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Adsorption Properties and Application of Modified Cellulose: A Review
Xing Lei, Yang Shiqi
Adsorption Properties and Application of Modified Cellulose: A Review
Cellulose is widely used as a natural bio-based material. The modification of cellulose and its application in adsorption have been the focus of research. In addition to introduce the basic structure of modified cellulose, this thesis summarizes the cellulose that modified by chemical modification and the high adsorption capacity of modified cellulose for various aquatic pollutants. We focus on the adsorption, adsorption mechanism of modified fiber and adsorption of metal ions and nitrogen and phosphorus in water. Moreover, this thesis also suggests that applying modified fiber material to soil could provide a comprehensive explanation for soil improvement and crop yield. Meanwhile, combining the modified cellulose with fertilizer improves the utilization rate of fertilizer and reduces the non-point source pollution caused by fertilization.
cellulose / chemical modification / aquatic pollutants / adsorption / natural bio-based material {{custom_keyword}} /
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Blending of biodegradable polymers in combination with low-price organic fillers has proven to be a suitable approach to produce cost-effective composites in order to address pollution issues and develop products with superior mechanical properties. In the present research work PBAT/PHB/Babassu composites with 25, 50, and 75% of each polymer and 20% of Babassu were produced by melting extrusion. Their thermal, mechanical, and morphological behavior was investigated by differential scanning calorimetry (DSC), tensile testing, and scanning electron microscopy (SEM). Blending PBAT with PHB inhibited the crystallization of both polymers whereas adding Babassu did not significantly change their melting behaviour. Incorporation of Babassu reduced the tensile strength of its respective blends between 4.8 and 32.3%, and elongation at break between 26.0 and 66.3%. PBAT as highly ductile and low crystalline polymer may be seen as a crystallization tool control for PHB as well as a plasticizer to PBAT/PHB blends and PBAT/PHB/Babassu composites. As PBAT content increases: (i) elongation at break increases and (ii) surface fracture becomes more refined indicating the presence of more energy dissipation mechanisms. As PBAT/PHB/Babassu composites are biodegradable, environmental friendly, and cost effective, products based on these compounds have a great potential since their mechanical properties such as ductility, stiffness, and tensile strength are still suitable for several applications even at lower temperatures (-40 °C).
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Water-insoluble oils, including crude petroleum and a wide variety of refined organic liquids, can cause major problems if spilled or leaked to aqueous environments. Potential environmental damage may be reduced if the spilled oil is promptly and efficiently removed from the water. This article reviews research that sheds light on the use of cellulose-based materials as sorbents to mitigate effects of oil spills. Encouraging results for oil sorption have been reported when using naturally hydrophobic cellulosic fibers such as unprocessed cotton, kapok, or milkweed seed hair. In addition, a wide assortment of cellulosic materials have been shown to be effective sorbents for hydrocarbon oils, especially in the absence of water, and their performance under water-wet conditions can be enhanced by various pretreatments that render them more hydrophobic. More research is needed on environmentally friendly systems to handle oil-contaminated sorbents after their use; promising approaches include their re-use after regeneration, anaerobic digestion, and incineration, among others. Research is also needed to further develop combined response systems in which biosorption is used along with other spill-response measures, including skimming, demulsification, biodegradation, and the use of booms to limit the spreading of oil slicks.
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In recent decades, increased domestic, agricultural and industrial activities worldwide have led to the release of various pollutants, such as toxic heavy metals, inorganic anions, organics, micropollutants and nutrients into the aquatic environment. The removal of these wide varieties of pollutants for better quality of water for various activities is an emerging issue and a robust and eco-friendly treatment technology is needed for the purpose. It is well known that cellulosic materials can be obtained from various natural sources and can be employed as cheap adsorbents. Their adsorption capacities for heavy metal ions and other aquatic pollutants can be significantly affected upon chemical treatment. In general, chemically modified cellulose exhibits higher adsorption capacities for various aquatic pollutants than their unmodified forms. Numerous chemicals have been used for cellulose modifications which include mineral and organic acids, bases, oxidizing agent, organic compounds, etc. This paper reviews the current state of research on the use of cellulose, a naturally occurring material, its modified forms and their efficacy as adsorbents for the removal of various pollutants from waste streams. In this review, an extensive list of various cellulose-based adsorbents from literature has been compiled and their adsorption capacities under various conditions for the removal of various pollutants, as available in the literature, are presented along with highlighting and discussing the key advancement on the preparation of cellulose-based adsorbents. It is evident from the literature survey presented herein that modified cellulose-based adsorbents exhibit good potential for the removal of various aquatic pollutants. However, still there is a need to find out the practical utility of these adsorbents on a commercial scale, leading to the improvement of pollution control.
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Deep understanding of the structure-property relationships of polysaccharide derivatives depends on the ability to control the position of the substituents around the monosaccharide ring and along the chain. Equally important is the ability to analyze position of substitution. Historically, both synthetic control and analysis of regiochemistry have been very difficult for cellulose derivatives, as for most other polysaccharide derivatives. With the advent of cellulose solvents that are suitable for chemical transformations, it has become possible to carry out cellulose derivatization under conditions sufficiently mild to permit increasingly complete regiochemical control, particularly with regard to the position of the substituents around the anhydroglucose ring. In addition, new techniques for forming cellulose and its derivatives from monomers, either by enzyme-catalyzed processes or chemical polymerization, permit us to address new frontiers in regiochemical control. We review these exciting developments in regiocontrolled synthesis of cellulose derivatives and their implications for in-depth structure-property studies.
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AbstractWhen native cellulose is treated by catalytic oxidation with 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)/NaBr/NaClO under aqueous conditions, significant amounts of carboxylate and aldehyde groups can be introduced on surfaces of cellulose I crystallites and into disordered regions without any changes in crystallinity of cellulose I or in the original fibrous morphology. In this study, behavior of ion exchange of carboxylate groups in the TEMPO-oxidized fibrous cellulose prepared from cotton linters was compared with that of fibrous carboxymethyl cellulose (F-CMC) with almost the same carboxylate content as that of the TEMPO-oxidized cellulose. These fibrous celluloses were soaked in various metal salt solutions, and metal ion contents in the celluloses were determined by X-ray fluorescence analysis after washing with water and drying of the celluloses. In all metal salts examined in the ion-exchange experiments, the TEMPO-oxidized cellulose had metal ion contents higher than those of F-CMC. Especially, lead, calcium and silver ions were greatly introduced into the TEMPO-oxidized cellulose with the metal ion/carboxylate molar ratio of about 1:1. The adsorption selectivity of metal ions on the TEMPO-oxidized cellulose was also studied using aqueous solutions containing multiple metal salts for soaking, and the following selectivity order was obtained:
Moreover, swelling ability of the TEMPO-oxidized celluloses having various metal carboxylate groups in water and wet tensile strength of handsheets prepared thereof were studied in terms of kinds of metal ion introduced. Degree of dissociation of the metal carboxylate groups in these celluloses is likely to affect the results of the above characteristics of the TEMPO-oxidized celluloses. {{custom_citation.content}}
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A novel method for D-glucose (D-Glu) and trimethylammonium chloride immobilization onto the surface of cellulose powder was studied. Cellulose powder was grafted with vinyl monomer glycidyl methacrylate (GMA), using ceric ammonium nitrate as an initiator, and further derived with quaternary ammonium groups to build the D-GluN(+)-type cellulose absorbent (Cell-g-GMA-D-GluN(+)). Epoxy cellulose was found to contain 5.48 mmol/g epoxy groups. The adsorption process of modified cellulose was described by the Langmuir model of adsorption well, the maximum adsorption capacity of chromium (VI) reaching a value of 71.79 mg/g. Adsorption desorption tests of the D-GluN(+)-type cellulose derivatives showed a good reproducibility of the adsorbent, so that the adsorbent could be reused for at least six times.
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Processing of solutions containing phenolics by adsorption-desorption enables the recovery and purification of bioactive compounds or fractions from plant. This work reviews the equilibrium and kinetic principles of adsorption, as well as the adsorption/desorption processing of solutions containing phenolic compounds. The description of relevant applications such as food-oriented processes, detoxification of fermentation media, color removal, and purification of sugar solutions and microbial metabolites is included. (C) 2011 Elsevier Ltd.
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AbstractThe standard solution-depletion method is implemented with SDS-gel electrophoresis as a multiplexing, separation-and-quantification tool to measure competition between two proteins (i and j) for adsorption to the same hydrophobic adsorbent particles (either octyl sepharose or silanized glass) immersed in binary-protein solutions. Adsorption kinetics reveals an unanticipated slow protein-size-dependent competition that controls steady-state adsorption selectivity. Two sequential pseudo-steady-state adsorption regimes (State 1 and State 2) are frequently observed depending on i, j solution concentrations. State 1 and State 2 are connected by a smooth transition, giving rise to sigmoidally-shaped adsorption-kinetic profiles with a downward inflection near 60 min of solution/adsorbent contact. Mass ratio of adsorbed i, j proteins (mi/mj) remains nearly constant between States 1 and 2, even though both mi and mj decrease in the transition between states. State 2 is shown to be stable for 24 h of continuous-adsorbent contact with stagnant solution whereas State 2 is eliminated by continuous mixing of adsorbent with solution. In sharp contrast to binary-competition results, adsorption to hydrophobic adsorbent particles from single-protein solutions (pure i or j) exhibits no detectable kinetics within the timeframe of experiment from either stagnant or continuously mixed solution, quickly achieving a single steady-state value in proportion to solution concentration. Comparison of binary competition between dissimilarly-sized protein pairs chosen to span a broad molecular-weight (MW) range demonstrates that selectivity between i and j scales with MW ratio that is proportional to protein-volume ratio (ubiquitin, Ub, MW = 10.7 kDa; human serum albumin, HSA, MW = 66.3 kDa; prothrombin, FII, 72 kDa; immunoglobulin G, IgG, MW = 160 kDa; fibrinogen, Fib, MW = 341 kDa). Results are interpreted in terms of a kinetic model of adsorption that has protein molecules rapidly diffusing into an inflating interphase that is spontaneously formed by bringing a protein solution into contact with a physical surface (State 1). State 2 follows by rearrangement of proteins within this interphase to achieve the maximum interphase concentration (dictated by energetics of interphase dehydration) within the thinnest (lowest volume) interphase possible by ejection of interphase water and initially-adsorbed proteins. Implications for understanding biocompatibility are discussed using a computational example relevant to the problem of blood–plasma coagulation. {{custom_citation.content}}
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Adsorption of food dyes acid blue 9 and food yellow 3 onto chitosan was studied. Stirring rate influence on kinetics and mechanism was verified. Infra-red analysis was carried out before and after adsorption in order to verify the adsorption nature. Adsorption experiments were carried out in batch systems with different stirring rates (15-400 rpm). Kinetic behavior was analyzed through the pseudo-first-order, pseudo-second-order and Elovich models. Adsorption mechanism was verified according to the film diffusion model and HSDM model. Pseudo-second-order and Elovich models were satisfactory in order to represent experimental data in all stirring rates. For both dyes, adsorption occurred by film and intraparticle diffusion, and the stirring rate increase caused a decrease in film diffusion resistance. Therefore, the film diffusivity increased the adsorption capacity and, consequently, intraparticle diffusivity increased. In all stirring rates, the rate-limiting step was film diffusion. Adsorption of acid blue 9 and food yellow 3 onto chitosan occurred by chemiosorption. (C) 2011 Elsevier B.V.
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A novel nanoadsorbent for the removal of heavy metal ions is reported. Cotton was first hydrolyzed to obtain cellulose nanocrystals (CNCs). CNCs were then chemically modified with succinic anhydride to obtain SCNCs. The sodic nanoadsorbent (NaSCNCs) was further prepared by treatment of SCNCs with saturated NaHCO3 aqueous solution. Batch experiments were carried out with SCNCs and NaSCNCs for the removal of Pb2+ and Cd2+. The effects of contact time, pH, initial adsorption concentration, coexisting ions and the regeneration performance were investigated. Kinetic studies showed that the adsorption equilibrium time of Pb2+ and Cd2+ was reached within 150 min on SCNCs and 5 min on NaSCNCs. The adsorption capacities of Pb2+ and Cd2+ on SCNCs and NaSCNCs increased with increasing pH. The adsorption isotherm was well fitted by the Langmuir model. The maximum adsorption capacities of SCNCs and NaSCNCs for Pb2+ and Cd2+ were 367.6 mg/g, 259.7 mg/g and 465.1 mg/g, 344.8 mg/g, respectively. SCNCs and NaSCNCs showed high selectivity and interference resistance from coexisting ions for the adsorption of Pb2+. NaSCNCs could be efficiently regenerated with a mild saturated NaCl solution with no loss of capacity after two recycles. The adsorption mechanisms of SCNCs and NaSCNCs were discussed.
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AbstractDiethylenetriamine-bacterial cellulose (EABC) was synthesized by amination with diethylenetriamine on bacterial cellulose (BC). Its adsorption properties for Cu(II) and Pb(II) were investigated. The parameters affecting the metal ions adsorption, such as contact time, solution pH, and initial metal ions concentration have been investigated. The adsorption kinetics and adsorption isotherms were further studied. The results show that the adsorption rate could be well fitted by pseudo-second-order rate model, and adsorption isotherm could be described by the Langmuir model. The regeneration of EABC was also studied. This study provides the relatively comprehensive data for the EABC application to the removal of metal ion in the wastewater. {{custom_citation.content}}
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Cellulose powder was grafted with the vinyl monomer glycidyl methacrylate using ceric ammonium nitrate as initiator and was further derived with β-CD and quaternary ammonium groups to build Cell-g-GMA-β-CDN(+) adsorbent. Epoxy cellulose was made up of Cell-g-GMA and Cell-hydro-g-GMA, and was found to contain 3.71 mmol g(-1) epoxy groups. The adsorption process of the modified cellulose was described by the Langmuir model of adsorption well, and the maximum adsorption capacity of chromium (VI) reached 61.05 mg g(-1). The adsorption-desorption tests of β-CDN(+)-type cellulose derivatives exhibited that the reproducibility of the adsorbent was well and the adsorbent could be reused five times at least.
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The aim of this study is to examine the efficiency of biobased Spanish broom (SB) surface modified cellulose fibers to remove bisphenol A (BPA), a well-known endocrine disruptor, from water. Spanish brooms are flowering plants, which are native and abundant to Mediterranean regions. The functionalized fibers (FF) were found to have the best adsorption efficiency at pH 5, due to the optimal hydrophobic interaction between the FF fiber and BPA. Adsorption kinetics of BPA was found to fit well a pseudo-second order reaction. Equilibrium isotherm data were fitted by Langmuir and Freundlich models. A very fast and simple regeneration method was developed and it was observed that adsorption capacity of the fibers was kept almost unchanged after 3 consecutive uses. Bottled water and synthetic wastewater were also tested to assess the efficiency of the process under more realistic water and wastewater treatment conditions. It was found that BPA removal was slightly decreased from 77% in ultrapure water to 64% in synthetic wastewater matrix, indicating that FF has a high selectivity toward BPA, even in the presence of other organic compounds. Overall, it was observed that SB-modified fibers can be a new promising green biotechnology for water purification.
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AbstractIn this study, a higher surface area spherical nanoscale zero valent iron (HNZVI) cluster (80 nm, 54.25 m2 g−1) was synthesized in ethanol–water mixed solvent in the presence of dispersion agent of polyglycol (PEG). At the same time, a lower surface area nanoscale zero valent iron (LNZVI) particle (80 nm, 8.08 m2 g−1) was also prepared with only de-ioned water as reaction media. Their structures, compositions and physical properties were characterized by transmission electron microscope (TEM), X-ray diffractometer (XRD), inductively coupled plasma atomic emission spectrophotometer (ICP-AES), and Brunauer–Emmett–Teller (BET) surface area analyzer and the results obtained for these two kinds of nanoscale iron were compared with each other and also with those reported in the literatures. The HNZVI clusters seemed to be accumulated by smaller iron particles (<10 nm). At the same time, whiskers were formed in the final produce. Reactivity of the HNZVI was affirmed via denitrification of nitrate. The factors controlling the reduction of nitrate, such as pH, dissolved oxygen (DO), iron content as well as the initial nitrate concentration were also discussed. Finally, kinetic analysis revealed that chemical reduction of nitrate by HNZVI could not be described by the first- or pseudo-first-order kinetic model. {{custom_citation.content}}
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采用碱液-超声波对小麦秸秆预处理后,在高温下用环氧氯丙烷和铝盐进行化学改性,制备了改性秸秆吸附剂.分别对改性前后秸秆的性质表征和吸附性能研究,探讨了改性和吸附机理.表征分析结果表明,改性后秸秆的有序度和结晶度都得到明显提高,并且成功引入了铝离子.改性秸秆吸附水体磷的主要机理包括:因改性而获得的凹凸有致状结构的物理吸附;表面羟基产生的氢键作用以及对磷酸根离子具有配位络合作用;带正电荷表面电位的改性秸秆,可与带负电荷的磷酸根离子之间产生静电吸附作用;改性秸秆对水体磷的空间网捕作用,生成混合磷酸盐晶体.
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