油页岩含油率测定方法及其影响因素的研究

借助煤的低温干馏方法及采用自制加热装置和温度控制调节仪,主要针对油页岩中含油率的测定方法以及影响因素进行了研究。实验中采用对油页岩进行低温干馏后测定产物中的水分,从而间接测定油页岩的含油率。同时,对测定过程中的影响因素进行了考察,得到最佳升温速率为15℃/min、干馏终温为500℃、持温时间为20 min、颗粒度<3 mm。     

川北某黑色页岩型铼矿工艺矿物学研究

通过矿相显微镜、扫描电镜、电子探针、X射线能谱元素面分析等多种手段综合研究了川北某黑色页岩型铼矿中铼的赋存状态。样品为黑色页岩,有机碳含量较高。粘土矿物总量为14.6%,黄铁矿含量16.2%,石英含量37.7%。样品具典型的粘土结构,矿物粒度微细。铼有两种赋存状态,一种呈类质同象形式赋存于黄铁矿内,另一种则以分散形式存在。典型黄铁矿测点Re平均含量为0.024%。黄铁矿是Re的重要载体矿物。建议通过浮选分离黄铁矿,从而实现Re的富集。      

油页岩矿物质催化半焦燃烧特性及机理

利用微型流化床反应分析仪（MFBRA）研究了油页岩矿物质催化半焦燃烧特性,重点考察了半焦内部矿物质和外部页岩灰床料对半焦燃烧的催化作用,揭示了流化床反应器中半焦燃烧过程和机理。结果表明：内部矿物质和外部床料对半焦燃烧均具有明显催化作用,而两者共同催化效果最为显著。矿物质中CaO和Fe₂O₃对半焦燃烧具有催化活性,CaO催化作用强于Fe₂O₃。油页岩半焦燃烧反应活化能在60.41~78.97 kJ/mol之间,矿物质的催化作用会明显降低反应活化能。流化床反应器中,矿物质对半焦燃烧的催化作用主要表现在四个反应,即：挥发分裂解和燃烧、半焦表面炭燃烧、半焦内部炭燃烧以及一氧化碳燃烧。     

Preparation of high strength foam ceramics from sand shale and steel slag

Foam ceramics with high strength were successfully fabricated by using sand shale and steel slag as the major materials and SiC as foam agent. The influence of raw materials ratio and heat treatment temperatures on crystalline phases, porosity, mechanical properties and pore structures was investigated via XRF, XRD, SEM, DTA-TG, Micro-CT. The results indicate that the raw materials composed of 94 wt% sand shale and 6 wt% steel slag enable the fabrication of foam ceramics possessing strength of 29.98 MPa, bulk density of 0.821 g/cm³, total porosity of 67.22%, closed porosity of 55.27% and thermal conductivity of 0.08 W/(m·K). Micro-CT result shows that the pores with an average size of 267.05 μm are isolated. Pore wall thickness conforms to normal distribution, and it ranges from 18 to 42 μm. The superior property makes it promising high-strength and lightweight material in application fields, including thermal insulation materials and lightweight building materials.     

钒和铝在含钒页岩草酸浸出液中的赋存状态研究

以某含钒页岩草酸浸出液为对象,研究了钒和铝在含钒页岩草酸浸出液中的赋存状态。首先采用Medusa软件初步确定了钒和铝在草酸体系中的存在形式,然后对钒和铝的负载有机相分别进行红外光谱和质谱研究。结果表明:钒负载有机相萃合物化学式为[(R_4N)_2·VO(C_2O_4)_2],铝负载有机相萃合物的化学式分别为[(R_4N)·Al(C_2O_4)_2]和[(R4N)3·Al(C_2O_4)_3],因此可以确定含钒页岩草酸浸出液中钒主要以VO(C_2O_4)_2~(2-)络合阴离子存在,而铝主要以Al(C_2O_4)_2~-和Al(C_2O_4)_3~(3-)形式同时存在。     

用油页岩渣制备白炭黑的工艺

以油页岩渣为原料,经950℃煅烧4 h, 加入3.30 mol/L NaOH溶液于100℃处理4 h,用HCl酸化至pH 8~9时,SiO2的浸出率为75.8%. 经X射线荧光分析,白炭黑产品中的SiO2纯度为91.8%;经FT-IR检测白炭黑的化学结构为水合二氧化硅;经XRD分析,白碳黑为无定型结构;TEM图像显示白炭黑的形貌近似为球状粒子,平均粒径在50 nm以下. 白炭黑的比表面积(BET)为114 m2/g, pH值为5.5~6.0,加热减量为5.82%, 1000℃灼烧减量为6.16%,产品符合中国行业标准HG/T 3061-1999的要求.     

升温速率对油页岩热解特性的影响

采用热分析方法,在非等温条件下对茂名和桦甸的油页岩进行了热解试验研究。研究了从常温到900℃之间不同升温速率(10,20,40,50,100℃/m in)对油页岩热分解反应的影响以及油页岩的H/C,O/C,Cdaf,Vdaf等因素与(dw/dt)m ax之间的关系。根据试验数据建立了热解动力学模型,利用积分法求得表观活化能和频率因子等动力学参数。试验结果表明,油页岩热解可分为3个阶段,其中第2阶段(200—600℃)是热解反应最激烈的区域,挥发份几乎全部析出。而第3阶段是碳酸盐热解阶段,茂名油页岩由于碳酸盐含量低,此阶段变化甚微。     

桦甸页岩油热加工生产燃料油的研究

对桦甸页岩油重油馏分(＞360 ℃)进行热加工实验,研究了桦甸页岩油重馏分热加工反应的影响因素,并分析了裂解油的基本性质.结果表明:随着反应时间的延长、反应温度的提高,裂解油收率逐渐降低,焦炭收率和气体及损失率逐渐升高;当反应温度为395 ℃、反应时间为2 h时,裂解油的密度、凝点、闪点、运动粘度、残炭、灰分分别为0.875 g/mL、21.50 ℃、64 ℃、19.90 mm2/s、0.400、0.047,裂解油的质量已经达到了20#重柴油的使用要求.     

抚顺页岩油综合利用的研究

为充分合理地利用抚顺页岩油资源,对抚顺页岩油柴油馏分(350℃)进行络合精制实验。结果表明:当溶剂比为0.2、络合比为0.25、络合温度为60℃、络合时间为4h的络合精制条件下,精制油的碱性氮含量由0.30%降低到0.069%。抚顺页岩油柴油馏分通过实验室络合精制后,页岩柴油的碱性氮含量由0.30%降到0.020%。结果表明:应将该页岩油的柴油馏分进行精制生产合格柴油,或是作为低凝点柴油的调和组分;蜡油馏分溶剂脱蜡后,蜡膏通过精制后生产商品石蜡,脱蜡油精制后作为中速柴油机燃料、热裂化或加氢裂化的原料油。     

Optimal design and operations of supply chain networks for water management in shale gas production: MILFP model and algorithms for the water‐energy nexus

The optimal design and operations of water supply chain networks for shale gas production is addressed. A mixed‐integer linear fractional programming (MILFP) model is developed with the objective to maximize profit per unit freshwater consumption, such that both economic performance and water‐use efficiency are optimized. The model simultaneously accounts for the design and operational decisions for freshwater source selection, multiple transportation modes, and water management options. Water management options include disposal, commercial centralized wastewater treatment, and onsite treatment (filtration, lime softening, thermal distillation). To globally optimize the resulting MILFP problem efficiently, three tailored solution algorithms are presented: a parametric approach, a reformulation‐linearization method, and a novel Branch‐and‐Bound and Charnes–Cooper transformation method. The proposed models and algorithms are illustrated through two case studies based on Marcellus shale play, in which onsite treatment shows its superiority in improving freshwater conservancy, maintaining a stable water flow, and reducing transportation burden. © 2014 American Institute of Chemical Engineers AIChE J, 61: 1184–1208, 2015