Applying Hexagonal Nanostructured Zeolite Particles for Acetone Removal

Abstract

This study examines the performance of a new adsorbent, hexagonal nanostructured zeolite particles (HNZP) for acetone adsorption and compares the results with that of commercial mobil synthetic zeolite-5 (ZSM-5) type zeolite. The HNZP is a pure siliceous adsorbent with different values of pore diameter and surface area being adjustable by the manufacturing condition. The results indicate that a slight increase in the average pore diameter (d) of HNZP from 2 to 2.5 nm leads to an increase in the acetone adsorption capacity, although its surface area is decreased, in which case (d = 2.5 nm) the adsorption capacity of fresh HNZP is better than that of ZSM-5 zeolite. Even for the fresh HNZP (d = 2 nm) of which the adsorption capacity is less than that of the ZSM-5 zeolite at relative humidity (RH) of 0%, its adsorption capacity is not deteriorated after repeated regeneration, but the adsorption capacity of regenerated ZSM-5 zeolite decays markedly. Thus, after only one regeneration, the adsorption capacity of HNZP (d = 2 nm) becomes better than that of the ZSM-5 zeolite. The decrease in the adsorption capacity of regenerated ZSM-5 zeolite might be because of its aluminum content that catalyzes the acetone into coke and, thus, blocks the adsorption sites. Furthermore, result on the moisture effect shows that because the pure siliceous HNZP was more hydrophobic than the ZSM-5 zeolite, the acetone adsorption efficiency of fresh HNZP (d = 2 nm) is better than that of ZSM-5 zeolite at RH = 50%.     

Physical and chemical regeneration of zeolitic adsorbents for dye removal in wastewater treatment

Natural zeolite and synthetic zeolite, MCM-22, were employed as effective adsorbents for a basic dye, methylene blue, removal from wastewater. Two methods, Fenton oxidation and high temperature combustion, have been used for regeneration of used materials. It is found that MCM-22 exhibits equilibrium adsorption at 1.7 x 10(-4) mol g(-1), much higher than the adsorption of natural zeolite (5 x 10(-5) mol g(-1)) at initial dye concentration of 2.7 x 10(-5)M and 30 degrees C. Solution pH will affect the adsorption behaviour of MCM-22. Higher solution pH results in higher adsorption capacity. The regenerated adsorbents show different capacity depending on regeneration technique. Physical regeneration by high temperature combustion will be better than chemical regeneration using Fenton oxidation in producing effective adsorbents. Regeneration of MCM-22 by high temperature treatment can make the adsorbent exhibit comparable or superior adsorption capacity as compared to the fresh sample depending on the temperature and time. The optimal temperature and time will be 540 degrees C and 1h. The Fenton oxidation will recover 60% adsorption capacity. For natural zeolite, regeneration can not fully recover the adsorption capacity with the two techniques and the regenerated natural zeolites by the two techniques are similar, showing 60% adsorption capacity of fresh sample. Kinetic studies indicate that the adsorption follows pseudo-second-order kinetics.     

Adsorption of nitrosamines in acidic solution by zeolites

Adsorption of N-nitrosopyrrolidine (NPYR) by zeolite NaZSM-5, Hbeta and NaZSM-11 in acidic solution with pH of 1 was investigated. The NPYR uptake process obeyed the first-rate Lagegren kinetic equation describing adsorption, and the equilibrium data were fitted to the Langmuir or Freundlich adsorption equation. Zeolite ZSM-5, Hbeta and NaZSM-11 possessed a higher adsorption capacity than amorphous silica or ordered mesoporous siliceous SBA-15, implying their potential application for adsorption of nitrosamines in gastric juice to anti-cancer.     

Attempt to adsorb N-nitrosamines in solution by use of zeolites

The strong adsorption of zeolite for N-nitrosamines in solution was first revealed by use of adsorption, and temperature programmed surface reaction (TPSR) techniques. N-nitrosodimethylamine (NDMA) and N-nitrosopyrrolidine (NPYR) as well as N-nitrosohexamethyleneimine (NHMI) can be adsorbed on zeolite Y, ZSM-5 and A in the solution of methylene chloride or water, which will be helpful for removal of the N-nitrosamines pollution in environmental protection. The equilibrium data were fitted to Freundlich-type isotherms, but the adsorption capacity of zeolites mainly depended on their pore size, surface area and acid-basic properties. Molecular size of adsorbate and solute-solvent interaction also strongly affected the adsorption of N-nitrosamines on zeolite in solution. The extraordinary adsorption properties of NaA zeolite for N-nitrosamines in aqueous solution is first reported and discussed.     

活性炭和沸石对氨氮的吸附特性及生物再生

采用活性炭和沸石作为吸附材料,分别考察了这两种吸附材料对水体中氨氮的吸附特性及其生物再生性能。实验结果表明,活性炭和沸石对水体中氨氮的等温吸附符合Freundlich等温式,其拟合度分别为0.9783和0.9303;静态吸附结果表明活性炭和沸石均具有较好的氨氮吸附性能,24 h内沸石对氨氮的吸附能力为1.27 mg/g,高于活性炭的0.53 mg/g;动态吸附中沸石达到吸附饱和的时间为96 h,较活性炭达到吸附饱和的时间长,沸石显示出作为氨氮吸附剂的优越性;活性炭和沸石经过96 h的生物再生后吸附性能获得一定程度的再生,出水中氨氮浓度比未进行生物再生前分别降低17.31 mg/L和8.32 mg/L,且都在表面形成了稳定的生物膜。     

溴化十六烷基吡啶改性沸石对水中甲基橙的吸附

采用溴化十六烷基吡啶(CPB)对天然沸石进行改性制备得到了CPB改性沸石,通过批量吸附实验考察了CPB改性沸石对水中阴离子染料甲基橙的去除作用。结果表明,天然沸石对水中甲基橙的吸附能力很差,而CPB改性沸石则可以有效吸附去除水中的甲基橙。CPB改性沸石对水中甲基橙的吸附能力随CPB负载量的增加而增加,CPB负载量最大的改性沸石对水中甲基橙的吸附能力最强。双分子层CPB改性沸石对水中甲基橙的去除率随吸附剂投加量的增加而增加,而CPB改性沸石对水中甲基橙的单位吸附量则随吸附剂投加量的增加而降低。双分子层CPB改性沸石对水中甲基橙的吸附平衡数据可以采用Langmuir等温吸附模型加以描述。根据Langmuir模型计算得到的CPB负载量为341 mmol/(kg沸石)的双分子层CPB改性沸石对水中甲基橙的最大吸附容量为63.7 mg/g(303 K和pH 7)。准二级动力学模型适合用于描述双分子层CPB改性沸石对水中甲基橙的吸附动力学过程。pH和反应温度对双分子层CPB改性沸石吸附水中甲基橙的影响较小。以上结果说明,双分子层CPB改性沸石适合作为一种吸附剂用于去除废水中的甲基橙。     

顶空气相色谱测试水中苯系混合物在不同材料上的吸附行为

设计了正交实验对5种材料吸附模拟废水中苯系混合物(苯、甲苯、二甲苯)的条件进行优化,CD02硅藻土与X型纳米分子筛以2∶1(质量比)进行复合后,对苯系混合物去除效果最好.采用顶空气相色谱法测定8种不同材料对水中苯系混合物的去除情况,结果表明复合材料对苯系混合物具有良好的去除效果,仅次于活性炭.复合材料在pH为7、搅拌时间为25 min、用量为1.8g/L时,对苯系混合物质量浓度为4.0 mg/L模拟废水的平均去除率为87.56％.经过4次再生后,复合材料的再生率仍高达84.90％,对苯系混合物的平均去除率为91.49％.     

Microwave regeneration of activated carbon used for removal of solvents from vented air

A microwave regeneration of activated carbon used to remove organic solvents from vented air has been investigated. Methyl ethyl ketone (MEK), acetone, and tetrachloroethylene (TCE) vapors were removed from vented air through adsorption onto granular activated carbon. The saturated carbon was then regenerated in a microwave field, where the solvent was quickly desorbed and recovered from the inner pores of the carbon granules. The microwave-induced regeneration restored the original adsorption capacity and surface area of the activated carbon.     

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.

     

高比表面积活性炭的制备及对Cr(Ⅵ)吸附的研究

以椰树壳为原料,运用水蒸汽和二氧化碳复合物理活化法在4 h内制备了2 162.84 m2/g的高比表面积活性炭,其孔径分布范围为1.1~2.5 nm。应用此吸附剂考察了溶液pH、吸附剂用量、接触时间和初始浓度对Cr(VI)离子吸附效果的影响,并讨论了固定吸附床中不同溶液流量对Cr(VI)去除效果的影响。结果表明:在温度为298 K、溶液pH为1.96、吸附剂用量为0.10 g、铬离子初始浓度为100 mg/L与接触时间为70 min的条件下,活性炭对铬离子具有较高的吸附容量,去除率高达99.32%;铬离子在吸附床中的穿透曲线具有陡峭的传质锋面,但随着铬离子溶液流量的增大脱除果率降低。     

Removal and Destruction of Organic Contaminants in Water Using Adsorption,Steam Regeneration,and Photocatalytic Oxidation: A Pilot-Scale Study

ABSTRACT

The overall objective of this pilot-scale study is to investigate the technical feasibility of the removal and destruction of organic contaminants in water using adsorption and photocatalytic oxidation. The process consists of two consecutive operational steps: (1) removal of organic contaminants using fixed-bed adsorption; and (2) regeneration of spent adsorbent using photocatalysis or steam, followed by decontamination of steam condensate using photocatalysis. The pilot-scale study was conducted to evaluate these options at a water treatment plant in Wausau (Wisconsin) for treatment of groundwater contaminated with tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), toluene, ethylbenzene (EB), and xylenes. The adsorbents used were F-400 GAC and Ambersorb 563.

In the first treatment strategy, the adsorbents were impregnated with photocatalyst and used for the removal of aqueous organics. The spent adsorbents were then exposed to ultraviolet light to achieve photocatalytic regeneration. Regeneration of adsorbents using photocatalysis was observed to be not effective, probably because the impregnated photocatalyst was fouled by background organic matter present in the groundwater matrix.

In the second treatment strategy, the spent adsorbents were regenerated using steam, followed by cleanup of steam condensate using photocatalysis. Four cycles of adsorption and three cycles of steam regeneration were performed. Ambersorb 563 adsorbent was successfully regenerated using saturated steam at 160 °C within 20 hours. The steam condensate was treated using fixed-bed photo-catalysis using 1% Pt-TiO₂ photocatalyst supported on silica gel. After 35 minutes of empty bed contact time, more than 95% removal of TCE, cis-DCE, toluene, EB, and xylenes was achieved, and more than 75% removal of PCE was observed.

In the case of activated carbon adsorbent, steam regeneration was not effective, and a significant loss in adsorbent capacity was observed.     

Microwave Regeneration of Activated Carbon Used for Removal of Solvents from Vented Air

ABSTRACT

A microwave regeneration of activated carbon used to remove organic solvents from vented air has been investigated. Methyl ethyl ketone (MEK), acetone, and tetrachloroethylene (TCE) vapors were removed from vented air through adsorption onto granular activated carbon. The saturated carbon was then regenerated in a microwave field, where the solvent was quickly desorbed and recovered from the inner pores of the carbon granules. The microwave-induced regeneration restored the original adsorption capacity and surface area of the activated carbon.     

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。     

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.

     

Removal of acutely hazardous pharmaceuticals from water using multi-template imprinted polymer adsorbent

Molecularly imprinted polymer adsorbent has been prepared to remove a group of recalcitrant and acutely hazardous (p-type) chemicals from water and wastewaters. The polymer adsorbent exhibited twofold higher adsorption capacity than the commercially used polystyrene divinylbenzene resin (XAD) and powdered activated carbon adsorbents. Higher adsorption capacity of the polymer adsorbent was explained on the basis of high specific surface area formed during molecular imprinting process. Freundlich isotherms drawn showed that the adsorption of p-type chemicals onto polymer adsorbent was kinetically faster than the other reference adsorbents. Matrix effect on adsorption of p-type chemicals was minimal, and also polymer adsorbent was amenable to regeneration by washing with water/methanol (3:1, v/v) solution. The polymer adsorbent was unaltered in its adsorption capacity up to 10 cycles of adsorption and desorption, which will be more desirable in cost reduction of treatment compared with single-time-use activated carbon.     

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。     

Simultaneous removal of potent cyanotoxins from water using magnetophoretic nanoparticle of polypyrrole: adsorption kinetic and isotherm study

Cyanotoxins, microcystins and cylindrospermopsin, are potent toxins produced by cyanobacteria in potable water supplies. This study investigated the removal of cyanotoxins from aqueous media by magnetophoretic nanoparticle of polypyrrole adsorbent. The adsorption process was pH dependent with maximum adsorption occurring at pH 7 for microcystin-LA, LR, and YR and at pH 9 for microcystin-RR and cylindrospermopsin (CYN). Kinetic studies and adsorption isotherms reflected better fit for pseudo-second-order rate and Langmuir isotherm model, respectively. Thermodynamic calculations showed that the cyanotoxin adsorption process is endothermic and spontaneous in nature. The regenerated adsorbent can be successfully reused without appreciable loss of its original capacity.     

Preparation and characterization of surfactant-modified hydroxyapatite/zeolite composite and its adsorption behavior toward humic acid and copper(II)

A novel composite material, i.e., surfactant-modified hydroxyapatite/zeolite composite, was used as an adsorbent to remove humic acid (HA) and copper(II) from aqueous solution. Hydroxyapatite/zeolite composite (HZC) and surfactant-modified HZC (SMHZC) were prepared and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and field emission scanning electron microscope. The adsorption of HA and copper(II) on SMHZC was investigated. For comparison purposes, HA adsorption onto HZC was also investigated. SMHZC exhibited much higher HA adsorption capacity than HZC. The HA adsorption capacity for SMHZC decreased slightly with increasing pH from 3 to 8 but decreased significantly with increasing pH from 8 to 12. The copper(II) adsorption capacity for SMHZC increased with increasing pH from 3 to 6.5. The adsorption kinetic data of HA and copper(II) on SMHZC obeyed a pseudo-second-order kinetic model. The adsorption of HA and copper(II) on SMHZC took place in three different stages: fast external surface adsorption, gradual adsorption controlled by both film and intra-particle diffusions, and final equilibrium stage. The equilibrium adsorption data of HA on SMHZC better fitted to the Langmuir isotherm model than the Freundlich isotherm model. The equilibrium adsorption data of copper(II) on SMHZC could be described by the Langmuir, Freundlich, and Dubinin–Radushkevich isotherm models. The presence of copper(II) in solution enhanced HA adsorption onto SMHZC. The presence of HA in solution enhanced copper(II) adsorption onto SMHZC. The mechanisms for the adsorption of HA on SMHZC at pH 7 may include electrostatic attraction, organic partitioning, hydrogen bonding, and Lewis acid–base interaction. The mechanisms for the adsorption of copper(II) on SMHZC at pH 6 may include surface complexation, ion exchange, and dissolution–precipitation. The obtained results indicate that SMHZC can be used as an effective adsorbent to simultaneously remove HA and copper(II) from water.     

The removal of hydrogen sulfide in solution by ferric and alum water treatment residuals

This work investigated the characteristics and mechanisms of hydrogen sulfide adsorption by ferric and alum water treatment residuals (FARs) in solution. The results indicated that FARs had a high hydrogen sulfide adsorption capacity. pH 7 rather than higher pH (e.g. pH 8-10) was favorable for hydrogen sulfide removal. The Yan model fitted the breakthrough curves better than the Thomas model under varied pH values and concentrations. The Brunauer-Emmett-Teller surface area and the total pore volume of the FARs decreased after the adsorption of hydrogen sulfide. In particular, the volume of pores with a radius of 3-5 nm decreased, while the volume of pores with a radius of 2 nm increased. Therefore, it was inferred that new adsorption sites were generated during the adsorption process. The pH of the FARs increased greatly after adsorption. Moreover, differential scanning calorimetry analysis indicated that elemental sulfur was present in the FARs, while the derivative thermal gravimetry curves indicated the presence of sulfuric acid and sulfurous acid. These results indicated that both oxidization and ligand exchange contribute to the removal of hydrogen sulfide by FARs. Under anaerobic conditions, the maximum amount of hydrogen sulfide released was approximately 0.026 mg g(-1), which was less than 0.19% of the total amount adsorbed by the FARs. The hydrogen sulfide that was released may be re-adsorbed by the FARs and transformed into more stable mineral forms. Therefore, FARs are an excellent adsorbent for hydrogen sulfide.     

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.