油砂燃烧特性与动力学的分布活化能模型

采用美国Pyris1TGA热重分析仪对印度尼西亚油砂进行了燃烧特性实验,并分析了升温速率等因素对油砂燃烧反应特性的影响,求得了着火温度、燃烧稳定性判别指数和燃烧反应性能参数等值。通过数据分析,利用分布活化能模型确定了印度尼西亚油砂在整个燃烧过程中活化能随着转化率的变化关系,反应初始阶段,2种油砂的活化能在50—90 kJ/mol之间;STB与STC转化率在0.28和0.27时活化能最大,分别为226 kJ/mol和103 kJ/mol。转化率大于0.6时,STB活化能为200 kJ/mol,STC活化能为160 kJ/mol。还分析了活化能和频率因子之间的补偿效应,为油砂的有效开发与经济利用提供了理论依据。     

油砂燃烧特性与动力学的分布活化能模型

采用美国Pyris1TGA热重分析仪对印度尼西亚油砂进行了燃烧特性实验,并分析了升温速率等因素对油砂燃烧反应特性的影响,求得了着火温度、燃烧稳定性判别指数和燃烧反应性能参数等值。通过数据分析,利用分布活化能模型确定了印度尼西亚油砂在整个燃烧过程中活化能随着转化率的变化关系,反应初始阶段,2种油砂的活化能在50—90 kJ/mol之间;STB与STC转化率在0.28和0.27时活化能最大,分别为226 kJ/mol和103 kJ/mol。转化率大于0.6时,STB活化能为200 kJ/mol,STC活化能为160 kJ/mol。还分析了活化能和频率因子之间的补偿效应,为油砂的有效开发与经济利用提供了理论依据。     

汪清油页岩燃烧反应动力学研究

采用Pyris-1TGA热重分析仪测定汪清油页岩不同升温速率(20,50,80,100℃/min)下的一组燃烧TG曲线,根据Popescu提出的一种新的多重扫描法,将不同机理函数式进行线性回归。结果表明,该油页岩燃烧反应符合三维扩散机理,从而确定了该油页岩机理函数的积分式与微分式,获得了活化能与频率因子的值。取转化率为0.1,0.2,…,0.9,将冉全印-叶素温度积分近似式与所求机理函数结合,利用迭代法求出转化率-温度的理论值。结果发现,理论TG曲线与实验曲线吻合较好,表明了所求得的油页岩燃烧机理函数的合理性。     

芦竹燃烧动力学不同反应机理的研究

利用热重分析仪进行了芦竹的燃烧试验,采用Coats-Redfern法分析热重曲线,研究不同升温速率(10,20,30℃/min)对燃烧过程的影响。结果表明,芦竹燃烧过程可分为3个阶段,即水分析出、挥发分析出与燃烧及焦炭表面燃烧三个阶段。主要反应集中在第二和第三反应阶段。随着升温速率的增大,最大失重速率增大,三个阶段向高温方向偏移。挥发分析出与燃烧及焦炭表面燃烧阶段的反应机理均满足随机成核A3模型,挥发分析出及燃烧阶段的活化能平均值为21.49 k J/mol,频率因子变化为1.31×10³3¹.83×101.83×10³min3min^(-1);焦炭表面燃烧阶段的活化能平均值为47.15 k J/mol,频率因子变化为325×10(-1);焦炭表面燃烧阶段的活化能平均值为47.15 k J/mol,频率因子变化为325×10³3⁷4.9×1074.9×10³min3min^(-1)。     

芦竹燃烧动力学不同反应机理的研究

利用热重分析仪进行了芦竹的燃烧试验,采用Coats-Redfern法分析热重曲线,研究不同升温速率(10,20,30℃/min)对燃烧过程的影响。结果表明,芦竹燃烧过程可分为3个阶段,即水分析出、挥发分析出与燃烧及焦炭表面燃烧三个阶段。主要反应集中在第二和第三反应阶段。随着升温速率的增大,最大失重速率增大,三个阶段向高温方向偏移。挥发分析出与燃烧及焦炭表面燃烧阶段的反应机理均满足随机成核A3模型,挥发分析出及燃烧阶段的活化能平均值为21.49 k J/mol,频率因子变化为1.31×10~3~1.83×10~3min~(-1);焦炭表面燃烧阶段的活化能平均值为47.15 k J/mol,频率因子变化为325×10~3~74.9×10~3min~(-1)。     

印尼油砂热重红外及基于AKTS动力学分析

通过热重分析仪、傅里叶红外光谱仪和质谱仪对印尼油砂的热解过程和热解产物进行了探究,基于不同升温速率下的TG-DTG曲线,将热解过程分为两个阶段,即热解低碳化合物析出段和无机物高温受热分解段。升温速率相同时,YN₂油砂比YN1油砂挥发分析出的温度低。油砂热解产物是由脂肪烃、芳香烃、含氧官能团和羟基等组成的混合物,利用傅里叶红外光谱仪探究印尼油砂在不同升温速率下气体产物H₂O、CO₂、CO、CH₄、C_nH_m等的析出特性,气态烃类、含氧有机物等有机气体是由羰基和羧基以及甲氧基、亚甲基、甲基在热解低温段受热分解产生的,根据质谱图,确定了各个时刻逸出气体的种类和产量。利用AKTS软件基于F-W-O和Kissinger模型计算了油砂脱挥发分的热解动力学参数,计算结果表明,在相同的转化率下,不同升温速率的活化能呈线性分布,YN1的活化能高于YN₂的活化能。     

果壳生物质燃烧特性与动力学分析

为充分利用果壳生物质废弃物,采用热重分析对油茶壳、核桃壳、澳洲坚果壳进行了燃烧实验研究,考察了不同升温速率下3种果壳生物质的燃烧特性及动力学参数。结果表明：3种果壳生物质燃烧特性不同,但燃烧特性参数均随升温速率升高而增大;随着升温速率的增加,着火点、燃尽温度、最大燃烧速率、平均燃烧速率及综合燃烧特性指数提高;10℃/min时,油茶壳、核桃壳、澳洲坚果壳综合燃烧特性指数分别为0.56×10^-7、1.18×10^-7、0.88×10^-7;3种果壳生物质的燃烧反应遵循一级反应动力学模型,相关系数（R²）均达0.93以上,低温阶段活化能为30.40~52.41 kJ/mol,高温阶段活化能为18.49~40.62 kJ/mol,低温阶段活化能均大于高温阶段。     

利用燃烧指数分析生物质型煤的燃烧特性

分别选用焦作无烟煤、山西烟煤、陕西神木烟煤、平顶山烟煤四种原煤和其生物质型煤,通过不同煤种原煤和生物质型煤的热重分析实验,计算原煤和生物质型煤的着火、稳定燃烧和燃尽特性指数.分析得出:灰分和挥发分是影响生物质型煤燃烧特性及其燃烧特点的主要因素.     

油砂沥青质对油砂沥青中甲苯残留的影响

利用热重质谱联用仪（TG-MS）分析了三种油砂沥青（印尼油砂沥青、伊朗油砂沥青、加拿大油砂沥青）中的甲苯残留以及油砂沥青质含量对油砂沥青中甲苯残留的影响,并在此基础上,进一步研究了油砂沥青质中的甲苯残留。结果发现,不同油砂沥青中甲苯残留量存在一定差异,其中印尼油砂沥青中的甲苯残留量最多。进一步对沥青质质量分数分别为10%、19%、30%的油砂沥青样品进行热重质谱实验,发现随着油砂沥青中沥青质含量的增加,甲苯的残留量会成倍增加。以加拿大油砂沥青质为例,研究了油砂沥青质对溶剂残留的影响,发现油砂沥青质具有对甲苯分子的夹带能力,导致甲苯分子在超过自身沸点40℃以上才能从沥青质中分离出来。油砂沥青中其他组分的存在也会加剧沥青质对甲苯的夹带作用。此外,研究还发现,在350~650℃时,油砂沥青质可以热解产生甲苯,而且油砂沥青中的沥青质含量越高,热解生成的甲苯越多。     

Composition of oils produced during an echoing, in-situ combustion of a Utah tar sand

The Laramie Energy Technology Center (DOE) has completed its second in-situ combustion experiment (TS-2C), which was carried out in the Northwest Asphalt Ridge tar sand deposit near Vernal, Utah. During the experiment (183 days) 92 m³ (580 barrels) of oil was produced, 25% of the original oil in place. The in-situ process utilized is best described as a series of reverse- and forward-combustion phases or echoes traversing the 405 m² (0.1 acre) pattern. Several of the chemical and physical properties of the oil produced are significantly altered with respect to the original bitumen. These include pour point, specific gravity, average molecular weight, wax and nickel content, and the percentage of residue boiling at >538 °C (1000 °F). These and other changes effected on the bitumen during this experiment result in a product oil that closely resembles a heavy fuel oil.     

Preparation of bitumen from oil sand by ultracentrifugation

Ultracentrifugation was investigated as a means to obtain solvent-free bitumen from oil sand. The bitumen from three oil sands of varying grades was separated by placing the sands in specially designed tubes and centrifuging for 2 h at 198 000 at 20 °C. For all grades of oil sand, approximately 70% of the bitumen was recovered. The recovered bitumen was compared to the residual remaining on the sand, and to that extracted by the conventional Soxhlet technique. The ultracentrifuged bitumen contained some emulsified water and a small amount of fine solids. The solvent-extracted material was water-free, but contained a small amount of residual solvent and fine solids. The ultracentrifuge caused some fractionation of the bitumen, resulting in a product slightly enriched in asphaltene components compared to the solvent-extracted material. The residual bitumen remaining on the sand was correspondingly slightly depleted in asphaltenes. However, as evidenced by gas Chromatographic simulated distillation data, ultracentrifugation did retain the light (180–220 °C) components of the bitumen which were lost during the solvent removal step following solvent extraction. Other analyses such as density, viscosity and elemental composition verified that ultracentrifugation resulted in some fractionation of bitumen components.     

Preparation of bitumen from oil sand by centrifugation

Centrifugation was shown to have certain advantages over solvent extraction for the separation of bitumen from oil sand for research purposes. No fractionation of the bitumen during centrifugation was detected by chemical analysis. Some limitations of the method are pointed out.     

新疆托里油砂分段热解机理

在热重分析仪中考察了不同升温速率下油砂的热解特性,结果表明:油砂样品失重过程分为少量气体脱附、低温热解、主要热解、半焦缩聚4个阶段。通过微型固定床与在线质谱耦合测得的气体释放顺序为CO₂、CO、C₂H₆、CH₄和H₂,所对应的初释温度分别为155、178、146、174、354℃。结合核磁和红外对不同温度段液固产物的化学结构进行分析,发现350℃前主要是油砂中轻质油脱附,还包括羧基和烷基侧链的断裂,轻质油品中芳碳率达7.92%;350～520℃之间为油砂的主要热解阶段,油砂油结构中芳碳率为23.51%。据Coats-Redfern法计算得到油砂低温热解和主要热解段的活化能分别为27.63和90.30 kJ·mol^-1,说明开环与裂解反应所需活化能大于油砂油脱附、羧基分解和弱键断裂反应的活化能,揭示了分段热解机理。     

Bitumen—sand interaction in oil sand processing

Bitumen—sand interaction was studied as a function of pH, particle size, temperature and solvent addition to bitumen. Sand particles can be easily detached from the bitumen surface at pH> 6. At pH < 6, strong attachment between bitumen and sand is observed. The bitumen—sand interaction is also particle-size dependent: the finer the particles, the stronger the attachment. The detachment of coarse particles from bitumen can be achieved by increasing the alkalinity of the solution, but not for fine particles, indicating that the particle size is one of the critical factors affecting liberation of bitumen from sand. Increasing temperature has two effects: it is not only reduces the viscosity to facilitate bitumen liberation, but also increases the electrostatic repulsion between sand and bitumen. This is confirmed by the DLVO theory and is in agreement with the batch extraction results on real oil sands.     

油页岩半焦燃烧反应活性分析

采用美国Perk in E lm er公司生产的Pyris1 TGA热重分析仪,对桦甸油页岩半焦进行燃烧特性试验研究,得到3种不同升温速率下的油页岩半焦燃烧特性曲线,并使用平均质量反应性指数和燃烧稳定性指数对半焦反应性加以评价。油页岩半焦燃烧分燃烧快速段、过渡段和燃烧慢速段3个阶段进行。随着升温速率的提高,在燃烧快速段,表观活化能为133.901 3—100.204 2 kJ/mol;在燃烧慢速段,表观活化能为146.317 1—211.409 3 kJ/mol。利用Coats-Redfern法确定了燃烧快速段反应级数为3,而燃烧慢速段则为5.5,从而得到油页岩半焦燃烧化学反应的动力学参数,为油页岩半焦的有效开发与经济利用提供了理论依据。     

Characterization of unextractable organic matter associated with heavy minerals from oil sand

Considerable quantities of organic matter are associated with heavy metal minerals recovered from Suncor aqueous sludge. This organic matter is not extractable with common organic solvents. Attempts were made to concentrate this organic matter by dissolving the mineral matter in acids. Various soluble fractions were also obtained by extraction with methanol/benzene (1:4) after each dissolution step. All these fractions were analysed by elemental analysis, infrared, proton and ¹³C nuclear magnetic resonance spectroscopy.     

油砂分离剂的实验研究

油砂是非常规能源的一种,随着国际油价的不断攀升,油砂分离技术的研究引起广大学者的重视。本文针对内蒙古图牧吉水润型油砂进行其分离剂的研究工作。结果表明,自制分离剂FLJ中加入3%体积的沸点小于350℃的页岩油可以提高油砂洗油率的3.37%。