委内瑞拉减压渣油的热解特性及其动力学研究

采用热重-质谱(TG-MS)联用对委内瑞拉减压渣油在不同升温速率下进行热解实验,研究其热解反应特性,并采用3种等转化率法和分布活化能模型(DEAM)求取减压渣油热解反应的动力学参数。实验结果表明,委内瑞拉减压渣油的热解主要反应温度区间为179～490℃,总质量损失率为77.54%,质量损失峰值在446℃达到最大,最大质量损失速率为317.38μg/min。Flynn-Wall-Ozawa(FWO)法比其他2种等转化率法能更好地描述减压渣油的热解过程,由其计算得到的热解活化能为56.77～178.91 kJ/mol。进一步采用DEAM模型将减压渣油分为4个假定组分,对升温速率为10℃/min条件下的热重分析(TG-DTG)数据进行分峰拟合,求得饱和分、芳香分、胶质和沥青质四组分动力学参数,并据此获得减压渣油总活化能分布曲线。结果表明,委内瑞拉减压渣油活化能主要集中在100～250 kJ/mol范围内,通过加权求和获得平均活化能为190.11 kJ/mol。     

基于TG-FT IR分析的木屑热解机理

采用热重 红外联用（TG-FT IR）方法考察了木屑的热解规律,选择Kissinger和Ozawa 2种算法对木屑热解动力学参数进行估算,并采用固定床实验装置考察了木屑热解反应温度对产物分布的影响。结果表明,在不同升温速率及热解终温为950℃的热解条件下,木屑底物的失重率维持在77%～83%,且热解产物以气相产物为主,包括CO₂、CH₄、CO等;当温度高于200℃时,底物出现明显的热解过程,最高失重率下对应的温度随着升温速率的增加而升高。Kissinger和Ozawa 2种算法得出木屑热解反应活化能E分别为130.14和133.21 kJ/mol,频率因子lnA分别为  26.28和26.47 min^-1。木屑热解较理想的热解温度应控制在700℃以上,此时热解产物以CO、CO₂、CH₄、H₂气体为主;随着温度的升高,CO体积分数迅速下降,H₂体积分数迅速上升,CO₂和CH₄的体积分数基本不变。木屑固定床热解实验结果与其TG-FT IR的结果基本一致。     

煤焦油渣热解特性及动力学分析

采用热重-红外(TG-FTIR)联用技术研究了煤焦油渣在不同升温速率(8、25、50 ℃/min)下的热解特性,得到热解反应特征参数;并利用Freeman-Carroll模型对热解过程进行动力学分析。结果表明：升温速率对煤焦油渣热解反应特征参数具有正相关的影响;对于热解过程,热重曲线呈现明显的三段式分布,升温速率对挥发分的总析出量影响不大;适当提高升温速率使热解产物释放更加集中,挥发分释放更加剧烈,热解速率加快;但过高的升温速率则使挥发分短时间集中释放,颗粒内挥发分与煤焦的接触几率增大,促进了二次反应,二次反应产物沉积在煤焦表面,反而使煤焦产率增大;煤焦油渣的热解反应活化能随升温速率的增加而增大,呈正相关性,适宜的升温速率有利于挥发分的析出和二次反应的发生;热解反应动力学参数在整个反应区间线性拟合效果较好,不同升温速率下的活化能和指前因子存在较好的动力学补偿关系。     

硅铝材料酸性和孔径对减压渣油接触裂化性能影响

以减压渣油为原料，采用热解色谱和热重质谱，考察了无序介孔硅铝材料(JSA)的酸性和孔径对其接触裂化性能的影响。结果表明：在一定的剂/油质量比条件下，当JSA的孔径相近时，随着JSA中弱B酸酸量和总酸量的增加，减压渣油的初始裂化温度逐渐降低，裂化能力增强，裂化产物中汽、柴油馏分的相对质量分数增大，C20+馏分相对质量分数减小；同时，减压渣油接触裂化的生焦率低，JSA上积炭的起始燃烧温度逐渐升高；在酸性相当条件下，JSA孔径小于15.85 nm时，孔径的变化对减压渣油起始裂化温度、裂化产物分布、生焦率、接触剂上的积炭影响不明显；JSA孔径增至15.85 nm以上时，C20-馏分相对质量分数减小，C20+馏分相对质量分数增大。     

含油污泥热解动力学特性研究

采用热重分析仪对胜华炼油厂的含油污泥在氮气气氛下进行热重分析，考察在5 ℃omin-1、10 ℃omin-1和15 ℃omin-1的升温速率下的热重曲线并分析其热解特性，实验结果表明，污泥热解分为二个阶段：水份的析出阶段和有机物的热解反应阶段。对主要的有机物热解阶段采用微分法对实验数据进行回归拟合，确定污泥热解机理方程，并求出反应动力学活化能E和频率因子A。温度范围为200℃-450℃反应级数为2级，温度范围为450℃-900℃反应级数为0.8级，在不同升温速率下两个温度范围的活化能变化不大。     

块状油页岩热解过程的研究——Ⅰ.热解反应动力学参数

对于抚顺及茂名沛页岩(粒径范围:0～60mm),利用单块页岩热解反应装置,以三种升温速率(1℃/min、2℃/min及5℃/min)进行了热解实验,得到了不同温度下热解总失重、页岩油收率、干馏气体收率及其组成等实验数据.考察了诸因素(粒度、升温速率、加热温度和载气流量)对热解过程的影响,发现加热温度、粒度以及升温速率是热解过程的主要影响因素.首次建立了包括传热因素在内的热解反应动力学模型,求得了块状页岩的热解总失重、热解出油及产气过程的动力学参数.结果表明:热解总失重、热解出油及产气过程的表观活化能分别约为105～120kJ/mol、125～165kJ/mol及100～120kJ/mol.     

模型化合物十六烷在超临界水中的热解

为了解重质油中饱和分在超临界水中的热解机理,将十六烷作为模型化合物,在间歇反应器内研究了它在超临界水中的热解反应,反应温度420~460℃,压力23~27M Pa。在超临界水中,十六烷热解为较轻、较重的碳氢化合物和气体。与无超临界水、常压下十六烷的热解反应相比,超临界水中十六烷热解反应的活化能(300.0kJ/m ol)低,因而反应速率快。通过对产物的分析,推断反应遵循自由基机理,反应过程包括自由基的产生、传递、分解和终结。在超临界水中,十六烷的热解反应存在超临界水的供氢机制,减压渣油在超临界水中的热解反应也存在这种供氢机制,而该机制有利于改善热解产物的质量。     

含油污泥热解及热解油加氢精制研究

采用热解法对油田污泥进行处理,通过热解分析及热解放大试验,考察不同温度下热解油收率的变化,并对热解油进行加氢精制研究。结果表明:随着热解温度升高,产油率降低,热解终温以600℃较为适宜,产油率为38.61%,产气率为6.52%;热解油的残炭、金属含量、硫含量、氮含量以及沥青质含量均较低;在反应温度为420℃、氢分压为12.0 MPa、氢油体积比为800、体积空速为1.0h~(-1)的条件下,热解油经加氢处理后,脱硫率为94.5%,脱氮率为89.4%,氢油馏分收率较高,可作为轻质燃料调合组分,而蜡油馏分及重油馏分可以作为优质的加氢裂化原料,进而获得更多的轻质燃料。     

利用催化加氢热解技术提取沉积 有机质中生物标志化合物

利用催化加氢热解技术提取了高演化沉积有机质中共价键结合的生物标志化合物,探讨了干酪根催化加氢热解反应机理,并考察了反应产物分布和影响反应的关键变量.实验表明,程序升温固定床催化加氢热解反应条件:温度上限为520℃,升温速率为5℃/min,氢压大于10MPa,氢气流量为5L/min,分散型催化剂为MoS₂(Mo的质量分数为1%).实验结果表明,催化加氢热解对提取高产率、结构重排少的干酪根中共价键结合的生物标志化合物有独特作用,该方法可以应用于有机地球化学领域.     

含油污泥热解特性和动力学研究

采用热重分析仪对胜华炼油厂的含油污泥在氮气气氛下进行热重分析,考察不同升温速率下含油污泥的热重曲线并分析其热解特性.采用微分法对实验数据进行回归拟合,确定含油污泥热解动力学方程,求出反应活化能E和频率因子A.结果表明,含油污泥有机物的热解反应第一阶段(200～450℃)反应级数为2.0;第二阶段(450～900℃)反应级数为0.8.升温速率分别为5,10,15℃/min时,有机物热解第一阶段的活化能分别为33.95,36.63,38.99 kJ/mol;第二阶段的活化能分别为16.31,12.98,15.97 kJ/mol,总体上变化不大.     

催化裂化油浆基缩合多环多核芳香烃树脂的热解过程及动力学研究

采用TG和DTG,在不同升温速率（10、 20 和 30 K min-1）下考察了缩合多核芳烃（COPNA）树脂的热解机理和动力学。采用FT-IR、SEM和元素分析研究了COPNA树脂经不同热处理温度（200、400和600 °C）后官能团、微观结构和元素组成的变化。结果表明,热解过程可以分为三个阶段:初始失重阶段（225–450 °C）、第二失重阶段（450–560 °C）和热稳定阶段（>560 °C）。加热速率对热解过程有影响,热失重初始温度Ti、热失重终止温度Tf和最大失重速率Tmax等热力学参数随着加热速率的增加而升高。随着热处理温度的提高,芳香环上的脂肪侧链和取代官能团逐渐减少,C/H比和气孔率升高。热解动力学研究表明,初始失重阶段和第二失重阶段的活化能分布分别为150–210 kJ/mol和210–275 kJ/mol,这表明两个失重阶段的热解机理不同。当活化能低于250kJ/mol时,指前因子k0的值介于1011 和1018 s-1之间,而当活化能高于250 kJ/mol时,指前因子k0随着活化能E线性增加。     

EFFECTS OF HEATING RATE AND PARTICLE SIZE ON THE PRODUCTS YIELDS FROM RAPID PYROLYSIS OF BEECH-WOOD

Effects of pyrolysis temperature (300-1000 ^°C), heating rates (100, 500, 1000, and 10,000 ^°C/s), and particle sizes (53-63,104-120,177-270, and 270-500 urn) on the yields and formation rates of tar, light oils, total gases, and char from pyrolysis of beech-wood under 1 atm helium pressure were studied. Wood particles were pyrolyzed in strips of stainless steel wire mesh in a captive sample apparatus; and yields of products were measured in weight percent of original wood as a function of temperature for different heating rates and particle sizes. The overall weight loss achieved from pyrolysis of this wood was about 90%. The total yields of tar and light oils from pyrolysis of this wood accounted for up to 80% of the original wood above 400 ^°C. Due to the post-pyrolysis reactions of tar and light oils, the tar and light oils yields go through a maximum with pyrolysis temperature for all particle sizes and most heating rates studied here. As particle size increases from 53-63 μm to 270-500 μm the maximum tar yield decreases from 53% to about 38%. The maximum tar yield also decreases with increasing the heating rate from 70% at 100 ^°C/s to 48% at 10,000 ^°C/s heating rate. Theses results indicate that as the intra-panicle post-pyrolysis cracking reactions of tar increases at higher heating rates and with larger particles the tar yield decreases. Tar was also analyzed with GPC for the effects of above pyrolysis parameters on the tar molecular weight. The tar average molecular weight. remains relatively constant (M     

Pyrolysis characteristics of a North Korean oil shale

Pyrolysis characteristics of a North Korean oil shale and its pyrolysates were investigated in this paper. The pyrolysis experiments were conducted below 600 °C at a heating rate of 10, 15, 20 and 25 °C/min, respectively. The kinetics data were calculated using both integral and differential methods with the assumption of first order kinetics. The results show that the averaged oil content of the North Korean oil shale is about 12.1 wt% and its heat value is 13,400 kJ/kg. The oil yields at different retorting temperatures show that the higher the retorting temperature the greater the oil and retorting gas yields. The optimal retorting temperature for the North Korean oil shale is about 500 oC. The properties of the North Korean shale oil including density, viscosity, flash point and freezing point are found to be relatively low compared with those of shale oil from FuShun, China. The gasoline fraction, diesel fraction and heavy oil fraction account for 11.5 wt%, 41.5 wt% and 47 wt%, respectively. The major pyrolysis gases are CH4(the most abundant), H2, CO2, H2 S, CO, and C2-C5 hydrocarbons. The heat value of retorting gas is more than 900 kJ/mol, and the retorting gas has high sulfur content.     

原料族组成对汽油馏分催化裂解反应性能的影响

利用多产低碳烯烃催化剂NHC-516,在小型固定流化床实验装置上对催化裂化汽油、焦化汽油和直馏汽油的催化裂解性能进行了实验研究,考察了不同原料族组成对催化裂解产物分布、低碳烯烃收率以及催化裂解液相产物族组成的影响.结果表明:乙烯的收率随着反应温度的升高呈抛物线增长;催化汽油和焦化汽油的丙烯收率远高于直馏汽油的丙烯收率;烯烃与链烷烃有协同作用,烯烃能够加速链烷烃的反应速率,这是焦化汽油干气收率高的主要原因;在有烯烃存在时,芳烃会生成大量的焦炭;烯烃和链烷烃是生成低碳烯烃的主要来源,是催化裂解的理想组分.     

延迟焦化装置掺炼大庆裂解焦油的研究

将裂解焦油以不同比例掺炼到延迟焦化原料油中，考察产品分布和产品性质。结果表明，掺炼裂解焦油后干气、液化气收率减少，汽油、柴油、蜡油收率变化不明显，焦炭收率增加，主要产品硫、氮、金属质量分数有所降低。     

EFFECTS OF HEATING RATE AND PARTICLE SIZE ON THE PRODUCTS YIELDS FROM RAPID PYROLYSIS OF BEECH-WOOD

ABSTRACT

Effects of pyrolysis temperature (300–1000 ^°C), heating rates (100, 500, 1000, and 10,000 ^°C/s), and particle sizes (53–63,104–120,177–270, and 270–500 urn) on the yields and formation rates of tar, light oils, total gases, and char from pyrolysis of beech-wood under 1 atm helium pressure were studied. Wood particles were pyrolyzed in strips of stainless steel wire mesh in a captive sample apparatus; and yields of products were measured in weight percent of original wood as a function of temperature for different heating rates and particle sizes. The overall weight loss achieved from pyrolysis of this wood was about 90%. The total yields of tar and light oils from pyrolysis of this wood accounted for up to 80% of the original wood above 400 ^°C. Due to the post-pyrolysis reactions of tar and light oils, the tar and light oils yields go through a maximum with pyrolysis temperature for all particle sizes and most heating rates studied here. As particle size increases from 53–63 μm to 270–500 μm the maximum tar yield decreases from 53% to about 38%. The maximum tar yield also decreases with increasing the heating rate from 70% at 100 ^°C/s to 48% at 10,000 ^°C/s heating rate. Theses results indicate that as the intra-panicle post-pyrolysis cracking reactions of tar increases at higher heating rates and with larger particles the tar yield decreases. Tar was also analyzed with GPC for the effects of above pyrolysis parameters on the tar molecular weight. The tar average molecular weight. remains relatively constant (M_w = 300 amu, M_n = 155 amu, and M_z = 483 amu) under helium atmosphere with pyrolysis temperature at 1000 ^°C/s heating rate and with 53/63 u m particle size. The average molecular weight of tar does not significantly varies with heaung rate, but it decreases as the particle size increases.     

直馏柴油催化裂化生产轻质芳烃的研究

采用小型固定流化床催化裂化装置,考察了分子筛类型和反应条件对直馏柴油催化裂化反应的影响以及不同烃类组成的直馏柴油催化裂化产物分布特点。结果表明:选用富含环烷烃和单环芳烃的直馏柴油有利于提高轻质芳烃收率;在Y型分子筛催化剂作用下的直馏柴油催化裂化转化率最高,轻质芳烃收率可达13.22%;反应温度对轻质芳烃收率影响显著,反应温度由510℃提高到610℃时,转化率增加12.95百分点,轻质芳烃收率增加7.16百分点,提高原料的转化深度有利于增加轻质芳烃收率,但是汽油收率降低;剂油比对轻质芳烃收率影响较小,剂油比过高时,汽油收率下降。与直馏柴油相比,其催化裂化产物烃类组成中环烷烃质量分数减少26.4百分点,环烷烃参与反应的比例高达80.49%,环烷烃环数越多,参与反应的比例越高。     

Production of high-quality gasoline by pyrolysis of oil residue

Gasoline is considered as a high caloric value fuel with high potential for commercial applications such as transportation, electricity generation and production of chemicals. Currently, the majority of gasoline at industrial scale is supplied from the distillation of crude oil. In the present paper, an experimental study of catalytic pyrolysis of oil sludge was carried out to produce gasoline. The influence of low-temperature operation on the char conversion was also studied. Results showed that the Ni content has also a positive effect on the char conversion; however, the reaction temperature has a higher effect. The effect of heating rate on the char conversion and gasoline yield was also studied, and concluded that the heating rate plays a major role in the char conversion and gasoline production.     

THE INFLUENCE OF KINETIC PARAMETERS ON THE FISCHER-TROPSCH PRODUCT DISTRIBUTION

The expected composition of Fischer-Tropsch products has been examined as a function of catalyst type, temperature, pressure and H₂/CO ratio. The complete product distribution, as well as gasoline and diesel yields as a percentage of total hydrocarbons, were calculated by applying an established distribution model to an ideal PFR reactor simulation. In this way we have examined the effect of operating conditions and the kinetic parameters of the model on the expected product distribution. This distribution is shown to be a function of the operating conditions and of catalyst formulation.

The results show that, in principle, one can make more gasoline by increasing the H₂/CO ratio and better quality gasoline by decreasing total pressure. However, for both gasoline and diesel production, there is a set of parameters which yields a maximum of these products. By understanding the influence of temperature and catalyst composition on the reaction parameters, we can predict how temperature or catalyst formulation should be changed so that the reaction parameters are shifted in the direction of maximum motor fuel yield.     

采用热解方法回收油泥中原油

 摘要: 应用热天平和管式热解炉对油泥的热解行为进行实验研究。考察了不同升温速率对油泥热解的影响和不同热解终温对油泥各热解产物分布的影响,求解了油泥热解的动力学参数,并采用元素分析、FT-IR和1H NMR对油泥热解产物进行了分析。结果表明,随着升温速率的加快,油泥的热失重曲线向高温侧偏移,反应活化能和指前因子也随之增大。油泥最宜热解终温为823K,此时热解油产率达40.36%,所含原油的回收率达83.46%。所得热解油的化学组成与柴油相似,可以回收利用。油泥热解残渣为黑色粉体,残油量为0.0662%,达到国家标准对农用土壤含油量的规定(<0.3％)。