique in the indoor air purification, especially in the case of very low volatile organic compound (VOC; toluene) concentration levels.

Implications: Exploring highly effective adsorptive materials with less expensive costs becomes an urgent issue in the indoor air protection. ACF-20 modified by SiO₂ with Pt/Ni catalysts shows stronger hydrophobicity, thermal stability, and adsorption capacity. This dual-function system composed of the regenerative materials and the combustion catalyst would be a promising technique in the indoor air purification, especially in the case of removal of very low concentration of toluene.     

MCM-41介孔分子筛的合成及其对铜离子的吸附性能

以微硅粉为硅源，CTAB和PEG-6000为模板剂，合成MCM-41介孔分子筛。采用XRD、N2吸附-脱附曲线、FT—IR以及TEM表征了其结构、比表面积、孔径分布及晶体形貌，并且以该样品为吸附剂，对含Cu2＋的溶液进行了静态吸附实验。结果表明，以微硅粉为硅源成功合成了具有典型六方排列孔道结构的MCM-41，其比表面积为869．5m。／g，孔容为0．97cm3／g，平均孔径为3．3nm；溶液pH为5—6时，MCM-41对Cu2＋的去除效果最好；MCM-41对Cu3＋的最大吸附吸附容量36．3mg／g；MCM-41对Cu2＋的吸附性能符合Langmuir吸附方程的特征。动力学研究表明，该过程符合准二级动力学模型。     

Synthesis and application of Cu-BTC@ZSM-5 composites as effective adsorbents for removal of toluene gas under moist ambience: kinetics,thermodynamics, and mechanism studies

Metal organic frameworks (MOFs) are excellent adsorbents that provide abundant specific surface area, adjustable pore structure, and rich active sites. The purpose of this study was to prepare composites with hydrophobic and high microporous specific surface area and to adsorb toluene gas in moist ambience. An ethanol activation-assisted hydrothermal method was proposed to synthesize copper-benzene-1,3,5-tricarboxylic acid (Cu-BTC) metal-organic framework, Cu-BTC, and ZSM-5 molecular sieve composites (Cu-BTC@ZSM-5). The dynamic adsorption process of toluene on different adsorbents was investigated, and the results showed that the toluene adsorption capacity of Cu-BTC@ZSM-5 (158.6 mg/g) was 2.53 times higher than Cu-BTC (62.7 mg/g), when the ZSM-5 content is 5% and the humidity is 30%RH. Compared with other factors, the humidity inhibited the adsorption of toluene on Cu-BTC@ZSM-5. Langmuir model and the pseudo-second kinetics model can better describe the adsorption behavior of Cu-BTC@ZSM-5. The thermodynamic results showed the adsorption process was a spontaneous exothermic process at low temperature and mainly physical adsorption. The relative regenerability can still up to 80.4% after six cycles. The adsorption mechanisms of Cu-BTC@ZSM-5 were pore-filling adsorption, π-π interaction, cation-π bonding, and hydrophobic interactions. This study will help to design a systematic route to evaluate the adsorption performance of Cu-BTC@ZSM-5 for toluene.

     

VOCs和水在Y型分子筛表面的竞争吸附

采用水热处理方法合成了具有不同硅铝比的超稳Y型分子筛,考察了苯、甲苯、二甲苯、苯乙烯和乙酸乙酯与水在Y分子筛表面的竞争吸附。结果表明,随着Si/Al比的增加,Y分子筛表面的有机分子选择性吸附位数量增加,有机分子竞争吸附能力增加。低硅Y型分子筛只有在吸附偶极距>1.0的高极性有机分子时才能与水分子产生有力的竞争吸附,而高硅超稳Y分子筛则对偶极距在0～0.5范围的有机分子就表现出很强的竞争吸附能力。     

Adsorption of mesitylene via mesoporous adsorbents

Mesitylene (or 1,3,5-trimethylbenzene) is a volatile organic compound emitted from various industrial processes, e.g., spray coating. Its emissions have become a critical issue because mesitylene is toxic and cannot be removed using traditional adsorbents, e.g., zeolite (H-ZSM-5; the diameter of mesitylene molecules is greater than the pore size of H-ZSM-5). Hence, an adsorbent with a large pore size, MCM-41, is used in this study to investigate its adsorption capacity for mesitylene and compare with that of H-ZSM-5. Experimental results reveal that MCM-41 without Al₂O₃ exhibits a good adsorption capacity (184 mg/g) for the gas stream containing 100 ppm of mesitylene at a relative humidity of 10%. The adsorption kinetics is well described by the Freundlich isotherm. Furthermore, experimental results reveal that MCM-41 is effective for the adsorption of low concentrations (10 ppm) of mesitylene. In addition, adsorption–desorption tests revealed that the sample MCM-41-AS is stable to sustain the adsorption capacity after 10 adsorption–desorption cycles. After 10 adsorption–desorption cycles, MCM-41-AS retains 92.4% of its initial adsorption capacity (170 vs. 184 mg/g). Finally, MCM-41 and H-ZSM-5 in series are effective for the simultaneous removal of mesitylene and toluene in the gas stream.

Implications: This study aims to improve the performance of adsorbent for mesitylene, which is typically applied in the spray-coating industry. The zeolite MCM-41-AS is selected as a candidate for the investigation. Experimental results reveal that MCM-41-AS exhibits a good adsorption capacity for mesitylene and that it can be integrated with H-ZSM-5-25 for the simultaneous adsorption of mesitylene and toluene.     

Synthesis of high-purity Na-A and Na-X zeolite from coal fly ash

Coal fly ash (CFA) was used as a raw material for the synthesis of zeolite molecular sieve. The synthesis began with the pretreatment of CFA to remove impurities (e.g., Fe₂O₃, CaO, etc.) under various acid types (HCl, H₂SO₄, and HNO₃) and acid/CFA ratios (5–25 mL_acid/g_CFA). High product purity (up to 97%) was achieved with HCl (20%wt), and acid/CFA ratio of 20 mL_HCl/g_CFA. The treated CFA was then converted to zeolite by the fusion reaction under various Si/Al molar ratios (0.54–1.84). Zeolite type A was synthesized when the Si/Al molar ratios were lower than 1, whereas sodium aluminum silicate hydrate was formed when the Si/Al molar ratio were higher than 1. The highest water adsorption performance of the zeolite product, i.e., the outlet ethanol concentration of 99.9%wt and the specific adsorption capacity of 2.31 × 10^?2 g_water/g_zeolite, was observed with the Si/Al molar ratio of 0.82. The zeolite was tested for its water adsorption capacity repeatedly 10 times without deactivation.

Implications: This work evaluated the technical feasibility in the conversion of CFA to zeolite, which would help reduce the quantity of waste needed to be landfilled. This adds value to the unwanted material by converting it into something that can be further used. The synthesized products were shown to be quite stable as water adsorbent for the dehydration of ethanol solution.     

Characterization and adsorption capacity of modified 3D porous aerogel from grapefruit peels for removal of oils and organic solvents

With the rapid industrialization, especially offshore oil exploitation, frequent leakage incidents of oils/organic solvents have adversely affected ecological systems and environmental resources. Therefore, great interest has been shown in developing new materials to eliminate these organic pollutants, which have become worldwide problems. In this study, a cost-effective, environmentally friendly porous aerogel with three-dimensional (3D) structure was prepared from grapefruit peel by a facile hydrothermal method as the adsorbent of oils/organic solvents. The as-prepared modified grapefruit peel aerogel (M-GPA) showed mesoporous structure with high specific surface area of 36.42 m²/g and large pore volume of 0.0371 cm³/g. The excellent hydrophobicity of M-GPA with a water contact angle of 141.2° indicated a strong potential for adsorption of oils and organic solvents. The high adsorption capacity of M-GPA for a series of oils and organic solvents was 8 to 52 times as much as its own weight. Moreover, the M-GPA was easily regenerated and a high adsorption capacity recovery above 97% was maintained after five adsorption–regeneration cycles. Therefore, the M-GPA is a promising recyclable adsorbent for the removal of oils/organic solvents from polluted water.

     

活性炭孔隙结构在其甲苯吸附中的作用

选用4种商用活性炭(AC),利用氮气绝热吸附、扫描电子显微镜(SEM)和傅立叶变换红外光谱(FTIR)测试了活性炭的物化性质。以甲苯为吸附质,在温度为298.15 K下进行了静态和动态吸附实验,研究了活性炭孔结构对其吸附性能、吸附行为、表面覆盖率和吸附能的影响。结果表明:活性炭的比表面积和孔容是其吸附性能主要影响因素,孔径在0.8～2.4 nm之间的孔容和甲苯吸附量之间存在较好的线性关系,且线性斜率随甲苯浓度增加而变大。甲苯吸附行为符合Langmuir吸附等温模型和准一阶动力学方程式。活性炭孔结构是甲苯吸附速率的主要制约因素。在甲苯快速吸附阶段,微孔为吸附速率主要制约因素,在甲苯颗粒内扩散阶段,微孔和表面孔为吸附速率的主要制约因素,在吸附末尾阶段,中孔和大孔为吸附速率的主要制约因素。4种活性积炭对甲苯的吸附能随其比表面变大而变大。     

Influence of dissolved organic matter and oil on the biosorption of BTEX by macroalgae in single and multi-solute systems

The effect of dissolved organic matter (DOM) and oil on the removal of the water-soluble compounds benzene, toluene, ethylbenzene, and xylene isomers (BTEX) by two low-cost biosorbents Macrocystis pyrifera and Ulva expansa) was evaluated. DOM decreased the adsorption capacity of toluene, ethylbenzene, and xylenes of the two biosorbents. In contrast, the removal of benzene increased under the same conditions in single and multi-solute systems: this effect was dominant in U. expansa biomass treatments. In the presence of DOM and oil in solutions, the removal of BTEX notoriously increased, being oil that contributed the most. Solubility and hydrophobicity of pollutants played a key role in the adsorption process. The attractions between BTEX molecules and biosorbents were governed by π–π and hydrophobic interactions. Affinities of biosorbents for BTEX were mainly in the order of X > E > T > B. The Langmuir and Sips equations adjusted the adsorption isotherms for BTEX biosorption in deionized and natural water samples, but in the case of oily systems, the Freundlich equation seemed to have a better fit. The biosorption processes followed a pseudo-second-order rate in all the cases.     

泥炭对甲苯的吸附-解吸行为研究

用热处理方法对泥炭进行活化改性,探讨了对甲苯的吸附性能及影响因素,并研究了甲苯在泥炭上的吸附/解吸行为。结果表明,粒径在0.6～1 mm之间的泥炭在160℃热处理5 h,在pH为7的条件下对甲苯有良好的吸附效果,对甲苯的吸附量为0.32 mg/g。泥炭对甲苯的吸附在20 min内基本达到平衡,可用二级吸附速率方程进行拟合。甲苯在泥炭上的吸附和解吸均呈现明显的非线性,用Langmuir模型能较好地描述,泥炭对甲苯的饱和吸附量为0.939 mg/g。甲苯在泥炭上的平均解吸率为6.393%,并且出现了滞后现象,表明苯系物与泥炭有较强的结合能力。研究结果为应用泥炭作为PRB装填介质进行原位修复甲苯污染的地下水提供了理论依据。     

用于氨氮去除的13X分子筛／PES膜吸附剂的制备与性能表征

针对氨氮排放对环境造成的污染以及给人类带来的危害这一问题，将分子筛吸附与膜技术相结合，以13x分子筛为功能颗粒，以聚醚砜（PES）为膜的基质材料，以二甲基乙酰胺（DMAc）为溶剂，通过相转化法制备了不同13x分子筛填充量的13x／PEs膜吸附剂。研究发现，随着13x分子筛填充量的增加，膜的指状孔变得细密、短小，其吸附容量，断裂强度都在增加，但是水通量逐渐降低。料液温度与pH值对吸附性能的影响表明，该膜吸附剂在293K，pH=7时对氨氮有较好的吸附容量，可达21．69mg／g；吸附热力学研究表明，该类型膜吸附剂对氨氮的吸附等温线符合Langmuir方程。     

纳米聚硅酸铝锌絮凝剂的制备及表征简

在SiO₂含量为3%，pH为3，活化时间为85 min，（Al+Zn ）/Si摩尔比为1.5，Al/Zn摩尔比为2，表面活性剂硬脂酸钠加入量为0.1%，超声频率为40 Hz，超声时间为60 min的最佳制备条件下制备出液体PSAZS絮凝剂，用超声法制成纳米级Nano-PSAZS，用环境扫描电子显微镜（ESEM）和智能型傅里叶变换红外光谱（FT-IR）等仪器进行分析。结果表明，硅有助于絮凝剂分子链的延伸，有助于生成更大分子的聚合物；铝盐和锌盐的加入到聚硅酸中，并不是简单的混合，而是发生了缩聚和配位反应，有助于生成链网状结构，能更好地发挥吸附架桥和网捕卷扫作用。同时Nano-PSAZS陈化时间为24 h时的结构有利于絮凝效果的发挥。     

Adsorption and photodegradation of microcystin-LR onto sediments collected from reservoirs and rivers in Taiwan: a laboratory study to investigate the fate, transfer, and degradation of microcystin-LR

Background, aim, and scope

This study demonstrated the adsorption capacity of microcystin-LR (MC-LR) onto sediment samples collected from different reservoirs (Emerald and Jade reservoirs) and rivers (Dongshan, Erhjen, and Wukai rivers) in Taiwan to investigate the fate, transport behavior, and photodegradation of MC-LR.

Main features

Langmuir adsorption and photodegradation studies were carried out in the laboratory and tested the capability of sediments for MC-LR adsorption. These data suggested that sediments play a crucial role in microcystins degradation in aquatic systems.

Results and discussion

The results of batch experiments revealed that the adsorption of MC-LR varied significantly with texture, pH, and organic matter content of sediments. Silty and clay textures of the samples were associated with larger content of organic matter, and they displayed the enhanced MC-LR adsorption. Low pH sediment showed increased adsorption of MC-LR. The effective photodegradation of MC-LR (1.6 ??g/mL) was achieved within 60 min under 254 nm light irradiation.

Conclusion

A comparative study of adsorption capacity of all sediment samples was carried out and discussed with respect to different aspects. Among all, sediments collected from Jade reservoir showed enhanced MC-LR adsorption (11.86 ??g/g) due to favored textural properties (BET surface area = 20.24 m2/g and pore volume = 80.70 nm).

Perspectives

These data provide important information that may be applied to management strategies for improvement of water quality in reservoirs and rivers and other water bodies in Taiwan.     

离子液体负载型分子筛的制备及对染料的吸附

为了有效地处理活性黑染料废水,对离子液体负载型分子筛去除水中的活性黑染料进行了研究。首先制备了离子液体负载型吸附材料,分别考察了分散剂种类、离子液体加入量、浸渍时间3种因素对离子液体负载率的影响,确定负载工艺条件为:二氯甲烷作为分散剂、[OMim]BF4离子液体与分子筛质量比1∶2,浸渍时间12 h。其次研究了负载型吸附材料对染料废水的处理效果,考察了吸附材料添加量、溶液pH值、吸附时间对模拟废水活性黑染料去除率的影响,确定吸附工艺条件为:[OMim]BF4离子液体为最佳离子液体、吸附材料添加量0.40 g、pH=6、吸附时间12 h。在此最佳工艺条件下,染料去除率达98.23%。     

镉溶液污染黏土微观结构演化规律

镉溶液在压实黏土中迁移会引起黏土微观结构的变化。通过一系列扫描电子显微镜与低温氮吸附实验,观察了镉溶液污染黏土的表面微观形貌与孔隙结构的演化规律。扫描电子显微镜观察结果显示,受镉溶液污染严重的土柱上表面孔隙明显,土颗粒之间主要以点-点排列方式为主;而受镉溶液污染较弱的下表面,土颗粒之间主要以片-片状排列为主。低温氮吸附实验结果表明,Z=0 cm、Z=10 cm、Z=20 cm、Z=30 cm处,污染黏土吸附量分别为682.65、631.72、583.25和523.36 cm3/g。随土柱中土层深度的增大,黏土颗粒间微孔增多,二次孔减少,孔隙体积与比表面积减小。镉溶液污染黏土孔隙主要集中在10 nm以下。     

微波活化制备加拿大一枝黄花活性炭及对Cd（Ⅱ）的吸附

以入侵植物加拿大一枝黄花为原料,在400℃氮气保护下,直接碳化90 min后,以KOH为活化剂,微波活化的方法制备了高比表面积微孔活性炭SCAC。结果显示活性炭SCAC的表面面积为1 888 m2/g,总孔容量为0.804 cm3/g,微孔容量为0.741 cm3/g,平均孔径0.567 nm,微孔平均孔径0.488 nm。通过静态吸附实验研究了活性炭添加量、溶液初始浓度、初始pH及吸附时间对SCAC吸附Cd(Ⅱ)的影响,通过动力学方程拟合探讨了活性炭对Cd(Ⅱ)的吸附机理。结果表明,吸附平衡时间、最佳pH及活性炭添加量分别为120 min、pH>7.5及0.05 g/50 mL,活性炭SCAC吸附动力学过程符合准二级方程模型。