灰分对焦炭溶损反应起始温度的影响

通过灰分添加实验得到不同灰分含量的焦炭,研究了灰分对焦炭溶损反应起始温度的影响。随着灰分的增加,焦炭的溶损反应起始温度逐渐降低,焦炭灰分由1.63%增加至20%时,溶损反应起始温度由941.6℃降低至927.7℃;Fe2O3、Ca O、Mg O对焦炭溶损反应起催化作用,而Si O2和Al2O3对焦炭溶损反应的影响较小。     

螺环原碳酸酯/环氧树脂体系固化反应动力学

采用示差扫描量热法(DSC)对螺环原碳酸酯膨胀单体(SOC)/双酚A型环氧树脂(EP)体系的固化行为、放热峰进行了分析;并用Kissinger方程和Crane方程求得体系表观活化能、表观反应频率因子、反应级数等固化反应过程动力学参数,结果表明:螺环原碳酸酯膨胀单体的加入,体系的表观活化能和表观反应频率因子增加,反应级数保持不变,而反应速率急剧下降。此外,利用外延法对体系起始固化温度、恒温固化温度以及后处理温度进行初步探讨,为固化工艺的确定提供了依据。     

矿物质负载方式对焦炭溶损反应的作用研究

比较了1 1种氧化物以添加和吸附两种方式负载到同种焦炭中对焦炭溶损反应作用的区别,并从催化作用、矿物质在焦炭中的分散方式和矿物质对焦炭显微结构作用三方面分析了导致作用不同的机理.同种矿物质无论以何种方式负载对炭的催化作用是相同的.吸附矿物质主要是均匀分散在焦炭表面,而添加矿物质则部分被炭基质包裹,两种方式提供的催化表面是不同的,添加到煤中的矿物质还可以通过对焦炭结构产生影响而导致对焦炭反应性的作用.     

典型碱金属、碱土金属对不同变质程度煤焦溶损反应的催化作用

试验研究发现,添加碱金属、碱土金属对低变质程度煤焦反应性的催化作用小于焦煤等中等变质程度煤焦反应性。它们对焦炭溶损反应的催化作用顺序为：K〉Na〉Ca〉Mg,且随着添加量的增加,催化作用越强。随反应时间和典型金属添加量的增加,以及温度的升高,焦炭转化率越大。     

富钙废渣配煤对焦炭溶损反应的影响

将1%富钙碱渣配入焦煤中制备焦炭,采用自制小型垂直固定床反应器研究了900~1200℃下所得焦炭的溶损反应过程. 结果表明,碳素溶损率小于15%时焦炭的溶损反应速率基本不变,碳素溶损率大于15%时溶损反应速率逐渐减小. 焦炭反应后的比表面积随碳素溶损率增加先增大后减小,在溶损率约为15%时最大. 配入富钙碱渣提高了焦炭的溶损反应速率,增大了焦炭的反应性,溶损温度越高,溶损速率增幅越大. 用随机孔模型描述了焦炭的溶损反应动力学过程,基础焦炭和添加1%碱渣的焦炭的溶损反应表观活化能分别为132.15和103.81 kJ/mol.     

双酚化合物改性氰酸酯树脂体系固化动力学的研究

采用Kissinger法对双酚A/双酚E氰酸酯和双酚M/双酚E氰酸酯进行了固化反应动力学研究,得到了不同双酚化合物作用下的表观反应活化能、指前因子、反应级数及135℃下的速率常数。对于双酚A/氰酸酯体系,起始固化温度为97.8℃,峰值温度为132.7℃,表观活化能为68.98kJ.mol-1,指前因子为1.27×108min-1,135℃下的速率常数为0.1889min-1;对于双酚M/氰酸酯体系,起始固化温度为88.7℃,峰值温度为131.1℃,反应活化能为64.58kJ.mol-1,指前因子为3.51×107min-1,135℃下的速率常数为0.1905min-1。研究表明,增加反应物结构的柔韧度有利于反应的进行。     

氧化铁对焦炭溶损反应的影响

在井式硅钼棒电炉中对焦炭溶损反应性进行研究,考察了反应条件(CO₂流量、反应时间)并重点研究负载氧化铁对焦炭溶损反应性的影响;通过扫描电子显微镜(SEM)和电子能谱(EDS)对反应前后负载氧化铁的焦炭进行分析,探究氧化铁负载方式对焦炭溶损反应影响差异的原因,并进一步分析比较其影响机理。结果表明:焦炭溶损反应性随CO₂流量和反应时间的增加而增大;以吸附法和添加法负载氧化铁对焦炭溶损反应均有促进作用,氧化铁吸附负载量存在一个饱和点(1%),超过该点后氧化铁吸附负载量对焦炭溶损反应性影响甚微;吸附法负载氧化铁对焦炭溶损反应性的影响大于添加法。SEM分析表明:添加法的部分铁氧化物被焦炭气孔壁基质包裹而无法发挥作用,吸附法的氧化铁均匀分布在焦炭表面使其能提供更多有效催化活性中心;且添加氧化铁时铁氧化物参与成焦,影响焦炭结构从而对焦炭溶损反应产生影响,吸附氧化铁则是影响焦炭溶损反应的催化作用,两种负载方式下氧化铁的影响机理不同。     

择形催化剂上α-蒎烯异构化反应动力学研究

用择形催化剂ＸＣ－９０催化α－蒎烯异构化反应,考察了反应时间、反应温度对反应结果的影响,研究了该反应的动力学,求出了反应的表观活化能、频率因子和反应级数,建立了反应速率常数与温度的关系式     

择形催化剂上α—蒎烯异构化反应动力学研究

用择形催化剂ＸＣ－９０催化α－蒎烯异构化反应,考察了反尖时间,反应温度对反应 影响,研究了该反应的动力学,求出了反应的表现活化能,频率因子和反应级数,建立了反应速率常数与温度的关系式。     

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。     

造纸黑液对石油焦-CO2气化的催化作用及动力学补偿效应

研究了以造纸黑液为催化剂,齐鲁石油焦-CO2的气化动力学.在950～1200℃测定了造纸黑液负载量为0～15%时石油焦的气化反应活性,发现造纸黑液使石油焦的气化反应活化能大幅度降低,表明造纸黑液具有催化作用.得到了齐鲁石油焦-CO2催化气化反应动力学的缩芯模型,并给出相应的动力学参数.催化剂用量对动力学参数的影响表明,...     

不同配比碱金属化合物对焦炭反应性的影响

通过将一定粒度焦炭浸入不同配比碱金属化合物（K2CO3＋Na2CO3）溶液的方法在实验室制得焦样,用热重天平对焦样进行了焦炭反应性实验及SEM扫描电镜和能谱分析。研究结果表明,不同配比碱金属K、Na复合催化剂催化效果不同,K2CO3对焦炭溶损反应的催化作用贡献较大,焦炭溶损反应主要催化作用时间为前10min,浸碱焦炭试样中K、Na含量随碱溶液中K、Na含量增加而增加。     

Pyrolysis kinetics of Athabasca bitumen using a TGA under the influence of reservoir sand

Pyrolysis kinetics of thermal decomposition of bitumen was investigated by thermogravimetric analysis (TGA). TGA experiments were conducted at multiple heating rates of 5, 10, 20°C min^–1 up to 800°C to obtain the pyrolysis characteristics of bitumen. Weight loss curve from TGA shows that two different stages occurred during bitumen pyrolysis. Differential method has been used for determining the kinetic parameters and the best fit for the order of reaction was found based on the R² values. Kinetics results confirm the presence of two different stages in bitumen pyrolysis with varying kinetic parameters. The average activation energy for the first and second stage was 29 and 60 kJ mol^?1 and the average order of the reaction was 1.5 and 0.25, respectively. Experiments have been conducted with different reservoir sand. The effect of different source of sand reveals no effect on the pyrolysis behaviour of bitumen. A considerable difference was found with the pyrolysis of bitumen–sand mixtures and bitumen alone based on coke yield and activation energy. © 2011 Canadian Society for Chemical Engineering     

Kinetics of steam regeneration of SAPO-34 zeolite catalyst in methanol-to-olefins (MTO) process

Methanol-to-olefins(MTO) is industrially applied to produce ethylene and propylene using methanol converted from coal,synthetic gas,and biomass.SAPO-34 zeolites,as the most efficient catalyst in MTO process,are subject to the rapid deactivation due to coke deposition.Recent work shows that steam regeneration can provide advantages such as low carbon dioxide emission and enhanced light olefins yield in MTO process,compared to that by air regeneration.A kinetic study on the steam regeneration of spent SAPO-34 catalyst has been carried out in this work.In doing so,we first investigated the effect of temperature on the regeneration performance by monitoring the crystal structure,acidity,residual coke properties and other structural parameters.The results show that with the increase of regeneration temperature,the compositions of residual coke on the catalyst change from pyrene and phenanthrene to naphthalene,which are normally considered as active hydrocarbon pool species in MTO reaction.However,when the regeneration temperature is too high,nitrogen oxides can be found in the residual coke.Meanwhile,as the regeneration temperature increases,the quantity of residual coke reduces and the acidity,BET surface area and pore structure of the regenerated samples can be better recovered,resulting in prolonging catalyst lifetime.We have further derived the kinetics of steam regeneration,and obtained an activation energy of about 177.8 kJ·mol~(-1).Compared that with air regeneration,the activation energy of steam regeneration is higher,indicating that the steam regeneration process is more difficult to occur.     

Cinétique de la calcination du coke de pétrole en atmosphères neutre et oxydante

A devolatilization kinetic study of oil coke samples under conditions close to those of industrial calcination furnace is presented. The effects of the surrounding conditions (neutral or oxydizing medium), the heating rate and the percentage of oxygen in an oxydizing environment are analyzed. Experiments are carried out in an induction oven and involved thermogravimetric and chromatographic analyses. Results show that, under certain conditions, the nature of the environment influence the devolatilization process. A slow heating rate and a low content in volatiles promote the coke degradation by oxygen in an oxydizing medium. The reactive schemes are derived by tracking the concentration of CH₄, H₂, CO and CO₂. In regions where the coke is not degraded, a kinetic model is used to compare the parameters describing the develotilization phenomena in the two media (neutral and oxydizing), i.e.: the reaction order, the activation energy and the pre-exponential factor. It is shown that the oxydizing medium promotes an increase in the activation energy.     

Demetallization of heavy oil through pyrolysis: A reaction kinetics analysis

By tracking the transfer of vanadium and nickel in pyrolysis products, a seven-lump reaction kinetic model for pyrolysis-based demetallization of heavy oil was established. During pyrolysis, the demetallization of heavy oil is achieved by condensing metal-rich resins and asphaltenes to coke. The condensation of oil components originally contained in heavy oil differs greatly in reaction behavior, having the activation energy between 167 and 361 kJ/mol. As the pyrolysis progresses, the newly formed heavy components show a condensation behavior close to that of the light components. Limited by high activation energy and low initial fraction, the condensation of asphaltenes to coke and the resulting removal of metals contained in asphaltenes are hindered. Meanwhile, the condensation of light components has a major contribution to coke formation. An increase in reaction temperature accelerates the demetallization, but hardly changes the yield and component distribution of liquid products at the same metal removal rate.     

煤在铜渣熔融还原铁尾渣降温中的热解特性

通过动力学计算,结合XRD和气相色谱分析,对降温条件下单煤及以铜渣熔融还原尾渣为载体的煤的热解行为进行了研究. 结果表明,在初始温度1200℃、降温速率6.667 K/min条件下,煤混渣中煤热解最大速率较单煤增大,时间提前6~7.5 min,失重增加4.51%~11.43%;煤混渣热解气体中H2含量增高,原因为渣中CaO组分对煤中芳香环的脱氢效应;单煤及煤混渣样在降温过程中热解及气化反应均属一级反应,煤混渣样初始热解及气化反应表观活化能低于单煤,但主热解区表观活化能大于单煤,原因为主热解区还原性气氛增强,同步发生渣中高价铁氧化物的还原,反应类型增加,表观活化能变大.     

Pyrolysis and combustion kinetics of Fosterton oil using thermogravimetric analysis

Thermogravimetric analysis (TGA) was used to examine the thermal behavior of Fosterton oil mixed with reservoir sand. TGA experiments were performed in nitrogen and air atmospheres at the heating rate of 10 °C/min up to 800 °C. In this study, four sets of TGA runs were performed to examine the thermal behavior of Fosterton whole oil, and the coke sample derived from the whole oil. Similar to previous studies in the literature, we also observed low-temperature oxidation (LTO), fuel deposition (FD), and high-temperature oxidation (HTO) in the non-isothermal combustion experiment. Higher activation energy values were obtained in reaction regions at higher temperatures. The mean activation energy for whole oil in nitrogen and air atmospheres was 33 and 126 kJ/mol, respectively. Fresh coke samples derived from whole oil were subjected to isothermal combustion at different temperatures from 375 to 500 °C. Arrhenius model was used to obtain the kinetic parameters from the TGA data. From the model, the Arrhenius parameters such as activation energy (E = 127 kJ/mol) and the pre-exponential factor (A = 1.6 × 10⁸/min) were determined for the coke combustion. The results showed a close agreement between the kinetic model and experimental data for different combustion temperatures. It was observed that the apparent order of combustion reaction for different temperatures approach unity.