无烟煤对超临界态CH4-CO2气体吸附特性研究*

为探究无烟煤对超临界态CH4-CO2混合气体的吸附特性,采用重量法开展无烟煤对纯CH4与纯CO2气体、3种体积浓度CH4-CO2混合气样的超临界等温吸附实验,应用过剩吸附理论和Langmuir单层吸附理论,通过校正绝对吸附量、计算吸附相密度、煤的比表面积以及测定吸附平衡后游离态气体组分,探究由亚临界状态到超临界状态下无烟煤吸附纯CH4、纯CO2以及混合气体的吸附相密度变化特征、混合气吸附特征以及吸附分子层数。研究结果表明:煤对纯CH4与纯CO2、混合气体过剩吸附量随着压力增大呈现出先增大后减小的峰值型曲线;CH4绝对吸附量随吸附压力增大不断增大,接近CH4临界压力时,绝对吸附量缓慢增加并趋于稳定。低压下CH4在煤颗粒中以单层吸附为主;超过临界压力后出现表面局部2层吸附的现象;1~3 MPa 时,CO2在煤颗粒中即表现出2层吸附为主的现象,随压力增大甚至出现局部4层吸附的现象,煤颗粒对CO2有更大的吸附能力。     

Preparation of Co–MgO mixed oxide nanocatalysts for low temperature CO oxidation: Optimization of preparation conditions

In this study, a series of Co–MgO mixed oxides (30 wt.% Co) were prepared by co-precipitation method and employed as catalyst in low temperature CO oxidation reaction. The preparation conditions were optimized by the Taguchi method of experimental design to synthesize a sample with high catalytic performance toward CO oxidation reaction. The effects of four variables, pH of solution, aging temperature, aging time and molarity of precursor solution at three levels were investigated. The optimized sample was characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of oxygen (O₂-TPD), N₂ adsorption/desorption, thermal gravimetric and differential thermal analysis (TGA/DTA), and transmission electron microscopy (TEM) techniques. The results revealed that the optimized sample showed a mesoporous structure with a narrow pore size distribution centered in the range of 7–17 nm and particle size about 5.5 nm. It was found that the molarity of solution and aging time had the most influence on the CO conversion, respectively. The catalytic results showed that the highest CO conversion obtained from samples synthesized by Taguchi orthogonal array was about 90% at 200 °C, while the CO conversion for optimized sample was 95%. In addition, the effect of operational conditions was studied over optimized sample.     

CO在烟煤中吸附与扩散的分子模拟研究*

为揭示CO在烟煤中的微观吸附和扩散机理,利用Wiser烟煤分子模型,通过巨正则蒙特卡洛（GCMC）和分子动力学方法,研究5种不同温度（293.15,303.15,313.15,323.15,333.15 K）下,压力为0.1～3.0 MPa时CO吸附量、吸附热的变化,采用能量分布分析CO在烟煤中的吸附行为,利用扩散系数和扩散活化能研究CO在烟煤中的扩散特性。研究结果表明:CO在烟煤分子中的模拟结果符合朗格缪尔（Langmuir）吸附规律,随着温度的升高,Langmuir参数a和b减小,CO在烟煤分子中饱和吸附量和吸附能力降低。温度越高,烟煤分子的等量吸附热越低,烟煤分子吸附CO分子的平均等量吸附热为21.20～23.11 kJ/mol,小于42 kJ/mol,属于物理吸附;随着压力的升高,CO分子由能量较高的优势吸附位点逐渐向相对较弱的吸附位点移动;在模拟的温度和压力条件下,CO在烟煤分子模型中的扩散系数随温度和压力的升高而增加,扩散活化能随压力的升高而减小。研究结果为揭示CO在烟煤分子中微观吸附与扩散规律,准确预测采空区封闭火区煤自燃情况具有重要意义。     

Removal mechanism of trace oxytetracycline by aerobic sludge

To investigate the mechanism of removal of selected pharmaceuticals in activated sludge systems, laboratory-scale batch experiments were conducted to assess the adsorption and degradation behavior of trace oxytetracycline (OTC). The adsorption equilibrium of OTC was observed in 30 min and the adsorption process could be well described by a pseudo-second-order model with a rate of 0.362 L μg^?1 min^?1. The OTC adsorption rate decreased with increasing temperature and could be fitted by the Freundlich isotherm. The linear partition coefficients (K_d) were 1.19, 0.999, and 0.841 L g^?1 at temperatures of 15, 20, and 25 °C, respectively. Thermodynamic analysis revealed that the adsorption of OTC onto the inactivated sludge was spontaneous (ΔG = ?16.7 to ?17.0 kJ mol^?1), enthalpy-driven (ΔH = ?24.9 kJ mol^?1), entropy-retarded (ΔS = ?27.4 J (mol K)^?1), and predominantly a physical adsorption.     

粒径损伤对原生煤和构造煤孔隙结构与分形特征的影响*

为了分析构造煤与原生煤因孔隙结构不同而导致的内部瓦斯存储和运移所存在的差异性。结合低温液氮实验,分析2种煤样的孔隙特征参数与分形维数之间的关系,发现破碎作用对原生煤和构造煤孔隙的破坏路径略有区别。对于原生煤,破碎作用先作用于较大孔隙,之后对微孔产生影响;而对于构造煤,破碎作用直接对较大孔隙和微孔隙产生影响。研究结果表明:原生煤孔隙表面越粗糙、微孔比表面积越大,吸附能力越强;构造煤孔隙结构越复杂、微孔孔容越大,吸附能力越强。研究结果可为构造煤与瓦斯突出的防治提供研究基础。     

粒状煤和块状煤等温吸附CH4试验研

为探究不同尺寸煤样吸附瓦斯特性的差异,以漳村矿3#煤为研究对象,利用自主研制的多功能煤吸附/解吸瓦斯参数测定试验装置,开展粒状煤和块状煤的等温吸附试验,测定不同吸附压力下的吸附量和变形量。试验结果表明:在相同的吸附平衡压力下,吸附量随煤样粒径的增大而减小;粒状煤吸附瓦斯的能力大于块状煤,原因是粒状煤的有效比表面比块状煤大,增加的微孔吸附瓦斯使得煤吸附瓦斯量增加。块状煤的变形量随吸附平衡压力而增大,但增加量逐渐减小。经讨论分析可知:煤体吸附膨胀变形是煤基质吸附膨胀和气体压力压缩共同作用的结果;粒状煤测定的吸附常数应用到煤层数值模拟中会引起一定的误差。     

注气条件对CO2置换驱替CH4影响的实验研究*

为研究不同注气压力与注气温度对CO2置换驱替煤层CH4的影响规律,利用Materials Studio分子动力学模拟软件,通过煤体在2元组分混合气体间的竞争吸附量、竞争吸附热及能量分布等变化规律,从微观研究煤吸附CH4与CO2之间的机理,并利用物理实验平台,选用3种高变质程度煤进行注CO2置换驱替CH4实验。结果表明:同一种变质程度煤,随着注气压力或注气温度的增大,置换率呈增长趋势、驱替比呈下降趋势、CO2突破时间变短;相同注气压力与注气温度时煤的变质程度越高,置换效率越大、驱替比越小、CO2突破时间越长。并且注气压力对于CO2置换驱替CH4的效果要优于注气温度。     

Artificial neural network modelling of As(III) removal from water by novel hybrid material

The present study reported a method for removal of As(III) from water solution by a novel hybrid material (Ce-HAHCl). The hybrid material was synthesized by sol–gel method and was characterized by XRD, FTIR, SEM–EDS and TGA–DTA. Batch adsorption experiments were conducted as a function of different variables like adsorbent dose, pH, contact time, agitation speed, initial concentration and temperature. The experimental studies revealed that maximum removal percentage is 98.85 at optimum condition: pH = 5.0, agitation speed = 180 rpm, temperature = 60 °C and contact time = 80 min using 9 g L⁻¹ of adsorbent dose for initial As(III) concentration of 10 mg L⁻¹. Using adsorbent dose of 10 g L⁻¹, the maximum removal percentage remains same with initial As(III) concentration of 25 mg L⁻¹ (or 50 mg L⁻¹). The maximum adsorption capacity of the material is found to be 182.6 mg g⁻¹. Subsequently, the experimental results are used for developing a valid model based on back propagation (BP) learning algorithm with artificial neural networking (BP-ANN) for prediction of removal efficiency. The adequacy of the model (BP-ANN) is checked by value of the absolute relative percentage error (0.293) and correlation coefficient (R² = 0.975). Comparison of experimental and predictive model results show that the model can predict the adsorption efficiency with acceptable accuracy.     

复合惰气在采空区遗煤中竞争吸附的分子动力学模拟研究*

为明确作用于采空区的复合惰气的竞争吸附,进行不同温度、压力及组分下烟煤对N2、O2、CO2多元气体竞争吸附分子的模拟研究。研究结果表明:当注入压力达到3 MPa后,竞争吸附效果不再明显,为高压注入提供一定的理论基础;随着CO2分压的增大,O2吸附量降低速度逐渐平缓,初步确定最佳注入配比范围为2∶1至3∶1,为进一步结合实际工程中成本等因素确定最佳注入配比提供参考;等量吸附热受吸附条件的影响较小,仅与吸附质本身有关;随着CO2分压的增大,范德华能升高56.9%,分子内能升高78.7%,静电能升高67.2%,CO2对整个系统内的吸附作用强度及吸附量有着较大的影响;随着CO2分压增大,N2竞争吸附能力逐渐弱于O2,竞争吸附能力大小顺序为CO2>O2>N2。     

Synthesis of CuO nanoparticles through green route using Citrus limon juice and its application as nanosorbent for Cr(VI) remediation: Process optimization with RSM and ANN-GA based model

In present investigation, an attempt has been made for the synthesis of cupric oxide nanoparticles (CuONPs) through a green route by utilizing lemon juice extract as a bioreductant. The synthesized CuONPs were characterized through UV–visible spectroscopy, Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The CuONPs were utilized for Cr(VI) removal from water through adsorption method in batch mode at different initial Cr(VI) concentration, pH, temperature and CuONPs dosage. The maximum uptake capacity of CuONPs was found to be 16.63 mg of Cr(VI)/g at pH 4.0. Implementation of response surface methodology (RSM) followed by artificial neural network hybridized with genetic algorithm (ANN-GA) approach has resulted maximum Cr(VI) adsorption of 98.8% under the optimized conditions of initial metal concentration 22.5 mg/L, pH 3.81, CuONPs dose 1.28 g/L and temperature 37.1 °C. Under optimum conditions, adsorption isotherm study was conducted, which showed that the fitness of experimental data was well achieved with Langmuir isotherm model illustrating monolayer pattern of adsorption. Thermodynamic study revealed that the process was spontaneous and endothermic in nature, while adsorption kinetics was best explained by pseudo-second order kinetic model.     

两种有机酸对茶园土微团聚体等温吸附锌的影响

为了明确茶园紫色土Zn容量及潜在污染状况,利用虹吸沉降和离心冻融法进行批量培养,研究区域土壤及不同粒径微团聚体等温吸附Zn~(2+)的水平,以及去除有机质和外源添加柠檬酸、乙二胺四乙酸(EDTA)对吸附的影响。结果表明:1)以专性吸附为主的多层吸附随Zn~(2+)质量浓度增至200 mg/L总体接近饱和,吸附量从大到小依次为0.002 mm、0.002~0.05 mm、原土、0.25~2 mm、0.05~0.25 mm,游离Zn~(2+)向较小粒径富集趋势明显,去除有机质弱化了微团聚体的吸附能力;2)吸附过程为自发吸热反应,热力学Freundlich方程(R2=0.9722~0.9995)整体拟合水平优于Langmiur方程(R2=0.9505~0.9987),土壤吸附能力与有机质、游离氧化铁、CEC呈正相关;3)两种有机酸均以0.1 mmol/L为阈值,随浓度增加均表现为低浓度增强Zn~(2+)积累、高浓度加快迁移,最大吸附量呈"峰形"变化,有机酸浓度"峰值"在去除有机质后增大到1 mmol/L;在未去除有机质土壤及结构单元中,EDTA对Zn~(2+)的释放能力更优,柠檬酸能更好地吸持,大粒径微团聚体0.25~2 mm及原土随有机酸浓度变化吸附量差异明显;去除有机质使两种有机酸促进及抑制功能削弱明显。     

水分对无烟煤瓦斯吸附影响的低场核磁试验研究

为研究水分对无烟煤瓦斯吸附的影响,以山西晋城集团王台铺煤矿无烟煤为研究对象,利用低场核磁共振技术,研究了煤样在不同水分含量下的核磁共振T2谱图,分析了T2谱图核磁信号与瓦斯吸附量的关系。结果表明:煤中水分质量分数较大时,水分在微孔、小孔、中大孔内均有分布;水分含量较小时,水分主要存在于微孔内。瓦斯吸附量随水分增加而减少,但水分对煤瓦斯吸附的抑制程度不同,水分质量分数从0增加到1.92%,水分主要存在于微孔隙中,瓦斯吸附量显著降低;而水分质量分数从1.92%增加到3.09%时,水分主要在小孔隙及中大孔隙内增加,瓦斯吸附量降低幅度较小。微孔隙中水分对瓦斯吸附的抑制作用较明显,随含水量增加,瓦斯吸附速度逐渐降低,吸附平衡所需时间增大。     

Development and physicochemical characterization of a new magnetic nanocomposite as an economic antibiotic remover

Maghemite (ϒ-Fe₂O₃) nanoparticles were impregnated to nanoporous carbon obtained from tomato waste (TWNC). The prepared magnetic composite (MTWNC) was characterized and used to remove tetracycline (TC) from water and then easily be separated from the medium by a magnetic technique. The morphologies and surface chemistries of both magnetic and non-magnetic nanoporous carbons were studied by FTIR, XRD, SEM, SEM-EDX, VSM, BET surface area, proximate and elemental analysis determinations. Batch adsorption studies were carried out and the effects of pH, initial TC concentration, adsorbent dose, ionic strength and temperature were investigated. The adsorption kinetics of TC on MTWNC could be expressed well by the pseudo-second order model, and sorption isotherms were described by Langmuir equation with maximum adsorption capacity of 60.60 mg/g at pH 4 and 50 °C. Thermodynamic parameters showed that the adsorption of TC onto MTWNC was feasible, spontaneous and endothermic. Furthermore, the recyclability of the adsorbent was tested with 0.01 M NaOH solution, and the results show that the synthesized composite adsorbent could be employed repeatedly in wastewater treatment.     

Experimental study on CO and CO2 emissions from spontaneous heating of coals at varying temperatures and O2 concentrations

Laboratory experiments were conducted to investigate carbon monoxide (CO) and carbon dioxide (CO₂) emissions from spontaneous heating of three U.S. coal samples in an isothermal oven at temperatures between 50 and 110 °C. The oxygen (O₂) concentration of an oxygen/nitrogen (N₂) mixture flowing through the coal sample was 3, 5, 10, 15, and 21%, respectively. The temperature at the center of the coal sample was continuously monitored, while the CO, CO₂, and O₂ concentrations of the exit gas were continuously measured. The results indicate that the CO and CO₂ concentrations and the CO/CO₂ ratio increased when the initial temperature was increased. As the inlet O₂ concentration increased, the CO and CO₂ concentrations increased, while the CO/CO₂ ratios tended to converge to the same value. The ratio of CO/CO₂ was found to be independent of coal properties, approaching a constant value of 0.2. The maximum CO production rate correlated well with the maximum coal temperature rise. The apparent order of reaction for coal oxidation was estimated to be between 0.52 and 0.72. The experimental results in this study could be used for early detection and evaluation of a spontaneous heating in underground coal mines.     

Adsorptive removal of basic dyes from aqueous solutions by surfactant modified bentonite clay (organoclay): Kinetic and competitive adsorption isotherm

Cationic surfactant (Hexadecyltrimenthylammonium chloride) modified bentonite clay was prepared and systematically studied for its adsorption behavior as an efficient adsorbent for the removal of basic dyes such as methylene blue (MB), crystal violet (CV) and Rhodamine B (RB) from aqueous phase. Organo modified clay shows better capacity for the removal of three dyes. The adsorption process was found to be dependent on pH and initial dye concentration. The maximum dye sorption was found to be at a pH of 9.0 (99.99% for MB, 95.0% for CV and 83.0% for RB). The adsorption capacity for the dyes was found to be 399.74, 365.11 and 324.36 μmol/g for MB, CV and RB, respectively at 30 °C. The equilibrium uptake was attained within 240 min. The kinetic studies were revealed that sorption follows a pseudo-second-order kinetic model which indicates chemisorption between adsorbent and adsorbate molecules. Adsorption isotherm indicates non-energetically adsorption sites which fit with Freundlich isotherm model. The fitness of kinetics and isotherm models was evaluated by using HYBRID error analysis function. Competitive adsorptions of dyes were studied by using binary component systems.     

Comparison studies of adsorption properties of MgO nanoparticles and ZnO–MgO nanocomposites for linezolid antibiotic removal from aqueous solution using response surface methodology

In this investigation, the adsorption measure of linezolid antibiotic onto MgO nanoparticles and ZnO–MgO nanocomposites were performed. The adsorbents were characterized by different techniques such as XRD, SEM, TEM and BET. The parameters influence such as the pH, adsorbent dosage and temperature was tested and evaluated by Box–Behnken Design combined with response surface methodology. Performing adsorption tests at optimal conditions set as 0.5 g L⁻¹ of adsorbent, pH 10 and 308 K make admit to obtain high adsorption turnover (123.45 and 140.28 mg g⁻¹ for MgO nanoparticles and ZnO–MgO nanocomposites, respectively). A good compromise between predicted and experimental data in this research was observed. The experimental equilibrium data fitting to Langmuir, Freundlich, Tempkin and Dubinin–Radushkevich models indicate that the Langmuir model is a best model for evaluation of adsorption behavior. Kinetic evaluation of experimental data indicated that the adsorption operations followed well pseudo-second-order models. The adsorption capacity of ZnO–MgO nanocomposites is higher than MgO nanoparticles that because of the ZnO–MgO nanocomposites have high specific surface area.     

构造煤原生结构煤微孔特征的多重统计对比及其差异成因机制

孔径小于2 nm的微孔孔隙控制着煤的吸附能力,开展构造煤与原生结构煤微孔特征的对比研究有助于厘清构造煤是否具有超强瓦斯吸附能力。为统计确证构造煤与原生结构煤孔径小于2 nm的微孔孔隙是否存在显著差异,判断造成微孔孔隙特征变化的主控因素并探讨其原因,对鹤壁六矿、平顶山八矿和淮南谢桥矿3组采自同一煤层共生的构造煤与原生结构煤煤样,采用CO2吸附法测定了孔径小于2 nm的微孔孔隙特征参数,并基于CART递归分割、LSD多重比较及多元方差分析等统计分析方法对构造煤与原生结构煤的微孔孔容进行了多重统计对比研究。结果表明:1)构造煤与原生结构煤孔径小于2 nm的微孔孔容没有显著差异;2)构造变形作用对孔径小于2nm微孔孔隙变化的影响远小于变质作用;3)构造煤的吸附能力不是构造煤发育煤层易突出的主要原因;4)煤类微晶结构参数的变化是煤微孔形成的主控因素。     

二氧化碳与水预处理煤样对甲烷吸附热效应特性的实验研究

研究煤体吸附甲烷的热效应对于深入揭示煤层气在煤表面的吸附机理有重要意义。通过C80微量量热仪测试了无烟煤、焦煤、褐煤在二氧化碳与水预处理前后的甲烷吸附热力学参数，得到甲烷的等温吸附曲线和吸附热曲线，并建立了甲烷吸附量—吸附热定量模型，从能量角度解释了煤样预处理前后对甲烷的吸附特性。研究结果表明:经二氧化碳与水预处理后，煤样对甲烷的吸附量以及吸附过程产生的微量吸附热均有所增加，且预处理对煤体造成的影响主要体现在能增大其表面孔隙结构。     

基于经典扩散模型不同粒径粒煤瓦斯扩散特征实验研究

为了获取多尺度粒煤在不同初始吸附平衡压力条件下的甲烷扩散特征，完成了0.25～1.00 mm，＞1.00～3.00 mm，＞3.00～6.00 mm和＞6.00～10.00 mm这4种粒径粒煤在1.0 和3.0 MPa初始吸附平衡压力下的甲烷扩散实验，并考察了经典扩散模型对各实验在0～10 min，0～60 min，0～180 min时间段的扩散拟合效果。研究结果表明:同实验时间，扩散率表现为随着粒径的减小呈增大趋势，0.25～1.00 mm相较＞6.00～10.00 mm粒径粒煤最大增大了73%；经典扩散模型不适用于描述甲烷在粒煤中的全阶段扩散，粒径越小拟合精度越低，仅对于初始扩散阶段（0～10 min）拟合效果较好；同初始吸附平衡压力，初始扩散系数D值随着粒径的增大呈递增趋势，＞6.00～10.00 mm相较0.25～1.00 mm粒煤扩散系数增大至7倍。不同尺度粒煤的瓦斯扩散特征，为煤层气达产、稳产、增产提供了储层改造方向。     

Removal of a cationic bisbiguanide using Functionalized Activated Carbons (FACs)

Functionalized Granular Activated Carbons (FACs) are used as adsorbents for treating pharmaceutical wastewaters containing Chlorhexidine Gluconate. Chemical modifications of Granular Activated Carbons (GACs) using functionalizing agents like HCl and HF produce FACs. The adsorption capacity of each of FAC-HCl and FAC-HF is found to be higher than GAC. The modelled maximum adsorption capacity for FAC-HCl is 1.02 g/g of adsorbent, 3.49 g/g of adsorbent for FAC-HF and 0.0682 g/g of adsorbent for GAC. This is mainly due to the additional chemisorptions by surface complexation at the functionalized surface sites of the modified GACs. This is also supported by the well-known pseudo-second-order kinetic model. Formation of surface complexes with the functional groups and weakly polar Chlorhexidine Gluconate is well supported by the physical characterization using Energy dispersive X-ray spectroscopy (EDAX), Brunner–Emmett–Teller (BET) test and Fourier Transform Infrared spectroscopy (FTIR) analysis after adsorption. The adsorption capacity of GAC and the FACs increases in the order of FAC-HF > FAC-HCl > GAC conforming to the proportion of the total acidity of the carbon surfaces. Intra-particle diffusion is not the sole rate-controlling factor. An agreement to pseudo-second-order kinetic model, Elovich kinetic model and Boyd's film diffusion model proves that chemisorption is the rate-controlling parameter in this adsorption study.