催化裂化吸附转化加工焦化蜡油工艺

分析了焦化蜡油（CGO）与直馏蜡油（VGO）的性质,焦化蜡油与直馏蜡油性质相差较大,主要表现在焦化蜡油残炭、碱氮化合物、胶质、沥青质及金属含量较直馏蜡油高,催化裂化（FCC）直接掺炼焦化蜡油,会造成转化率降低,产物分布恶化,运转周期缩短。通过常规催化裂化加工焦化蜡油工艺与FCC通过吸附转化工艺加工焦化蜡油比较,得出催化裂化吸附转化加工焦化蜡油工艺可以明显改善产物分布,提高转化率,降低碱氮化合物对催化剂的毒害作用,提高装置的整体经济效益。     

混合废塑料与焦化蜡油共催化裂解制取燃料油

以混合废塑料和焦化蜡油为原料,共催化裂解制备燃料油,克服了废塑料裂解中塑料粘稠度大且传热效率低、裂解炉中温度极不均匀、反应时间长、气体和固体收率高、液体收率低和易结焦等难题。详细考察焦化蜡油与混合废塑料质量比和催化剂用量对产物组成的影响以及FCC催化剂的重复使用性能。结果表明,在焦化蜡油与混合废塑料质量比为2、FCC催化剂用量为混合废塑料质量的10%、终温460 ℃并保持4 h条件下,燃料油收率达到96.67%,气体收率和釜残率分别仅有0.27%和1.53%。焦化蜡油的添加使液相产物中重组分增多,轻组分减少。FCC催化剂的重复使用性能好,催化剂重复使用5次,液体收率大于85%。采用混合废塑料与焦化蜡油共催化裂解的工艺不仅为“白色污染”的处理开辟了一条新途径,而且扩大了焦化蜡油的应用范围。     

辽河焦化蜡油脱芳烃实验研究

以辽河石化焦化蜡油(CGO)为研究对象,采用糠醛将其中的芳香组分和碱性氮化物选择性地脱除,并确定最适的反应条件为温度50℃、剂油体积比1.5.在此条件下,抽余油收率为67.55％,碱性氮含量为712.72 mg/kg,饱和分由61.00％提高到77.83％,芳香分由34.94％降至18.76％.碱性氮和四组分数据表明抽出油性质优于直馏蜡油,完全可以作为催化裂化的原料,而抽出油则可作为原料生产高附加值的化工产品.     

焦化轻蜡油掺炼加氢柴油试验研究

通过实沸点蒸馏仪对加氢柴油进行精密分离,得到不同馏程温度段的窄馏分油,分析了不同窄馏分油的收率分布与烃类组成分布,分析结果表明：随着馏程温度升高,窄馏分油收率逐渐降低,加氢柴油中的链烷烃主要富集在馏程温度点高的窄馏分中,环烷烃与芳烃主要富集在馏程温度低的窄馏分中。焦化轻蜡油回炼加氢柴油窄馏分油后,加氢裂化产物65~175 ℃馏分收率增加,>175 ℃馏分收率均降低。由于窄馏分油中的烃类组成不同,所得加氢裂化产物性质有所差异。掺炼富含环烷烃与芳烃的窄馏分油所得65~175 ℃馏分芳潜值最高,掺炼链烷烃窄馏分油所得>175 ℃馏分的十六烷值指数最高。     

焦化蜡油对含聚氯乙烯混合塑料热裂解产物的影响

以含聚氯乙烯(PVC)的混合塑料和焦化蜡油为原料,在N_2流量3 mL·s~(-1)吹扫条件下进行分段热裂解,裂解温度(25～250)℃、(250～360)℃及(360～480)℃。考察油固比、PVC含量对产物组成的影响,检测裂解油的有机氯含量。结果表明,PVC含量为质量分数5%,焦化蜡油与混合塑料的油固质量比为2,FCC催化剂用量为质量分数10%时,燃料油收率达到92. 04%,气体和固体收率仅有6. 89%和1. 07%。添加焦化蜡油增加液相产物中的重组分,减少轻组分。以焦化蜡油为溶剂进行混合塑料的催化裂解的工艺不仅为"白色污染"的处理开辟了一条新途径,而且为获得较低氯含量塑料裂解油提供了工艺参考。     

Effect of multistage hydroprocessing on aromatic and nitrogen compositions of shale oil

Geokinetics crude shale oil, a distillate and processing intermediates sampled during four-stage catalytic hydroprocessing of the distillate were analysed for total nitrogen, basic nitrogen and olefinic and aromatic contents. Successive hydroprocessing stages yielded products containing 80, 46, 16 and 2% of the nitrogen content in the feedstock. Total nitrogen, basic nitrogen and aromatic contents were also reduced. Apparent relative reactivities of aromatic hydrocarbons and nitrogen-containing compounds are in agreement with reactivities observed in model compound studies. Hydrodenitrogenation of nitrogen-containing compounds occurred concurrently with hydrogenation of non-nitrogen-containing aromatic hydrocarbons. Hydroprocessing conditions necessary for essentially complete removal of nitrogen yielded a refined oil with low aromatic content.     

Identification of nitrogen bases in a coker gas oil and influence of catalytic hydrotreat ment on their composition

The investigation of nitrogen bases occurring in a coker gas oil before and after catalytic hydrotreatment has shown important differences in reactivity of azaarenes. Compounds with a low degree of aromaticity are relatively resistant compared with higher benzologues. Particularly stable are α-methylated azaarenes, which are also major nitrogen bases found in crude oils. Alkyl anilines, the last intermediates before denitrogenation, are the most abundant bases in hydrotreated samples.     

植物油加氢制备高十六烷值柴油组分研究进展

介绍了植物油加氢制备柴油的主要化学反应、工艺方法以及该项技术的工业化状况,分析了植物油直接加氢、先加氢后异构、直接脱羧工艺以及植物油与矿物柴油掺炼工艺的特点,阐述了各工艺采用的催化剂类型、工艺条件以及产品属性。指出了该领域存在的问题和研究方向。     

Identification of carbazoles and benzocarbazoles in a coker gas oil and influence of catalytic hydrotreatment on their distribution

Fractions highly enriched in pyrrole benzologues have been extracted from a coker gas oil before and after hydrotreatment under selected operating conditions. Carbazole, methyl- and dimethylcarbazoles and benzocarbazoles have been identified by means of g.c. coelutions with standards. The study of these compounds after catalytic hydrotreatment has shown that benzocarbazoles are more effectively removed than carbazoles in highly hydrogenating conditions (partial pressure of hydrogen, 10 MPa; temperature, 360 °C) whereas alkyl carbazoles and more particularly 1-methyl derivatives are more altered at a high temperature (380 °C, partial pressure of hydrogen, 5 MPa).     

Y/composite titania-silica (CTS) supported catalyst for hydrotreating coker gas oil

Y/composite titania-silica (CTS) support was prepared by the in situ growth of CTS on HY zeolite. The effects of HY zeolite pretreatment and Y/CTS modification with P and F for adjusting the acidity of the support were studied. The results showed that the structure of Y/CTS was in the form of CTS as shell and HY zeolite particles as core. The content of HY zeolite affected the acidity, acidity distribution and pore structure of Y/CTS. The density of strong acid sites on the HY zeolite surface could be partly reduced by dealumination with citric acid. This reduced the CTS coverage on the outer surface of the HY zeolite, leading to the increased acidity of Y/CTS. The acidity distribution of the support could also be adjusted by P and F modification. Hydrotreating catalysts were prepared with Y/CTS as support. The catalysts were tested using the hydrotreating reaction of a coker gas oil (CGO). The experimental results showed that the catalyst hydrodenitrogenation (HDN) performance could be remarkably improved by adjusting the acidity of the catalyst support via HY zeolite pretreatment and P and F modification. The catalysts with proper Brönsted (B) acidity and Lewis (L) acidity behaved well in hydrodesulfurization (HDS) and HDN performances.     

塔河原油生产高等级道路沥青原料选择与评价

针对西部发展对高等级道路沥青的市场需求及塔河原油生产高等级道路沥青的问题,本文依据塔河炼化现有生产结构,从原料组成和结构、调和沥青性能、混合料性能等方面,开展适宜于生产高等级道路沥青的原料选择对比研究,并通过实际生产对技术方案进行了评价。研究得出,焦化辐射油胶体不稳定指数I_c为0.76,其实沸点大于430℃的渣油PI值较低,闪点满足90A道路沥青要求。塔河原油焦化辐射油适宜于高等级道路沥青生产。并以此设计生产工艺流程,生产出了符合指标要求的高等级道路沥青。满足了西部道路建设的需求。     

"反应-吸附法"精制焦化柴油的研究

以物质A为反应物,白土为脱色物质,研究用反应-吸附的方法提高焦化柴油的质量。实验表明:精制油的色度、氧化安定性沉渣、实际胶质均可达到国标合格柴油的要求,焦化柴油中的硫、氮等杂原子化合物和不饱和烃类化合物等不安定组分得到有效脱除,柴油质量大大提高,精制柴油收率在98%以上。     

Gas phase catalytic hydroprocessing of trichlorophenols

The catalytic hydrodechlorination of four trichlorophenol (TCP) isomers (2,3,5‐TCP, 2,3,6‐TCP, 2,4,5‐TCP and 2,4,6‐TCP) was studied in the gas phase using an Ni/SiO₂ catalyst over the temperature range 473 K ≤ T ≤ 573 K. The catalyst was 100% selective in removing chlorine(s), leaving the hydroxyl group and benzene ring intact. Dechlorination proceeds via stepwise and concerted routes and the relative importance of each is dependent on the nature of the isomer where steric rather than resonance effects appear to determine the ultimate product distribution. Dechlorination efficiency is quantified in terms of phenol yield, chlorine removal rate and the ultimate partitioning of chlorine in the parent organic or product inorganic host. The reaction pathways, with associated pseudo‐first order rate constants, for the conversion of 2,3,6‐TCP and 2,4,6‐TCP are presented. The effect of time and temperature on process selectivity is discussed and the nature of catalyst deactivation is considered. © 2000 Society of Chemical Industry     

Kinetic modeling of the hydrotreatment of light cycle oil and heavy gas oil using the structural contributions approach

The kinetics of the hydrodesulfurization of light cycle oil (LCO) and heavy gas oil (HGO) over a CoMo/Al₂O₃ catalyst were investigated in a perfectly mixed flow reactor with stationary basket of the Robinson-Mahoney type at temperatures of 330, 310 and 290 °C, H₂/HC molar ratios of 2.8, 3.6 and 7.2 and a pressure of 65 bar. Hougen-Watson type rate equations were derived for the conversion of dibenzothiophene, substituted (di)benzothiophene and their products. To avoid having to deal with a huge number of model parameters, a methodology based upon structural contributions was applied. In the absence of own kinetic data on key components a number of kinetic and adsorption parameters were taken from published work on a very similar catalyst. For a given value of H₂/HC only a small number of experiments was required to determine the value of the very complex denominators DEN_σ and DEN_τ appearing in the rate equations for the hydrodesulfurization of LCO and of HGO and of their evolution with the conversion of the feedstock. With the rate equations constructed in this way the calculated total conversion of DBT, its conversion into biphenyl and into cyclohexylbenzene were in excellent agreement with the experimental values.     

Characterization of dispersed hydroprocessing catalysts prepared in reversed micelles

Fe, Co and Ni particles were prepared in water/polyoxyethylene-4-laurylether/n-hexane and water/polyoxyethylene-4-laurylether/decahydronaphthalene microemulsions by reduction of metal nitrates dissolved in the water pools of the reversed micelles. The particles were mostly monodispersed with average diameters in the range 8 to 23 nm, as determined by dynamic light scattering (DLS). However, significantly smaller size estimates were obtained using transmission electron microscopy (TEM). The average DLS particle diameters increased with increased average diameter of the reversed micelles, and the diameter of the reversed micelles increased with an increase in the microemulsion water: surfactant ratio and metal ion concentration. The diameter of the reversed micelles was also dependent upon the metal dissolved in the water pool, increasing in the order Ni < Co < Fe. These trends are explained in terms of changes that occur to the microemulsion hydrophilic-lipophilic balance. Preparation of nickel and cobalt sulfides by sulfidation of the metal salt with H₂S at low temperature, yielded much larger diameter particles (average diameter 75 nm). Measurement of the activity of the sulfided catalysts showed that the Co catalyst was more active than the Ni catalyst for the hydrocracking of diphenylmethane, and Co was more effective than Fe in reducing coke yield during Cold Lake residue hydroprocessing.     

A modeling study of the effect of reactor configuration on the cycle length of heavy oil fixed-bed hydroprocessing

This article analyses how the configuration of an industrial fixed-bed reactor affects the cycle length of a heavy oil hydroprocessing unit. It is well-known that during the hydroprocessing of heavy feeds, catalyst aging is counterbalanced by continuously increasing reaction temperature. In addition, the exothermality of the reaction provokes a huge temperature rise along the reactor, which is why quenching is necessary. Thus, there is an increasing temperature profile that evolves with time until a maximum allowable temperature is reached and then the operation is shut down. For this reason, there is an optimum reactor configuration (i.e. number of quenches and their positions) that must be established when designing new processes in order to maximize unit run length. To evaluate this problem, a reactor performance model with time varying catalyst activity was constructed. Kinetic and catalyst aging data were obtained from bench-scale tests. The model showed to reproduce sufficiently well the experimental data set. The analysis of various reactor designs indicated that for this process the use of single-bed or double-bed reactors is unpractical in terms of cycle length. A more complex configuration consisting of multiple beds of increasing lengths is necessary to delay shut down.     

Prediction of product quality for catalytic hydrocracking of vacuum gas oil

The main objective of this work is to develop a predictive model for predicting the product quality of vacuum gas oil (VGO) hydrocracking process. Experimental data were obtained using a pilot plant hydrocracking catalytic reactor loaded with the same catalyst type used in a local refinery. Two sets of experimental runs were conducted under various operating conditions. The first one consisted of 18 runs and was used for parameter estimation, while the second set consisted of 29 runs and was used for model validation. Distillation curves of the cracked products were obtained using the simulated distillation (SimDist) test. A distribution model based on probability density function was used to develop the predictive model. The distribution model presents the boiling point as a function of the distilled weight fraction. Model parameters were estimated and related to the specific gravity of the cracked product. Model validation results showed that the proposed model is capable of predicting the distillation curves of the hydrocracked products accurately, especially at high operating severity. Simplicity and accuracy of the developed model makes it suitable for online analysis, to estimate the conversion as well as the product distribution of hydrocracking units in refineries.     

天然气催化燃烧在燃气轮机和锅炉中的应用

综述了天然气催化燃烧技术在燃气轮机和热水锅炉中的应用和研究现状及其发展方向,介绍了几种不同形式的催化燃烧器和一些典型的设计实例,指出催化燃烧技术仍存在的问题。     

天然气催化燃烧器独石通道内气体温度分布

研究了天然气催化燃烧器蜂窝状独石通道内气体温度分布。由于催化反应区在独石通道内10 mm左右基本结束,将催化剂独石长度减至20 mm进行实验,由于在高热强度下燃烧不易稳定,为降低独石入口前端腔内混合气温度,将一块20 mm长的无催化剂独石连接在镀钯催化剂独石的入口前组成组合催化剂独石,发现组合催化剂独石燃烧稳定。