油页岩干酪根热解产物特性研究

采用裂解色谱（PY-GC-MS）、电子顺磁共振波谱（EPR）和红外光谱（FTIR）等技术手段，分析了Estonia油页岩中干酪根及其热解产物的结构特性，研究了不同温度下中间产物与最终产物的关联性。结果显示：油页岩热解符合干酪根热解为中间产物热沥青，热沥青再热解为页岩油、干馏气和半焦等产物反应路径，中间产物热沥青的生成趋势反映了终产物的生成速率变化；H₂、CH₄和C₂~C₅组分主要来自热沥青中脂肪烃的芳构化、芳香族化合物烷基侧链的断裂及含氧化合物的缩聚等，干酪根热解产生的烷烃和烯烃类化合物是产油气的主要组分。干酪根和页岩油的自由基自旋浓度明显低于热沥青和半焦；半焦g值最大，干酪根次之，热沥青和页岩油的g值偏低。     

不同热解工艺下半焦的微观结构特点及其对燃烧性能的影响

摘要：对比研究了3种直立内热炉半焦(熄焦方式分别为水泡熄焦、喷水熄焦及烟气干熄焦)及一种流化床热解半焦的微观结构及燃烧性能。通过对半焦组成、孔隙结构、有机官能团、碳化学结构及半焦微晶结构分析，获得了不同低温热解工艺半焦的组成及微观结构特点，明确了组成及微观结构与燃烧性能之间的关系。结果表明，不同热解工艺半焦的组成和微观结构差异明显，其对半焦的燃烧性能影响显著。干熄焦碳化学结构缺陷比例大，快速热解半焦孔隙结构发0达、挥发分高，与水喷焦相比水泡焦石墨化程度低；水喷焦燃烧性能优于水泡焦，干法所得半焦的燃烧性优于湿法；半焦的挥发分含量决定其燃点，在快升温速率条件下孔隙结构对半焦的燃烧性能影响较大，而慢升温速率条件下有序化度对半焦的燃烧性能影响较大。     

利用热解-气相色谱/质谱联用仪研究减压渣油及其胶质亚组分的热解规律

以长庆减压渣油及其胶质亚组分为原料，利用热解-气相色谱/质谱联用仪对其在不同条件下热解的产物进行分析，考察反应温度和升温速率对减压渣油热解的影响。结果表明：随着反应温度升高，热解产物中低碳烯烃含量增加，汽柴油馏分含量先增加后减小，在700 ℃ 时达到峰值；升温速率为1℃/ms时，汽柴油馏分含量最高；芳碳率越大、缩合程度越高的重胶质裂解能力越差。     

Activated Carbon Supported CaO from Waste Shells as a Catalyst for Biodiesel Production

In the wake of increasing environmental constraints, this work is aimed at developing a catalyst purely prepared from waste biomass source as the raw material. The catalyst is investigated for its applicability in transesterification of vegetable oil with the objectives: (i) to use waste shells of mollusk as raw material for the preparation of activated carbon and CaO; (ii) to use it as heterogeneous catalyst in the transesterification of waste cooking oil; (iii) to optimize the different parameters affecting the transesterification reaction; and (iv) to study its reusability. Under optimized conditions it was observed that a conversion >90% was possible and the catalyst could be reused five times with a slight loss in activity. This study indicates that the biomass source could also be used as a potential raw material in the synthesis of environmentally benign catalysts.     

高分子絮凝剂处理高浓度化妆品原料生产废水研究

化妆品原料生产过程中产生的废水水质成分复杂、有机物含量高、难降解，利用混凝工艺处理该废水能够减缓生化处理单元的负担，提高污水处理效率。为揭示无机高分子混凝剂混凝过程中污染物的去除机制和污泥性质的变化，考察了不同的絮凝剂聚合氯化铝（PAC）、聚合硫酸铁（PFS）、聚合氯化铝铁（PAFC）和助凝剂聚丙烯酰胺（PAM）投加浓度对污染物去除率和污泥性质的影响。采用傅里叶变换红外光谱（FTIR）、X射线能谱（EDX）、扫描电镜（SEM）、热重分析仪（TGA）分析污泥絮体官能团、表面形貌、元素组成和热稳定性的变化，采用三维荧光光谱（3D-EEM）和超滤技术分析出水中有机物分子量的分布规律和有机物成分的变化，优化最佳混凝工艺运行条件。结果表明：进水中的天然有机物（NOM）荧光强度高，有机物分子量主要分布在>100×10³和<3×10³区间，其所占比例分别为22.89%和50.57%。当进水COD为6700~7500 mg/L时，在助凝剂PAM投加浓度为0.03 g/L，PAC、PFS和PAFC投加浓度分别为2.8 g/L、2.8 g/L和3.0 g/L的条件下，COD去除率分别为87.20%、79.89%和83.74%，出水浊度分别为2.54 NTU、9.3 NTU和5.51 NTU，NOM荧光强度大大减弱。其中，PAC+PAM对废水中有机物去除效果最好，出水有机物分子量主要分布在(10~30)×10³和<3×10³范围内，其所占比例分别为31.84%和25.92%，形成的混凝污泥具有较好的热稳定性，污泥表面蓬松,呈多孔网状结构。混凝工艺可吸附脂类大分子物质，提高了高浓度化妆品原料生产废水的可生化性。     

污泥基生物炭处理酸性含U(Ⅵ)废水的效能与机理

通过城市污泥（SS）慢速热解制备污泥基生物炭（SSB），并研究初始pH、投加量、共存离子、吸附时间和温度等因素对SSB去除U(Ⅵ)的影响，探讨吸附动力学和吸附等温线特征。通过元素分析、扫描电镜（SEM）、傅里叶红外光谱（FTIR）、X射线衍射（XRD）和X射线光电子能谱（XPS）分析U(Ⅵ)吸附去除的机理。结果表明SSB去除U(Ⅵ)的适宜条件为：pH=3、投加量1 g/L、吸附时间240 min；在此条件下，在温度30℃时最大吸附量为34.51 mg/g。吸附动力学符合拟二级动力学模型；Langmuir吸附等温模型能更好描述生物炭对U(Ⅵ)的吸附行为。U(Ⅵ)吸附去除机理主要包括静电作用，与Si—O—Si的n-π相互作用，与羟基（—OH）、羧基（—COOH）的配位络合。通过5次吸附-解吸试验发现，U(Ⅵ)去除率和SSB再生率均在80%以上。本研究表明污泥基生物炭具备处理与修复酸性含U(Ⅵ)废水污染的潜力。     

Preparation of Al2O3 coating on TiN coating by polymer-assisted deposition to improve oxidation resistance in coking inhibition applications

In order to inhibit the metal catalytic coking and improve oxidation resistance of single TiN coating, the TiN/Al₂O₃ double layer coatings were designed as a chemically inert coating for methylcyclohexane supercritical pyrolysis. Internal TiN coatings were prepared by atmospheric pressure chemical vapor deposition using TiCl₄–H₂–N₂ system. The external Al₂O₃ coatings with different thicknesses were prepared on the TiN surface by polymer-assisted deposition, and the coating with the most suitable thickness was further annealed at different temperatures of 600, 700, 800 and 900 °C. The morphology, elemental and phase composition of TiN/Al₂O₃ coatings were characterized by SEM, EDX and XRD respectively. The chemical state information of the coating elements was based on Ti 2p, Al 2p core level X-ray photoelectron spectroscopy (XPS) spectra. The results indicated that the external Al₂O₃ coating will partially peel off at 900 °C annealing temperature. The thermogravimetric analysis results indicated that all TiN/Al₂O₃ coatings show better oxidation resistance than single-layer TiN coating. The anti-coking test with methylcyclohexane supercritical pyrolysis showed that the TiN/Al₂O₃ coatings can effectively cover the metal catalytic sites and eliminate metal catalytic coking. However, the acid sites of external Al₂O₃ coating slightly promoted coking, so the anti-coking ratios of TiN/Al₂O₃ coatings were smaller than that of TiN. Thus, the addition of external Al₂O₃ coating can greatly improve the oxidation resistance of TiN coatings with little loss of coking resistance.     

低阶煤热解条件对高炉喷吹半焦燃烧性能及动力学特性的影响

采用热重分析法研究了不同热解条件下半焦的燃烧性能和动力学特征，利用Ozawa法求取动力学参数。结果表明，热解温度越低、保温时间越短时，半焦的燃烧性能越好；热解升温速率对半焦燃烧过程的反应程度影响不大；粒度越大，燃烧性能差异性越明显。热解温度对半焦燃烧性能影响较大，550℃是本研究中制备高燃烧反应性半焦的适宜热解温度。两种不同粒度原煤制得的半焦均随转化率增大，活化能减小。1~3 mm原煤在热解温度为550℃时所得半焦在燃烧过程中符合反应级数模型，化学反应为限制性环节，反应最概然机理函数为f(α)=(1–α)2。     

赤泥对玉米秸秆催化热解生物油的影响规律研究

将经过不同温度煅烧的赤泥与玉米秸秆按照一定质量比混合，在500℃下进行催化热解实验，研究赤泥对玉米秸秆生物油组成的影响规律。经TG-DTG和XRD分析发现：600℃煅烧后赤泥（RM600）中含水矿物失水，1 000℃煅烧后赤泥（RM1000）中碳酸盐类化合物分解完全，并且发生了烧结反应。对生物油进行GC/MS分析发现：经过干燥的赤泥（RM）和600℃煅烧的赤泥对羧酸酮基化反应具有明显促进作用，酸类的量降低，酮类的量相应增加，同时对呋喃类的生成也有促进作用。其中，干燥赤泥降酸作用更明显，玉米秸秆与赤泥质量比1：5时，生物油中酸类的量由未添加赤泥时的23.85%降至0.90%。此外，2种赤泥对糖类和醛类都有抑制作用，而1 000℃煅烧的赤泥发生烧结反应，催化作用大幅降低，对生物油组分影响较小。     

Microwave pyrolysis of polystyrene and polypropylene mixtures using different activated carbon from biomass

In this study, microwave pyrolysis was experimented with mixed types of plastic waste. Two different plastic wastes polystyrene waste (PSW) and polypropylene waste (PPW) were used as feedstock. Carbon and activated carbon were synthesized from different biomass; rice husk (RH), corn husk (CH) and coconut sheath (CS) respectively which are used as microwave susceptors. The effect of impregnation on product yields was studied. Microwave pyrolysis at 900 W and with a polymer to an absorbent ratio of 10:1, produced the highest oil yield of 84.30 wt% when coconut sheath activated carbon (CSAC) was used as an absorbent. The reaction time was 10 min for the complete decomposition of polymer mixtures. Oil properties were determined and a high calorific value of 46.87 MJ kg⁻¹ was obtained. These properties were compared to conventional fuel properties and the product oil has a density of 0.76 g ml⁻¹ and viscosity of 2.4 cSt which is an equivalent fraction obtained to that of gasoline. Product oil has a styrene recovery of 67.58% from microwave pyrolysis. The results demonstrate that, microwave pyrolysis has a great potential for energy recovery from mixed plastic waste and the use of agricultural residues as absorbents enhanced the production efficiency of the process.