Adsorption of lignite-derived humic acids on coal-based mesoporous activated carbons

The adsorption by a coal-based mesoporous activated carbon of humic acids (HAs) isolated from two Polish lignites was studied. For comparison, a commercial Aldrich humic acid was also included into this study. The differences in chemical structure and functional groups of HAs were determined by elemental analysis and infrared spectroscopy DRIFT. Two activated carbons used differed in terms of mesopore volume, mesopore size distribution, and chemical properties of the surface. The kinetics of adsorption of HAs have been discussed using three kinetic models, i.e., the first-order Lagergren model, the pseudo-second-order model, and the intraparticle diffusion model. It was found that the adsorption of HAs from alkaline solution on mesoporous activated carbon proceeds according to the pseudo-second-order model. The correlation coefficients were close to 1. The intraparticle diffusion of HA molecules within the carbon particle was identified to be the rate-limiting step. Comparing the two activated carbons, the carbon with a higher volume of pores with widths of 10-50 nm showed a greater removal efficiency of HA. An increase in the Freundlich adsorption capacity with decreasing carbon content of HA was observed. Among the HAs studied, S-HA shows characteristics indicating the highest contribution of small-size fraction. The S-HA was removed by both activated carbons to the highest extent. The effect of pH solution on the adsorption of HA was examined over the range pH 5.4-12.2. It was found that the extent of adsorption decreased with decreasing pH of the solution.     

Effects of activation conditions on the structural and adsorption characteristics of pinecones derived activated carbons

This study was conducted to understand and optimize the activation process for the production of a low-cost activated carbon (AC) using a renewable and plentiful biomass waste, pinecones. This was achieved by tracking the changes in porous structure, surface chemistry and adsorption properties of the AC produced using different activating agents, activation temperatures, holding times and heating rates. Generally, produced ACs were predominantly microporous with small external surface area and were different in terms of H/C and O/C ratios. Study of Pb²⁺ cations adsorption on these samples proved the high affinity of the pinecones derived ACs to this cation. The best adsorption behaviour was recognized in sample prepared by impregnation with H₃PO₄ at weight ratio of 2, then heating at 400?°C for 2?h at 5?°C/min heating rate. This sample possessed the highest BET surface area (1335 m²/g). The adsorption process obeyed the pseudo-first-order and Freundlich model slightly better than the pseudo-second-order kinetics and Langmuir model. The high Langmuir maximum adsorption capacity of 418?mg/g supports the applicability of the produced AC for the removal of Pb²⁺ cations from wastewater.     

Hydrothermal modification of carbon adsorbents

The effects of high-pressure autoclave treatments on porous structure and surface properties were studied for a variety of activated carbons (AC, synthetic and produced from plum stones) treated with water vapour, hydrogen peroxide (10–50%) or 10% aqueous ammonia solution at relatively low temperatures (250, 350, 400^○C). Surface and structural parameters of modified ACs were determined using nitrogen, water, ammonia and benzene adsorption isotherms. It was found that the effects of AC modification resulting in changes in their porous structure and surface chemistry depend on the kind of initial ACs, modifier type and concentration of modifier and treatment temperature. At the same conditions synthetic ACs are modified to a larger extent than ACs prepared using natural raw materials. Repeated treatment of a given carbon intensifies changes in its porous structure.     

活性炭的改性研究及对四环素的吸附

研究了改性对活性炭的物理化学性质及其对四环素吸附性能的影响。结果发现,硝酸氧化改性可增加活性炭表面的酸性基团,提高比表面亲水性,降低pHPZC值,同时也改变了活性炭的表面微观形貌。低温、低浓度硝酸氧化改性,增加了活性炭的比表面积,对四环素的吸附以物理吸附为主。高温氧化改性使得比表面积降低,酸性基团增加,且吸附容量与活性炭比表面积、表面总酸度呈一定的线性关系。     

Humic acid fractionation upon sequential adsorption onto goethite

Mineral-humic complexes are commonly distributed in natural environments and are important in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study investigated the structural and conformational changes of humic acid (HA) and mineral-HA complexes after sequential HA adsorption by goethite, using UV-visible spectroscopy, high performance size exclusion chromatography (HPSEC), Fourier transform infrared (FT-IR) spectroscopy, and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The HA remaining in the solution after adsorption showed low polarity index values ((N+O)/C), which indicates that polar functional moieties are likely to adsorb on the goethite surface. In addition, we observed decreased E4/E6 and E2/E3 ratios of unbound HA with increasing number of coatings, implying that aliphatic rich HA fractions with polar functional moieties readily adsorb to the goethite surface. According to IR spectra, carbohydrate carbon would be the important fractions associated with goethite. NMR spectra provided evidence for HA fractionation during adsorption onto the mineral surface; that is, aliphatic fractions were preferentially adsorbed by goethite while aromatic fractions were left in solution. Relatively small molecular weight (MW) HA fractions had a greater affinity for the goethite surface based on analyses of the HPSEC chromatograms, which differs from the results reported in the literature. Finally, our results suggest that the polar aliphatic fractions of HA were mainly adsorbed to goethite via electrostatic attraction and/or ligand exchange reactions.     

Simultaneous adsorption of copper ions and humic acid onto an activated carbon

In this study, simultaneous adsorption of copper ions and humic acid (HA) from Aldrich onto an activated carbon is investigated. It is found that the HA adsorption in the absence of copper decreases as the pH is increased. It leads to a reduction of 34.7% in the specific surface area of carbon. There exists a critical concentration (CC) of HA for copper adsorption. At HA concentrations < CC, a decrease in copper adsorption is observed; however, the HA improves the adsorption at HA concentrations > CC. An increase in ionic strength can enhance the copper uptake; however, zinc and/or cobalt ions have an insignificant influence on copper adsorption. The adsorption is significantly increased by citric acid, whereas addition of EDTA slightly decreases the uptake. An intraparticle diffusion model is successfully used to describe the copper adsorption kinetics.     

Effect of ozone treatment on ammonia removal of activated carbons

In this work, activated carbons (ACs) were modified by ozone treatment to enhance the efficiency of removal of ammonia gas over the ACs. Surface properties of the ACs were confirmed by X-ray photoelectron spectroscopy (XPS) analysis and N2 adsorption isotherms at 77 K were investigated by BET and D-A methods to characterize the specific surface area, total pore volume, and micropore volume. The ammonia removal efficiency was confirmed by the gas-detecting tube technique. The results showed that the specific surface area and micropore volume of ACs were slightly destroyed as the ozone treatment time increased. However, the ozone treatment led to an increase in ammonia removal efficiency of ACs, mainly due to an increase of acid functional groups, such as carbonyl and ether groups, on carbon surfaces. It was revealed that the improvement of ammonia removal efficiency of ACs was greatly affected by the interfacial acid-base interactions between modified ACs and basic ammonia adsorbate.     

Comparative study on composition, structure, and adsorption behavior of activated carbons derived from different synthetic waste polymers

The composition, structure, and adsorption behavior of activated carbons (ACs) derived from three different types of waste polymers, i.e., tire rubber (TR), polyvinyl chloride (PVC), and polyethyleneterephtalate (PET), by KOH activation were compared. The AC derived from PET exhibited the largest surface area (2831 m(2)/g) and pore volume (1.68 cm(3)/g) due to the homogenous aromatic composition of PET. The AC derived from PVC exhibited relatively lower surface area (2666 m(2)/g) but more narrowed pore size distribution (2-3 nm). The complex composition and high ash content of tire particles resulted in AC product with significantly lower surface area (398.5 m(2)/g) and heterogeneous pore width. Adsorption data of methylene blue (MB) were fitted well by Langmuir equation, indicating monolayer coverage on the ACs. The high oxygen content of PET-derived AC heavily affected its adsorption to MB and iodine. Due to the remarkable surface area and highly mesoporous structures, ACs based on both PET and PVC exhibited much higher adsorption capacities than that of TR and commercial coal-based AC (F400). This study demonstrates that the properties of ACs are highly dependent on their starting polymers and the potential of converting synthetic polymer waste into effective adsorbents for environmental remediation and cleanup.     

Association of humic acid with metal (hydr)oxide-coated sands at solid-water interfaces

Mineral-bound humic acid (HA) can significantly modify the physicochemical properties of the mineral surfaces and vice versa, thereby influencing the fate and transport of organic pollutants in the subsurface. The effect of various mineral surfaces on the adsorption-desorption of dissolved bulk, terrestrial HA was evaluated using three model sorbents [uncoated, alpha-FeO(OH)-coated, and Al2O3-coated sands] at two equilibrium pH values. The results of SEM/EDS and XPS analyses revealed relatively uniform and stable metal (hydr)oxide coatings on quartz surface and the presence of the HA coating. Strong hysteresis effects were observed for both metal (hydr)oxide-coated sands whereas a weaker hysteresis effect was observed for uncoated sand, suggesting that the adsorption-desorption of HA to model sorbents is dependent on the affinity of chemical interactions between the HA and surface composition of model sorbents. Adsorption of HA molecules onto metal (hydr)oxide-coated sands can be attributed to ligand exchange for lower molecular weight (MW) HA fractions and hydrophobic interaction for higher MW HA fractions, illustrating that both kinetic and fractional adsorption-desorption of HA subcomponents are important considerations.     

Competitive adsorption of organic matter with phosphate on aluminum hydroxide

The effects of orthophosphate on the adsorption of natural organic matter (NOM) on aluminum hydroxide were investigated using three organic compounds as surrogates, including humic acid (HA), phthalic acid, and 2,3-dihydroxybenzoic acid (2,3-DHBA). The adsorption of phthalic acid and 2,3-DHBA was very limited compared to that of HA, whereas their adsorption was reduced much more significantly than that of HA by phosphate. The efficiency of phosphate in reducing HA adsorption increased with increasing phosphate concentration. Phosphate adsorption was slightly reduced by phthalic acid and 2,3-DHBA but moderately suppressed by HA. The adjacent carboxylic groups mainly contributed to the adsorption of humic acid at low pH, while the adjacent phenol groups were responsible for the adsorption of humic acid at high pH. HPLC-SEC and SUVA analysis revealed that HA molecules with high molecular weight were adsorbed preferentially but were easily displaced by the specifically adsorbed phosphate. TM-AFM images revealed that the aggregation of HA molecules and the protonation of carboxylic groups at low pH facilitated the adsorption under acidic conditions. The presence of phosphate increases the coagulant dosage for NOM removal as some sites on the coagulant precipitates become utilized by phosphate.     

Adsorption of humic acids onto goethite: effects of molar mass, pH and ionic strength

In this paper, the LCD (ligand charge distribution) model is applied to describe the adsorption of (Tongbersven) humic acid (HA) to goethite. The model considers both electrostatic interactions and chemical binding between HA and goethite. The large size of HA particles limits their close access to the surface. Part of the adsorbed HA particles is located in the compact part at the goethite surface (Stern layers) and the rest in the less structured diffuse double layer (DDL). The model can describe the effects of pH, ionic strength, and loading on the adsorption. Compared to fulvic acid (FA), adsorption of HA is stronger and more pH- and ionic-strength-dependent. The larger number of reactive groups on each HA particle than on a FA particle results in the stronger HA adsorption observed. The stronger pH dependency in HA adsorption is related to the larger number of protons that are coadsorbed with HA due to the higher charge carried by a HA particle than by a FA particle. The positive ionic-strength dependency of HA adsorption can be explained by the conformational change of HA particles with ionic strength. At a higher ionic strength, the decrease of the particle size favors closer contact between the particles and the surface, leading to stronger competition with electrolyte ions for surface charge neutralization and therefore leading to more HA adsorption.     

铁酸锰/腐植酸复合材料制备及其对亚甲基蓝吸附性能

采用化学共沉淀法合成了一种腐植酸(Humic Acid,HA)包覆铁酸锰型磁性复合材料(MnFe₂O₄/HA)。采用扫描电子显微镜(SEM)、粉末X射线衍射(XRD)和傅里叶变换红外光谱(FT-IR)等技术手段对其进行表征和分析表明,合成产物颗粒大小约200 nm,具有典型的尖晶石结构,腐植酸成功包覆在MnFe₂O₄颗粒表面,饱和磁化强度为34.01 A·m²/kg,在外界低磁场作用下30 s内便可从水溶液分离。 MnFe₂O₄/HA对亚甲基蓝的吸附是一个准二级动力学过程,在2 h达到平衡,较好的符合Langmuir吸附模型。 与MnFe₂O₄相比其对亚甲基蓝的吸附能力显著增强,室温下pH=9时最大吸附量可以达到29.94 mg/g。 MnFe₂O₄/HA可以作为一种有效去除水体中亚甲基蓝污染物的吸附材料。     

Experimental and Theoretical Study of the Effect of Moisture on Methane Adsorption and Desorption by Activated Carbon at 273.5 K

Adsorption and desorption of methane by activated carbon (AC) at constant temperature and at various pressures were investigated. The effect of moisture was also studied. A volumetric method was used, up to 40 bar, at a temperature of 273.5 K. Results of a dry AC sample were compared with those obtained from a moist sample and two different ACs with different physical and surface properties were used. As expected, the results showed that the existence of moisture, trapped in the AC pores, could lead to a decrease in the amount of methane adsorbed and a decrease in the amount of methane delivered during desorption. To model the experimental results, a large variety of adsorption isotherms were used. The regressed parameters for the adsorption isotherms were obtained using the experimental data generated in the present study. The accuracy of the results obtained from the different adsorption isotherms was favorably compared.     

活性炭孔径和比表面积对TiO2/AC光催化性能的影响

采用“同步物理-化学活化法”二次活化商品活性炭, 制备不同孔径和比表面积的系列活性炭(AC)载体, 以偏钛酸为钛源, 利用均匀沉淀法制备TiO2负载型光催化剂(TiO2/AC), 用氮吸附、XRD、SEM等方法表征, 研究活性炭的孔径和比表面积对TiO2/AC性能的影响; 并通过降解水溶液中的亚甲基蓝(MB)研究TiO2/AC光催化氧化特性, 考察催化剂投加量、不同MB浓度等因素对光催化氧化的影响. 结果表明, 负载的TiO2粒子粒径为12-20 nm, 活性炭的比表面积大、平均孔径大有利于TiO2的均匀分散, 阻止TiO2晶粒生长, 有利于充分发挥TiO2小尺度效应; 另外, 活性炭吸附和TiO2光解的协同效应使TiO2/AC光催化剂对MB降解的效率显著提高. 动力学研究表明, TiO2/AC光催化降解MB反应符合表观一级动力学特征.     

Impact factors and thermodynamic characteristics of aquatic humic acid loaded onto kaolin

The adsorption of humic acid (HA) on kaolin particles was studied at various conditions of initial solution pH, ionic strength and solid-to-liquid ratio. The resulting affinity of interactions between humic acid and kaolin was attributed to the surface coordination of HA in ambient suspensions of mineral particles and the strong electrostatic force at low pH. Addition of inorganic salt can also influence the adsorption behavior by affecting the HA molecular structure, the clay particle zeta potential and so on. Equilibrium data were well fitted by the Freundlich model and implied the occurrence of multilayer adsorption in the process. In addition, the enthalpy dependent of system temperature was 79.17 kJ/mol, which proved that the mechanism of HA adsorption onto kaolin was comprehensive, including electrostatic attraction, ligand complexation and hydrogen bonding.     

Pore structure and surface properties of chemically modified activated carbons for adsorption mechanism and rate of Cr(VI)

Effects of hydrochloric acid and sodium hydroxide treatments of activated carbons (ACs) on chromium(VI) reduction were studied. The surface properties were determined by pH, acid-base values, FT-IR, and X-ray photoelectron spectrometer (XPS). And the porous structure of the activated carbons was characterized by adsorption of N(2)/77 K. The Cr(VI) adsorption experiments were carried out to analyze the influence of porous texture and surface properties changed by the chemical surface treatments of ACs on adsorption rate with carbon-solution contact time. From the experimental results, it was observed that the extent of adsorption and reduction processes depends on both microporous structure and functional groups. And the adsorption of Cr(VI) ion was more effective in the case of acidic treatment on activated carbons, resulting from the increases of acid value (or acidic functional group) of activated carbon surfaces. However, basic treatment on activated carbons was not significantly effective on the adsorption of Cr(VI) ion, probably due to the effects of the decrease of specific surface area and basic Cr(VI) in nature.     

Critical evaluation and comparison of enrichment efficiency of multi-walled carbon nanotubes, C18 silica and activated carbon towards some pesticides from environmental waters

In this work, optimization of multi-residue solid phase extraction (SPE) procedures coupled with high-performance liquid chromatography for the determination of Propoxur, Atrazine and Methidathion from environmental waters is reported. Three different sorbents were used in this work: multi-walled carbon nanotubes (MWCNTs), C18 silica and activated carbon (AC). The three optimized SPE procedures were compared in terms of analytical performance, application to environmental waters, cartridge re-use, adsorption capacity and cost of adsorbent. Although the adsorption capacity of MWCNT was larger than AC and C18, however, the analytical performance of AC could be made close to the other sorbents by appropriate optimization of the SPE procedures. A sample of AC was then oxidized with various oxidizing agents to show that ACs of various surface properties has different enrichment efficiencies. Thus researchers are advised to try AC of various surface properties in SPE of pollutants prior to using expensive sorbents (such as MWCNT and C18 silica).     

Study on CM-chitosan/activated carbon hybrid gel films formed with EB irradiation

A series of novel hybrid gel films were prepared from carboxymethylated chitosan (CM-chitosan) and activated carbon (AC) by irradiation of compression-molded CM-chitosan/AC mixture in physical gel state with electron beam (EB) at room temperature. The formation, properties and structure of CM-chitosan/AC hybrid gel films were discussed in terms of gel fraction, swelling, mechanical property, SEM image and XPS spectra. Compared with pure crosslinked CM-chitosan gel, the gel fraction and mechanical property of the hybrid sample were obviously improved after adding AC into CM-chitosan film. The morphology analyses indicated that the hybrid gel films exhibited a rough and folded surface and a relatively interior uniform structure was sustained between CM-chitosan and AC. XPS revealed that the content of protonated amino groups of CM-chitosan macromolecule was promoted by AC. In addition, the adsorptive property of the gel films against humic acid was investigated by batch adsorption method. It was found that the adsorption efficiency of CM-chitosan is significantly improved by adding AC. These preliminary evaluations suggest that the CM-chitosan/AC gel films have great potential for applications in industrial field and biomedical field.     

Synthesis of Novel Poly[2-(dimethylamino) ethyl methacrylate]/Pumice Stone Hydrogel Composite for the Rapid Adsorption of Humic Acid in Aqueous Solution

In this study, a novel hydrogel composite, poly[2-(dimethylamino) ethyl methacrylate]/pumice (PDMAEMA/Pmc) was designed and its sorption behavior for humic acid (HA) was produced by using batch adsorption techniques. FTIR results showed that pumice was well incorporated with the PDMAEMA matrix. A scanning electron microscopy (SEM) was used in order to determine the morphology of composite hydrogel. In the batch experiments, the adsorption capacity was evaluated depending on different variables such as ionic strength; initial HA concentration; pH and adsorbent dosage. The adsorption capacity was found to be 86.27 mg/g under the optimized conditions. The results revealed that HA adsorption onto PDMAEMA/Pmc was well expressed by the Freundlich isotherm model and the adsorption process was followed by the pseudo second order kinetic model. The reusability tests also indicated that novel PDMAEMA/Pmc adsorbent was an efficient and cost-effective adsorbent for removal of HA.     

Adsorption behavior and mechanism of Cu(II) onto carbonate-substituted hydroxyapatite in the presence of humic acid

In this study, adsorption behavior and mechanism of Cu(II) onto carbonate-substituted hydroxyapatite (CHAP) in the absence and presence of humic acid (HA) were studied in batch experiments. The results showed that carbonate incorporation in HAP could significantly enhance the adsorption of Cu(II). In ternary systems, the presence of HA led to an increase in Cu(II) adsorption, dependent on HA concentration. Kinetic studies showed that pseudo-second-order kinetic model better described the adsorption process of Cu(II) onto CHAP and equilibrium data were best described by Sips models. The order of addition sequences of substrates was found to have a noticeable effect on Cu(II) adsorption onto CHAP. The general trend with respect to Cu(II) adsorption being: (CHAP–Cu)–HA?>?(CHAP–HA)–Cu?>?(Cu–HA)–CHAP. The present findings were important for estimating and optimizing the removal of Cu(II) ions by using CHA as a potential adsorbent.