小麦秸秆生物炭吸附诺氟沙星特性

采用孔径与比表面积分析仪、SEM、FTIR及Boehm滴定对小麦秸秆生物炭(XM300、XM450、XM600)进行表征,考察了生物炭对诺氟沙星(NOR)的吸附机制。结果表明,随着热解温度的升高,生物炭比表面积与孔容积增大,孔径变小,表面羧基、内酯基与酚羟基等酸性官能团数量减少。伪二级动力学方程和Langmuir等温模型更适合描述3种生物炭对NOR的吸附,颗粒内扩散方程拟合发现生物炭对NOR的吸附包括快速外扩散与缓慢内扩散;XM300对NOR的吸附容量最大(40.30 mg/g),得益于低热解温度生物炭中存在大量非碳化有机质的分配作用。     

改性玉米芯生物碳对氨氮的吸附特性

以农业废弃物玉米芯为原料,采用限氧热解法（600℃）制备生物碳,分别采用盐酸、双氧水和硝酸对其进行改性。通过元素分析、FTIR、BET-N₂、Boehm滴定法及扫描电镜等手段表征了生物碳的组成与结构。通过序批实验,研究了生物碳对氨氮的吸附性能及影响因素,探讨了其吸附机理,为生物碳在污水处理中更好的应用提供参考。结果表明,未改性生物碳和经过盐酸、硝酸和双氧水改性的生物碳其比表面积分别为17.74、212.89、208.74和209.15 m²·g^-1;表面酸性含氧官能团数量分别为0.11、0.95、5.73和2.15 mmol·g^-1。等温吸附曲线符合Freundlich方程。动力学研究表明,生物碳对氨氮吸附行为符合准二级动力学方程。且经硝酸改性生物碳由于表面酸性含氧官能团的增加,其对氨氮的吸附能力显著提高。     

生物炭对重金属(Zn)的吸附特性及动力学

在300～700℃下制备了水葫芦炭和玉米秸秆炭,研究了生物质种类、热解温度、溶液初始pH和Zn(Ⅱ)初始浓度对两种生物炭吸附溶液中Zn(Ⅱ)的影响,并结合吸附过程曲线拟合获得了吸附动力学模型。结果表明：随着热解温度的升高,生物炭理化特性发生显著变化,生物炭的挥发分、氧含量、氢含量以及O/C和H/C显著降低,而固定碳、灰分和热值显著升高,生物炭的比表面积、总孔容、微孔容、pH以及KCl等盐类物质均得到了显著增加。随着溶液初始pH增加,生物炭对Zn(Ⅱ)的吸附能力呈现先快速增加然后逐步趋于稳定或稍有下降的趋势,不同生物炭的最大平衡吸附量出现在pH=4~6之间。Zn(Ⅱ)初始浓度<30mg/L时,生物炭对Zn(Ⅱ)平衡吸附量随溶液Zn(Ⅱ)初始浓度的增加呈线性快速增长,而当Zn(Ⅱ)初始浓度>30mg/L,其平衡吸附量增长趋势变缓。在相同Zn(Ⅱ)初始浓度下,随着热解温度的提高,生物炭对溶液中Zn(Ⅱ)平衡吸附量逐渐提高,且在同一热解温度下制备的水葫芦炭对Zn(Ⅱ)的平衡吸附量显著高于玉米秸秆炭。两种生物炭对溶液Zn(Ⅱ)的吸附符合Lagergren准二级动力学模型,其吸附过程均受化学吸附控制,水葫芦炭和玉米秸秆炭对Zn(Ⅱ)吸附机制主要包括含氧官能团的络合作用和无机盐离子的沉淀作用。     

不同热解温度生物炭对溶液中镉的吸附性能研究

以玉米秸秆、枫杨树枝、花生壳为生物质材料,分别在450、550、650℃下,对3种生物质材料进行厌氧热解制备了9种生物炭,对溶液中的Cd2+进行吸附试验,研究了pH、生物炭投加量、吸附时间和Cd2+初始质量浓度对Cd2+吸附效果的影响。结果表明,吸附过程与Langmuir、Freundlich和准一级动力学方程拟合的相关性较好。pH对吸附的影响较大,吸附率与生物炭的投加量呈正比,650℃制备的3种生物炭的吸附能力更强,花生壳生物炭对溶液中的Cd2+具有更好的吸附能力。     

A combined effect of adsorption and reduction potential of biochar derived from Mentha plant waste on removal of methylene blue dye from aqueous solution

ABSTRACT

Plant biochars were prepared by slow pyrolysis of Mentha plant waste to remove cationic dye methylene blue (MB) from aqueous solution. The biochars were characterized by X-Ray diffraction, IR-spectroscopy, thermogravimetric analysis, scanning electron microscope, cyclic voltammetry (CV), Brunauer-Emmett-Teller analysis, and zeta potential analyzer. Adsorption isotherms and kinetics applied on the MB dye removal by biochars showed monolayer chemisorption of MB dye. Present investigation revealed that removal of MB dye was due to synergistic action of chemisorption coupled with reductive electron transfer mechanisms. CV test showed a reversible, coupled redox reaction at interface of MB dye and biochar particles.     

原料种类和热解温度对生物炭吸附Cd2+的影响

以稻秆（RS）、稻壳（RH）、木屑（SD）为原料，在小型流化床实验台上制备生物炭，分析了原料种类和热解温度（400℃、500℃、600℃）对生物炭理化性质及吸附Cd²⁺性能的影响规律，并定性和定量分析了吸附过程中的作用机制。实验结果表明：准二级动力学方程和Langmuir方程能够较好地描述生物炭样品对Cd²⁺的吸附过程。生物炭RS500的平衡吸附量达到30.19mg/g，远远高于生物炭SD500，其中无机矿物的离子交换和沉淀反应吸附贡献值为24.95mg/g，是主导吸附机制；而生物炭SD500吸附Cd²⁺过程中，无机矿物和π键的贡献百分比分别为49.70%和38.21%。随着热解温度的升高，生物炭吸附Cd²⁺过程中含氧官能团的络合反应不断削弱而Cd²⁺-π键作用不断增强；稻秆炭和稻壳炭中无机矿物的吸附贡献值则呈先上升后下降的趋势，并在500℃热解温度下达到最大值。生物炭样品吸附Cd²⁺的作用机制中，离子交换和沉淀反应占比最大，Cd²⁺-π键作用次之，络合反应最小。     

Synthesis of ternary ceramics (Cr2AlC) by using biochars

In this paper, we report the synthesis of Cr₂AlC by using biochars derived from lignin, Distiller's dried grains with solubles (DDGS), and hemp fibers. Initially, the powders were pyrolyzed at 1350°C for 4 h in Ar atmosphere to form biochars. The ball-milled and sieved biochar powders were then mixed with Cr and Al powders in different stoichiometric ratios according to the C-content of the biochars. The mixed powders were reacted at 1350°C for 4 h in Ar atmosphere. Detailed scanning electron microscopy and X-ray diffraction analysis showed the powders derived from hemp and DDGS biochars were > 90% pure as compared to powders derived from lignin biochar which was 76% pure. It is expected that ternary ceramics derived from biochars can be an addition avenue for carbon-storage.     

High-efficiency remediation of cadmium (Cd2+) from aqueous solution using poultry manure– and farmyard manure–derived biochars

Farmyard manure (FYM-BC) and poultry manure (PM-BC) derived biochars were applied as adsorbents to remove Cd²⁺ from water. Results indicated that PM-BC was a more efficient adsorbent than FYM-BC at all experimental conditions. Maximum Cd²⁺ adsorption was observed at pH 4, temperature 318 K and contact time 1 h, regardless of biochar type. The Langmuir model predicted maximum adsorption capacity of 90.09 mg g^?1 for PM-BC. The data fitting to pseudo-second-order model proposed chemisorption of Cd²⁺ onto biochars. Thermodynamics indicated that adsorption was spontaneous and endothermic. Post-adsorption analysis provided evidences of strong chemical interactions between biochars’ functional groups and Cd²⁺ ions.     

生物炭基材料在抗生素废水处理中的研究进展

生物炭是一种由生物质原料热解而成的稳定多孔碳材料。目前，生物炭及其碳基材料作为功能材料因其在一定程度上不仅实现了废弃物的合理资源化利用，而且兼具经济与环境效益而倍受研究者关注。本文综述了生物炭的生物质原料种类、生物炭在不同成分下（纤维素、半纤维素、木质素）的形成机制及表面特性；重点介绍了生物炭的改性技术，主要包括物理化学处理、杂原子掺杂、金属元素掺杂、多种元素共掺杂以及制备工艺的改良等，生物炭改性的目的是为了增加其比表面积、反应活性位点和官能团，改良孔隙结构和无机成分，从而提高它在修复环境污染的性能；然后综述了生物炭作为优良吸附剂或催化剂在用于抗生素废水的具体应用及其去除机理。最后指出生物炭虽被证明了具备去除水中各类抗生素的潜力，但在材料本身的优化以及工程抗生素废水应用中仍有一些需要填补的知识空白。     

Amination of biochar surface from watermelon peel for toxic chromium removal enhancement

Watermelon peel residues were used to produce a new biochar by dehydration method. The new biochar has undergone two methods of chemical modification and the effect of this chemical modification on its ability to adsorb Cr(VI) ions from aqueous solution has been investigated. Three biochars, Melon-B, Melon-BO-NH_2 and Melon-BO-TETA, were made from watermelon peel via dehydration with 50% sulfuric acid to give Melon-B followed by oxidation with ozone and amination using ammonium hydroxide to give Melon-BO-NH_2 or Triethylenetetramine(TETA) to give Melon-BO-TETA. The prepared biochars were characterized by BET, BJH,SEM, FT-IR, TGA, DSC and EDAX analyses. The highest removal percentage of Cr(VI) ions was 69% for Melon-B,98% for Melon-BO-NH_2 and 99% for Melon-BO-TETA biochars of 100 mg·L~(-1) Cr(VI) ions initial concentration and 1.0 g·L~(-1) adsorbents dose. The unmodified biochar(Melon-B) and modified biochars(Melon-BO-NH_2 and Melon-BO-TETA) had maximum adsorption capacities(Qm) of 72.46, 123.46, and 333.33 mg·g~(-1), respectively.The amination of biochar reduced the pore size of modified biochar, whereas the surface area was enhanced.The obtained data of isotherm models were tested using different error function equations. The Freundlich,Tempkin and Langmuir isotherm models were best fitted to the experimental data of Melon-B, Melon-BO-NH_2 and Melon-BO-TETA, respectively. The adsorption rate was primarily controlled by pseudo-second–order rate model. Conclusively, the functional groups interactions are important for adsorption mechanisms and expected to control the adsorption process. The adsorption for the Melon-B, Melon-BO-NH_2 and Melon-BO-TETA could be explained for acid–base interaction and hydrogen bonding interaction.     

污泥与生物质共热解制备生物质炭工艺优化及吸附性能

通过污泥与秸秆（玉米秸秆、水稻秸秆、小麦秸秆、芝麻秸秆）慢速共热解的方法,在不同热解温度（300℃、400℃、500℃、600℃）、热解时间（0.5h、1h、1.5h、2h）及配比（污泥与生物质1∶0、1∶0.5、1∶1、1∶2）条件下制备4种生物质炭,即SCBC（污泥-玉米秸秆生物质炭）、SRBC（污泥-水稻秸秆生物质炭）、SWBC（污泥-小麦生物质炭）、SSBC（污泥-芝麻生物质炭）,研究了不同热解条件对生物质炭产率、pH、元素组成、表面特征、吸附性能的影响,并根据吸附性能筛选出各生物质炭的最优制备工艺。结果表明,热解温度为500℃、热解时间为2h、污泥与玉米秸秆、芝麻秸秆配比为1∶1时,污泥与水稻秸秆、小麦秸秆配比为1∶2时,制备的生物质炭吸附性能最优。最优制备工艺条件下,4种生物质炭吸附性能相比：SWBC > SRBC > SCBC > SSBC。     

不同粒径污泥热解制备生物炭及其特性分析

以3种不同粒径污泥为原料,采用固定床反应器在500℃下制备生物炭。考察了3种不同粒径污泥的热解特性及其生物炭中重金属的分布特征,并运用TCLP对污泥及其生物炭的重金属浸出毒性进行了系统研究。结果表明,随着污泥粒径的增大,热解生成的生物炭和热解气产率均有所降低,而焦油产率则逐渐升高;在3种不同粒径污泥热解过程中,重金属除As外主要富集在固体产物生物炭中,相对富集系数均高于90%。随着污泥粒径的增大,污泥中Cu、Zn和Ni的含量增加,而Cr和Pb的含量则减少;虽然3种不同粒径污泥制备的生物炭中重金属的浸出规律不一致,但是污泥热解可以有效抑制重金属的浸出。生物炭中除As和Zn外其他重金属元素的浸出率均低于3.0%。     

Photochemical and acoustic interactions of biochar with CO2 and H2O: Applications in power generation and CO2 capture

A critical literature review suggests that carbonaceous compounds react with (CO₂ +H₂O) mixture through thermal, photochemical, and sonochemical/sonophysical routes. A biochar was selected for studying these effects at 60°C and 1 atm for its potential benefits on power generation and CO₂ capture. All treatments remove sizable minerals (K, Na, and Si) detrimental in power generation, and introduce carbon (up to 16% of original carbon in biochar) into the biochar matrix. Most treatments show increased hydrogen (up to 24%). Treatments lead to notable increased heating value of biochar (up to 50%). Treated biochars show increase (up to 19 fold) in internal surface area. The ultrasound energy output is a fraction of the increased heating value. Thus, pretreatment is potentially attractive for increasing the energy efficiency in combustion and gasification. Moreover, better understandings of the salient reactions of these processes will be advantageous for the development of advanced adsorbents for CO₂ capture. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1054–1065, 2014     

Enhanced Lead Sorption by Biochar Derived from Anaerobically Digested Sugarcane Bagasse

This study examined the ability of two sugarcane bagasse biochars to remove lead from water. The sorption of lead by biochars made from raw (BC) and anaerobically digested sugarcane bagasse (DBC) was compared with a commercial activated carbon (AC) using batch sorption experiments. DBC was a more effective sorbent of lead from water than AC, and far more effective than BC. The maximum lead sorption capacity of DBC (653.9 mmol kg^?1) was about double that of AC (395.3 mmol kg^?1) and about twenty times higher than that of BC (31.3 mmol kg^?1). Post-sorption characterizations using X-ray diffraction (XRD) and scanning electron microscopy (SEM) indicated that the enhanced sorption of lead by DBC was at least partly related to a precipitation mechanism, while surface adsorption was the principal mechanism of sorption of lead onto BC. These results suggest that biochars made from bagasse and other agricultural residues may be effective alternative, low-cost environmental sorbents of lead or other metals. In addition, the enhanced lead sorption ability of the digested bagasse biochar introduces the possibility of developing a novel carbon production method to use anaerobic digestion as a means of biological activation to create high-efficiency sorbents.     

水热制生物炭对含Cr(Ⅵ)废水吸附特性的研究

用废弃生物质制备生物炭以期提供处理含重金属废水的低成本、环境友好的材料。实验探讨了生物质炭的制备及生物质炭处理含Cr(Ⅵ)废水的影响因素。结果表明,相同的制备条件下,玉米芯生物炭的吸附效果优于松子壳生物炭。对于200mL50mg/L的含Cr(Ⅵ)废水,当pH=2,转速为100r/min时,室温下0.2g生物质炭在10min内对Cr(Ⅵ)的吸附率可达99.20%。吸附反应较好地符合拟二级动力学。在功率为800W的定频微波中对吸附后的样品进行解吸,30min后样品中基本不存在Cr(Ⅵ)。     

Cassava (Manihot esculenta Crantz) stump biochar: Physical/chemical characteristics and dye affinity

Aiming investigated the pyrolysis of the agricultural waste known as cassava stump, the portion of the plant to which the tuberous roots and aerial parts of the plant are attached, this study had as objective to produce biochars from cassava stump by conducting vacuum pyrolysis at 400, 500, or 600?°C. The biochars were characterized by proximate analysis, thermogravimetric analysis, Fourier-transform infrared absorption spectroscopy, X-ray diffraction, scanning electron microscopy, and nitrogen adsorption. Adsorption affinity tests were performed with four different dyes: methylene blue, basic fuchsin, acid fuchsin, and alizarin. Biochar obtained at 500?°C, heating rate of 20?°C.min^?1, and 90?min of residence at the final temperature, had 22% higher fixed carbon content as compared to the other biochars and 3.16 times greater fixed carbon content than the original cassava stump. This biochar showed the best adsorption capacity (0.0679?mmol/g) and percentage of removal (87.6%) of methylene blue dye from aqueous solution. The material characterization reveals that biochars from Manihot esculenta Crantz stump may have potential application in carbon sequestering. Besides that, these biochars could be applied with efficiency as adsorbent of dyes.     

炭化工艺对脱水沼渣炭理化性质的影响

以一级脱水沼渣为原料,通过热重-红外联用分析其失重行为及热解气相产物的组成,采用单因素试验方法,考察炭化温度、升温速率、保温时间对沼渣炭的得率、理化性质的影响。结果表明：360～480℃区域为热解的主要阶段。随着温度的升高,炭得率、挥发分含量降低,灰分含量增加,固定碳含量在700℃最高（18.37%）;随着升温速率提高,灰分、固定碳含量提高,炭得率及挥发分含量降低;随着保温时间的延长,炭得率逐渐降低,对灰分、挥发分、固定碳影响不显著;原料及炭热值较低;重金属Cd和Pb含量低于“有机-无机复混肥料”标准限值（GB 18877—2009）;Hg和Cr含量较低,符合肥料用有害重金属元素限值标准,而有益于植物生长的元素Mn和Zn含量较高,本研究为减量化处理复杂沼渣提供了理论依据。     

9种树叶生物炭作为染料敏化太阳电池对电极的光电性能

将9种由树叶经单步热解获得的生物炭作为对电极催化材料引入染料敏化太阳电池（DSSC）,并在分析生物炭的组织结构和电化学性能的基础上,着重探讨了引起器件光电性能差异的内在原因。结果表明：9种树叶热解获得的生物炭组装的DSSC的转换效率在1.00%~1.85%之间,其中棕叶最佳,樟树叶和杨树叶其次,三者的转换效率均高于1.3%,随后依次为枫叶、红继木叶、椿树叶、杉树叶和松针,桂叶最低。生物炭的孔隙结构是引起相应器件光电性能各异的主要原因。由于棕叶生物炭具有独特的取向孔隙,能缩短电解质扩散距离以及提升催化活性,因此其器件的转换效率最佳。此外,9种生物炭器件的转换效率均高于石墨器件（0.77%）。更优的光电性能主要归功于生物炭具有的多级孔结构和玻璃态碳骨架。     

The surface acidity of acid oxidised multi-walled carbon nanotubes and the influence of in-situ generated fulvic acids on their stability in aqueous dispersions

The oxidation of multi-walled carbon nanotubes (MWCNTs) with nitric acid was studied. In addition to the formation of oxygen-containing surface functional groups, the oxidative digestion of graphene caps and layers generated polycyclic aromatic substances, classified as fulvic acids (FAs). The latter remained immobilised on the MWCNT surface in acidic and neutral solutions but were released in basic pH solutions, which were subsequently separated, purified and characterised by high-performance liquid chromatography and mass spectrometry. Using acid-base titrations, the number of surface acidic functional groups was determined, which was shown to significantly decrease after FAs were removed. Depending on the length of oxidation, FAs account for up to 43% of the surface acidity of MWCNTs. The protonated solubilised fulvic acids can be readsorbed on the surface of oxidised or unfunctionalised MWCNTs, which assists the stability of carbon nanotube suspensions in the aqueous phase.     

Biochar soil amendments for increased crop yields: How to design a “designer” biochar

The development and testing of a transient adsorption/desorption model that describes the response of biochar particles to nutrient pulses simulating the application of fertilizer is presented in this study. Intraparticle nutrient transfer occurs both by diffusion through liquid‐filled pores and by surface diffusion, and nutrient adsorption is described by Langmuir–Freundlich (Sips) isotherms. Simulation results show that the ability of a biochar to adsorb and then slowly release the nutrient is modulated by a complex interplay of external mass transfer, intraparticle diffusion (both pore and surface diffusion), and adsorption dynamics. The nutrient retention potential of biochar‐amended soils is quantified and is shown to depend on multiple factors that include chemical and physical biochar properties, soil permeability, water flow, and the method of fertilizer application. These findings may explain why biochars with similar properties can potentially have widely different impacts on crop yields, as has been repeatedly reported in the literature. © 2017 American Institute of Chemical Engineers AIChE J, 63: 5425–5437, 2017