细菌纤维素制备及吸附金属离子的研究进展

细菌纤维素(BC)是一种由微生物发酵技术制备的纤维素,分子内存在大量的羟基,具有超细网状纳米纤维结构,比表面积高,其独特的结构和物理化学性质对溶液中金属离子吸附性能起着重要作用。为了加快BC的发展及其对重金属吸附的应用,首先介绍了影响细菌纤维素的制备因素,例如:菌种、常用碳源及添加助剂。其次重点介绍了BC对Cu~(2+)、Pb~(2+)、Cd~(2+)、Cr~(6+)及其他金属离子(如Pd~(2+)、Ag~+、Au~(3+)、Fe~(2+)、Sb~(3+))等的吸附性能。然后对BC吸附金属离子机理进行了综述。最后,对BC的应用前景进行了展望。     

利用糖蜜制备细菌纤维素的研究

细菌纤维素（BC）是一类由微生物产生的纤维素。细菌纤维素以其独特的物理和化学性质被广泛应用于医药、食品、造纸、纺织等领域。然而，BC应用的最大挑战是其生产成本，尤其是发酵生产碳源的成本相对较高。以相对廉价的糖蜜为原料，研究比较了不同预处理方法（硫酸-热处理、热处理和未处理）以及生产菌种（木葡糖醋杆菌和红茶菌）对细菌纤维素产量的影响。结果表明，硫酸-热处理之后的糖蜜获得的细菌纤维素产量最高，可达6．0g/L，比用葡萄糖制备细菌纤维素的产量提高了78％。当以红茶菌为菌种，细菌纤维素的产量可达12．0g/L，是木葡糖醋杆菌作为菌种的两倍。与葡萄糖和果糖相比，糖蜜制备的细菌纤维素同样具有三维网状结构，但是含水率较低，杨氏模量较小。     

细菌纤维素及其酯化产物与聚乳酸的复合材料的制备与表征

细菌纤维素(BC)经由多种有机酸(乙酸、正己酸、月桂酸)表面酯化,得到细菌纤维素乙酸酯(C2-BC)、细菌纤维素正己酸酯(C6-BC)、细菌纤维素月桂酸酯(C12-BC),将BC及酯化产物分别加入到聚乳酸(PLA)溶液,采用热致相分离技术(TIPS)制备出BC(BC酯化产物)/PLA复合材料,红外光谱、扫描电镜、差热分析和热重分析结果显示,BC以及酯化产物均匀分布在PLA中,制备的复合材料具有多孔结构,酯化产物的添加提高了PLA的结晶度,但是对PLA链的移动性没有太大影响。同时,BC及其酯化产物的的引入,提高了PLA的降解温度,并且随着酯化支链的长度增加,杨氏模量和抗拉强度也相应有所提高。     

木质素复合细菌纤维素材料的制备及其吸油性能研究

为制备低成本且绿色环保的新型吸 油材料，本文以细菌纤维素（BC）为基质，脱碱木质素(DL)为疏水改性剂，通过低温浸渍法制备木质素复合细菌纤维素材料（BC-DL）；考察了原料预处理、反应时间、温度以及物料比等对BC-DL疏水及吸油性能的影响。利用FTIR、XPS、SEM、BET、接触角仪对材料的化学结构及微观形貌进行表征。结果表明，与改性前相比，DL改性后BC的比表面积由33.15 m2/g提升至71.09 m2/g，水接触角由未改性BC的19.5°增大到116.8°。吸油实验结果显示，BC-DL对花生油、柴油、真空泵废油的吸油量（OCA）分别为34.8 g/g、33.7 g/g、34.6 g/g；在经过8次循环后，OCA保留在19.1 g/g、18.3 g/g和18.8 g/g，BC-DL对三种油品均有良好的吸附性能和循环利用性。     

细菌纤维素苯甲酸酯的合成与表征

以细菌纤维素（BC）为原料,通过酯化反应制备细菌纤维素苯甲酸酯（BBC）,探讨了硝基苯用量、反应时间、反应温度以及苯甲酰氯用量对细菌纤维素苯甲酸酯取代度的影响。分别用红外光谱（FTIR）、差示扫描量热法（DSC）、偏光显微镜（POM）和广角X-射线衍射（WAXD）对产物结构、热致液晶织构和性能进行了表征。结果表明,细菌纤维素苯甲酸酯在281．7～356．3℃之间可以形成近晶型液晶相,其熔点和清亮点比已报道的植物纤维素苯甲酸酯的更高。     

木质素复合细菌纤维素材料的制备及其吸油性能

为制备低成本且绿色环保的新型吸油材料,以细菌纤维素(BC)为基质,脱碱木质素(DL)为疏水改性剂,通过低温浸渍法制备了木质素复合细菌纤维素材料(BC-DL);考察了原料预处理、反应时间、温度以及物料比等对BC-DL疏水及吸油性能的影响.利用FTIR、XPS、SEM、BET、接触角测量仪对材料的化学结构及微观形貌进行了表征.结果表明,DL改性后BC的比表面积由未改性BC的33.15 m2/g提升至71.09 m2/g,水接触角由未改性BC的19.5°增大到116.8°.BC-DL对花生油、柴油、真空泵废油的饱和吸附量分别为34.8、33.7、34.6 g/g;在经过7次循环后,饱和吸附量保留在19.067、18.355和18.820 g/g,BC-DL对3种油品均有良好的吸附性能和循环利用性.     

细菌纤维素膜的合成及表征

以海南椰子水为主要培养体系,实验室自行筛选的木醋杆菌(Acetobacter xylinum)为菌种,采用静态培养方法制备了细菌纤维素（BC）。对该BC和商业BC的结构和性能进行了测试对比,观察BC的微结构特点。结果表明: 制备的BC和商业BC在结构和一些性能方面是相似的,都是无色透明膜,呈三维网状结构和孔洞结构,具有良好的纳米纤维网络特征, 具有良好的吸湿性和极佳的持水能力,本实验制备的BC生产成本低,可根据需要大量制备,在生物医学领域具有良好的、广泛的应用前景。     

聚乳酸/细菌纤维素复合材料制备研究

采用溶液浇铸的方法制备了聚乳酸／细菌纤维素（PLA／BC）复合膜,研究了不同用量的BC对PLA力学性能的影响。将制备的薄膜置于模拟体液与磷酸盐缓冲稀释液中做降解实验,考察了BC对PLA降解性能的影响。结果表明：随着BC用量的增加,改性PLA的断裂伸长率、拉伸强度明显提高,降解速率加快。     

小径纳米纤维素管的生物制备及其表征

以透氧硅胶双套管为模具,设计组装了一套新型生物反应装置,利用红茶菌和套管法生产细菌纤维素（BC）小径人工血管材料。研究发现,细菌纤维素可以分别在内外两根硅胶管的外表面和内表面同时生成,并最终长到一起形成整体BC管。获得的BC管不仅具有较好的强度和光滑平整的内外表面,而且纳米纤维交织紧密,无纤维分层现象,具有突出优点和应用潜力。该制备方法简便易行,成本低廉,生产效率高,可工业化生产。     

葡糖醋杆菌G31产细菌纤维素的结构表征及性能测试

以葡糖醋杆菌G31为菌种,用HS培养基发酵制备细菌纤维素（BC）。利用蒽酮比色法、酶水解法初步证明发酵产物为纤维素,采用FTIR、SEM、XRD、CP/MAS 13C-NMR、DSC和TG对BC的形貌和结构进行表征并对其进行性能测试。结果显示：发酵产物具有超细三维网状结构,属于结晶度为92.42%的纤维素Ⅰ型,具有良好的持水性和拉伸性。同时对其分子量进行测定,Mw为5737,属于低分子量BC,其氧气透过率和水蒸气透过率分别为913.55?3.23 cm3/m2?24h?0.1MPa和656.15?3.92 g/m2?24h,表明该BC具有更好的锁水能力,为其在面膜领域的应用奠定了基础。     

细菌纤维素对重金属离子的吸附机理研究

以细菌纤维素(BC)为吸附剂,对重金属离子Cu2+,Pb2+和Cd2+的吸附等温线和吸附动力学特性进行了研究,并采用红外光谱分析法探讨了吸附作用机理。结果表明:BC对Cu2+,Pb2+和Cd2+吸附更好地符合Langmuir吸附等温方程和准二级反应动力学模型,说明吸附过程为单分子层吸附,化学吸附作用为主。粒子内扩散拟合曲线均不经过原点,证明粒子内扩散并不是唯一速率控制步骤。FT-IR分析表明吸附金属离子后的BC中—OH最大吸收位发生不同程度的蓝移,说明BC中部分—OH参与吸附,即与重金属离子之间发生反应,从而使—OH的数量减少。     

重金属离子吸附材料的研究进展

综述了以无机吸附材料（碳质类、矿物类和金属氧化类）、高分子吸附材料（人工合成高分子材料和天然高分子材料）和复合型吸附材料（有机/有机型、有机/无机型和无机/无机型）为代表的重金属离子吸附材料的结构特征和吸附性能。重点介绍了离子选择性吸附材料（螯合型吸附材料和离子印迹型吸附材料）和可降解生物质基离子吸附材料（纤维素、壳聚糖、木质素和农林废弃物）等新型重金属离子吸附材料的研究进展,同时展望了重金属离子吸附材料的发展方向。     

改性纤维素材料对金属离子吸附研究进展

纤维素在地球上含量十分丰富,且表面含有大量的羟基,可以通过羟基一系列的衍生反应,对纤维素进行改性,将纤维素制成离子型的吸附剂。本文就纤维素改性,综述了近些年来国内外以纤维素为原料改性制得的吸附剂相关的研究进展。     

Preparation of amidoximated bacterial cellulose and its adsorption mechanism for Cu2+ and Pb2+

Amidoximated bacterial cellulose (Am‐BC) was prepared through successive polymer analogous reactions of bacterial cellulose with acrylonitrile in an alkaline medium followed by reaction with aqueous hydroxylamine. It was used as an adsorbent to remove Cu²⁺ and Pb²⁺ from aqueous solutions. The adsorption behaviors of Cu²⁺ and Pb²⁺ onto Am‐BC were observed to be pH‐dependent. The maximum adsorption capacity of 84 and 67 mg g^–1 was observed, respectively, for Cu²⁺ and Pb²⁺ at pH 5. Scanning electronic microscopy (SEM) indicated that the microporous network structure of Am‐BC was maintained even after the modifacation. The adsorption mechanisms for Cu²⁺ and Pb²⁺ onto Am‐BC were investigated by fourier transform infrared spectroscopy (FTIR), ζ potential measurement and X‐ray photoelectron spectroscopy (XPS). The results revealed that the mechanism for the adsorption of Cu²⁺ onto Am‐BC could be mainly described as between metal ions and nitrogen atom in the amidoxime groups or oxygen atom in the hydroxyl groups. However, in the adsorption process for Pb²⁺, precipitation played the important role along with electrostatic interactions, although chelation action also existed in the process accounted for the adsorption process. The regeneration of Am‐BC was studied by treatment with a strong complexing agent, ethylenediaminetetracetic acid (EDTA). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Removal of metal ions from aqueous solution by adsorption onto activated carbon cloths: adsorption competition with organic matter

Activated carbon cloths are recent adsorbents whose adsorption properties are well known for monocomponent solutions of organics or metal ions. However, to treat wastewaters with these materials, their performance has to be determined in multicomponent solution. This work studies adsorption competition between metal ions (Cu²⁺, Pb²⁺) and organic matter (benzoic acid). The first part investigates adsorption equilibrium of monocomponent metal ions solutions and shows the dependence of adsorption capacities on adsorbent porosity and metal ions chemical properties (molecular weight, ionic radius and electronegativity). The influence of pH is also demonstrated. The second part focuses on adsorption competition: (1) between both metal ions (a decrease of adsorption capacities is observed, whose value is related to adsorption kinetics of metal ions); (2) between metal ions and organic matter, in solution or adsorbed onto the activated carbon cloth (a strong influence of pH is shown: when benzoic acid is under benzoate form, in both cases adsorption is increased due to the formation of ligands between adsorbed benzoate ions and metals).     

聚酰胺接枝纤维素的合成及对金属离子的吸附性能

以葡萄秸秆为原料提取纤维素,以环氧树脂为交联剂,将聚酰胺交联到纤维素上制得聚酰胺-葡萄纤维素吸附剂。测定聚酰胺-葡萄纤维素吸附剂对Co2+和Fe2+的吸附性能,并研究环氧树脂用量、反应温度和吸附平衡时间对吸附性能的影响。结果表明,当反应温度25℃、吸附平衡时间60 min和m(聚酰胺)∶m(葡萄纤维素)∶m(环氧树脂)=2∶1∶1.5时,制备的聚酰胺-葡萄纤维素吸附剂的吸附性能最好。聚酰胺-葡萄纤维素吸附剂对Co2+和Fe2+的吸附均在60 min后达到平衡,Fe2+和Co2+的最大吸附容量分别为22.40 mg·g-1和16.82 mg·g-1。     

Adsorption removal of Cu2+ and Ni2+ from waste water using nano‐cellulose hybrids containing reactive polyhedral oligomeric silsesquioxanes

Cellulose is an important biomass in natural material fields. Reactive polyhedral oligomeric silsesquioxane (R‐POSS) bearing multi‐N‐methylol groups is novel high reactive POSS monomer. The nano‐cellulose hybrids containing R‐POSS were synthesized by crosslinking reaction. It was interesting to investigate properties and applications of hybrids containing R‐POSS. In this work, nano‐cellulose hybrids as novel biosorbent were used for adsorpting copper and nickel ions in aqueous solution. Adsorption kinetics and equilibrium isotherm of Cu²⁺ and Ni²⁺ on the nano‐cellulose hybrids were investigated. The results showed that R‐POSS had been grafted to cellulose macromolecule. The nano‐cellulose hybrids could form new adsorptive position for heavy metal ions. The adsorption capacities of hybrid materials were obviously higher than that of control cellulose. The adsorption of heavy metal ions on nano‐cellulose hybrids followed the second‐order model. The equilibrium isotherms for adsorpting copper and nickel ions on the hybrids followed Langmuir isotherm model. Nano‐cellulose materials containing POSS as biosorbents or ultrafiltration membranes would be used in separation of toxic heavy metal ions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

丙酮酸改性壳聚糖对金属离子的吸附性能研究

丙酮酸经Schiff碱反应对壳聚糖进行修饰 ,合成了高取代的水溶性丙酮酸缩壳聚糖 (PCTS) ,研究了PCTS、SCTS(水杨醛改性壳聚糖 )、CTS(壳聚糖 )对Cu(Ⅱ )、Zn(Ⅱ )、Co(Ⅱ )的静态吸附性能 ,并采用正交实验法考察了金属离子浓度、介质酸度、吸附量和吸附时间对吸附剂去除金属离子能力的影响。结果表明 ,PCTS的吸附性能优于SCTS与CTS ,对Cu(Ⅱ )、Zn(Ⅱ )、Co(Ⅱ )的吸附容量 (pH =7 0 )分别为 2 79 56、1 96 63、70 2 1mg/g ,金属离子浓度、介质酸度对吸附性能影响大 ,而吸附剂用量、吸附时间对吸附性能影响较小。     

生物炭/凹凸棒土的制备及对磺胺嘧啶的吸附

利用凹凸棒土（ATP）和碱性木质素（AL）慢速限氧热解制备生物炭/凹凸棒土（BC/ATP）吸附水中的磺胺嘧啶（SDZ）,研究原料比例和热解温度对产品组分含量和吸附效果的影响,并探讨初始pH、BC/ATP投加量、吸附时间和SDZ初始浓度等因素对去除率的影响。分别采用拟一级、拟二级和颗粒内扩散方程拟合吸附过程动力学,用Langmuir和Freundlich方程拟合等温吸附线。通过扫描电镜、傅里叶红外光谱、X射线衍射、拉曼光谱和比表面积测定分析BC/ATP的表面形貌、孔结构和官能团。结果表明ATP能有效促进热解过程中挥发性中间产物二次热解,提高BC得率,改善BC/ATP吸附性能,并通过ATP的金属离子作用扩宽BC/ATP的pH敏感度。吸附动力学均符合拟二级动力学模型,且由颗粒内扩散模型拟合说明该扩散行为不是限制吸附速率的唯一因素,等温吸附线更符合Langmuir等温吸附模型,0＜R_L＜1,为优惠吸附,说明吸附过程易于进行,最大吸附量为109.53mg/g。不同pH条件下吸附机理可分为两部分：①在酸性和中性条件下,主要依靠BC/ATP的上BC表面负电荷与SDZ静电作用;②碱性条件下主要依靠ATP表面金属离子与SDZ氢键的金属阳离子桥接作用。     

Removal of heavy metals by polysaccharide: a review

ABSTRACT

Industries produce large amounts of heavy metal waste that are hazardous to the environment. Thus, heavy metal ions such as nickel (II), lead (II), copper (II), cadmium (II), and zinc (II), must be removed from wastewater. One commonly employed method is biosorption, which is the adsorption of metal ions by biomaterials such as polysaccharides. In this review, polysaccharides are classified into four groups: polysaccharide homopolymers, polysaccharide blends, copolymers, and polysaccharide composites. Pristine natural polysaccharides like chitin, chitosan, cellulose, starch, and alginate which have multiple functional groups. Additional functionalization is introduced in the form of blending, grafting, or mixing with various nanomaterials having additional functional group to make it more efficient for heavy metal ion adsorption. Introduction of second component onto the main polymer chain not only introduce functionality but enhance mechanical strength which is one of the vital requirements for the recyclability of adsorbent. Longer the time adsorbent is reused more economical is the removal process of metal ions from wastewater. Heavy metal ions undergo various types of interaction like π-π interactions, dipole–dipole interaction, hydrogen bonding or van der walls force with homopolymer, copolymers, blends, or nanocomposite having anions or electron-rich group. Adsorption process is studied by adsorption kinetics and adsorption isotherms. This review represents the adsorption behavior of chitosan, cellulose, starch, alginate, and their derivatives.