Kinetics of aromatics hydrogenation of bitumen-derived gas oils

Using pilot scale trickle-bed reactors with commercial NiMo/Al₂O₃ catalysts, hydrotreating of five bitumen-derived gas oils was conducted. Aromatic carbon was determined by ^l3C NMR spectra. A simple power law kinetic model of aromatics hydrogenation was developed, assuming a first order reversible reaction which accounts for both forward and reverse rate constants. The model includes power terms for space velocity and hydrogen partial pressure, and the ratio of naphthenes and aromatics in the feed. The model was tested with our experimental results and kinetic parameters were determined. Aromatic carbon calculated with these parameters is in good agreement with observed results.     

Correlation of reactivity to hydrogenation and chemical structure of lignites

Three North Dakota lignites with almost the same percentage carbon have been used to determine the relation between chemical structure and reactivity to hydrogenation. Average structural indices of the lignites were estimated using the pyridine-soluble products after alcohol-alkali treatment, the structural indices obtained at various reaction times being extrapolated to zero reaction time. Hydrogenation was influenced by the average structure, with the lignite having higher aromaticity, higher molecular weight of the pyridine extract from the alcohol-alkali reaction product, larger aromatic ring size and lower content of aliphatic structure, showing a smaller degree of conversion.     

The relationship between chemical structure and reactivity of alberta bitumens and heavy oils

Long residues (424°C +) from Athabasca, Cold Lake, Lloydminster, and Peace River were hydrocracked over a commercial NilMo on y-alumina catalyst at 430°C, 13.9 MPa (2000 psia). The conversion of residue fraction ranged from 55 to 68%, and was correlated with the concentration of carbon bound to aromatic rings in the feeds. Conversions of sulfur, Micro-Carbon Residue, and metals were all highest for Peace River feed, following the same ranking as residue conversion. Estimates for the breakage of carbon-carbon bonds and the uptake of hydrogen were diagnostic in interpreting the reactor performance.     

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。     

Kinetics of catalytic transfer hydrogenation of some vegetable oils

Catalytic transfer hydrogenation of corn, peanut, olive, soybean, and sunflower oils has been studied with aqueous sodium formate solution as hydrogen donor and palladium on carbon as catalyst. Kinetic constants and selectivity have been determined under intensive stirring in the presence of stabilizing agents. Hydrogenation reactions followed first-order kinetics with respect to fatty acids. Besides good selectivity and short reaction time, this method offers safe and easy handling. The presence of linolenic acid retards the migration of double bonds, which explains why soybean oil is the most appropriate for this hydrogenation process.     

A second-order model for catalytic-transfer hydrogenation of edible oils

A second-order kinetic model for hydrogenation of fatty acids in series has been developed and analyzed. The model is applied to the data obtained for sodium formatecatalyzed hydrogenation of soybean, peanut, corn, and olive oils. There is good agreement between the experimental data and predicted values obtained from the model as evidenced by the analysis of r ² and F-test values. The effect of individual fatty acid composition of various edible oils on the rate of hydrogenation has been explained in view of the mathematical model developed. The individual rate constants seem to obey the Arrhenius rate law. The second-order kinetic analysis discussed is found to be suitable for mathematically describing hydrogenation of vegetable oils by hydrogen donors as compared to the traditional first-order kinetic analysis     

过滤器在石油炼厂的应用

燃料型、燃料-润滑油型、燃料-化工型、燃料-润滑油-化工型原油加工方案是根据国民经济对石油产品的需求及原油特性决定的。各类型原油加工过程中的催化、裂化、加氢处理等工艺过程都与过滤器有关。过滤器在原油加工过程中起着重要作用。     

模拟酸性气预硫化加氢催化剂工艺研究

在常压下采用固定床反应器,研究了以H2S,H2,N2,CO2气体模拟炼油厂酸性气为硫化介质,对加氢催化剂进行器外预硫化;考察了硫化温度、硫化时间、空速、模拟气组成等因素对催化剂硫化效果的影响.用裂解汽油一段加氢油为原料,对催化剂进行高压微反活性评价.实验结果表明:以模拟酸性气为硫化介质对加氢催化剂进行器外预硫化是可行的...     

Hydrotreating of light gas oil using a NiMo catalyst supported on activated carbon produced from fluid petroleum coke

Nitric acid functionalized steam activated carbon (NAFSAC) was prepared from waste fluid petroleum coke (FPC) and used as a support material for the synthesis of a NiMo catalyst (2.5 wt-% Ni and 13 wt-% Mo). The catalyst was then used for the hydrotreatment of light gas oil. The support and catalysts were characterized by Brunauer-Emmett-Teller (BET) gas adsorption method, X-ray diffraction, H₂-temperature programmed reduction, NH3-temperature programmed desorption, CO-chemisorption, mass spetrography, scanning electron microscopy (SEM), Boehm titration, and Fourier transform infrared spectroscopy (FTIR). The SEM results showed that the carbon material retained a needle like structure after functionalization with HNO₃. The Boehm titration, FTIR, and BET results confirmed that the HNO₃ functionalized material had moderate acidity, surface functional groups, and mesoporosity respectively. The produced NAFSAC had an inert nature, exhibited the sink effect and few metal support interactions, and contained functional groups. All of which make it a suitable support material for the preparation of a NiMo hydrotreating catalyst. Hydrotreating activity studies of the NiMo/NAFSAC catalyst were carried out under industrial operating conditions in a laboratory trickle bed reactor using coker light gas oil as the feedstock. A parallel study was performed on the hydrotreating activity of NiMo/γ-Al₂O₃ as a reference catalyst. The hydrodesulfurization and hydrodenitrogenation activities of the NiMo/NAFSAC catalyst were 62% and 30%, respectively.     

还原条件对镍/氧化铝油脂加氢催化剂的影响研究

采用沉淀法制备了镍/氧化铝催化剂前驱体,前驱体经焙烧、还原、包油成型制得镍/氧化铝油脂加氢催化剂。通过对催化剂进行TPR、氮吸附测定以及棕榈油加氢评价实验,考察了还原条件（还原温度、还原时间和氢气流速等）对催化剂孔结构和加氢活性的影响。结果表明,还原温度对催化剂孔结构和加氢活性影响最明显;催化剂前驱体最适宜的还原条件为还原温度500 ℃、还原时间3.0 h、氢气流速150 mL/min。在此条件下制备的催化剂用于棕榈油加氢反应,能够使每100 g棕榈油碘值由56.0 g降到0.81 g。     

Structural changes in catalytic hydroprocessing of syncrude coker gas oil

A method of Structural Group Analysis (SGA) was used to characterize feed and liquid products from catalytic hydroprocessing using a commercial Ni-Mo catalyst. Comparison of the structural profiles revealed significant changes in the concentration of various structural groups. SGA is a promising tool for investigating chemical changes in complex reacting systems.     

油脂氢化三元金属催化剂制备及性能研究

在相同的加氢条件下,对自制Cu-Ni-Cr三元金属催化剂与Cu-Ni二元金属催化剂和进口单元镍催化剂的加氢性能进行了比较。结果表明,三元金属催化剂的活性高于二元金属催化剂,选择性高于单元金属催化剂。关于氢化油的固体脂肪指数,多元催化剂和单元催化剂的性能接近。     

Thermal stability of polyurethanes based on vegetable oils

A series of polyurethanes from polyols derived from soybean, corn, safflower, sunflower, peanut, olive, canola, and castor oil were prepared, and their thermal stability in air and nitrogen assessed by thermogravimetric analysis, FTIR, and GC/MS. Oil‐based polyurethanes generally had better initial thermal stability (below 10% weight loss) in air than the polypropylene oxide‐based polyurethane, while the latter was more stable in nitrogen at the initial stage of degradation. If weight loss at a higher conversion is taken as the criterion of stability, then oil polyurethanes have better thermal stability both in air and in nitrogen. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1723–1734, 2000     

Chemical structure of heavy oil from coal hydrogenation 1. Hydrogenation with zinc chloride catalyst

Oil product from the hydrogenolysis of a high-volatile bituminous coal was separated by solubility, fractionated by gel permeation chromotography and characterized by structural analysis. The average structural unit in the hexane-soluble, aromatic oil fraction consists of 1–3 aromatic rings with 0.3-0.5 of the ring carbons substituted by alkyl groups and oxygen containing groups. Molecular weights vary from 200 to 500. The larger molecular weight fractions have longer alkyl chains and lower carbon aromaticities. The molecules are mainly of single unit structures. The average structural units in asphaltene fractions contain from 2.5-4 aromatic rings, are of higher carbon aromaticities and contain shorter alkyl groups. The asphaltene molecules consist of two or more structural units, crosslinked together, and have molecular weights of 300–1400. The oxygen content of the fractions decreases with decreasing molecular weight. Increasing the amount of ZnCl₂ catalyst during hydrogenolysis resylts in an increased yield of lower-molecular-weight material, but no change in the structural properties of the product. This is interpreted to mean that ZnCl₂ is active in the scission of covalent bonds between structural units during liquefaction and that the hydrogenolysis reaction is mostly cleavage of crosslinks between structural units with minimal reaction of the units themselves.     

JT-1G型和JT-4型炼厂干气加氢精制催化剂的开发及工业应用

介绍了炼厂焦化干气加氢精制催化剂的开发研制过程及其在炼厂制氢、大中型合成氨原料路线改造工程中的应用概况。并对研制开发的JT-1G和JT-4型加氢催化剂应用于国内炼厂富气汽柴油吸收串绝热等,炼厂干气绝热床循环法加氢以及等温-绝热加氢等三种工艺流程的操作运行工况作了说明。     

免硫化型克劳斯尾气加氢催化剂工业应用

介绍了中国石油化工股份有限公司齐鲁分公司研究院开发的免硫化型克劳斯尾气加氢催化剂在某石化企业20 kt/a硫磺回收装置上的应用情况,结果表明:免硫化尾气加氢催化剂具有较好的SO₂加氢和CS₂水解活性,开工期间装置排放烟气ρ(SO₂)稳定低于50 mg/m³。装置稳定运行一个月后,进行了工业应用标定,标定结果表明:装置运行平稳,各项参数在正常范围内,免硫化催化剂运行良好,催化剂表现出优异的活性,装置排放烟气ρ(SO₂)在3～10 mg/m³,远低于国家标准。     

进口油脂加氢催化剂氢化性能的研究

在同一条件下，研究了几种进口催化剂（PRICAT 9908，PRICAT9910，Harshaw Nysosel222,Harshaw DM-Ⅱ）的氢化性能，发现其活性顺序为：222＞9910＞9908＞DM－Ⅱ；其选择性顺序对亚麻酸为：9910＞222＞DM－Ⅱ＞9908，对亚油酸为：DM－Ⅱ＞222＞9908＞9910；氢化反应活化能大小顺序为：DM－Ⅱ＞9908＞9910＞222。     

原油深度加氢复合多金属硫化物催化剂的制备方法

复合多金属硫化物（MMS）催化剂主要用于原油的深度加氢,用于生产高十六烷值、低硫和低芳族化合物柴油。MMS催化剂包含NiMoS、NiWS、NiMoO、NiWO、NiMoWS和ZnMoWS催化剂等。综述MMS催化剂中二元复合金属硫化物催化剂和三元复合金属硫化物催化剂的制备方法,采用二步法即添加有机物作孔成形剂先制得催化剂前驱体,再由前驱体制得的MMS催化剂结构更松散,具有较大的比表面积（90 m²·g^-1）和大孔容（大于0.3 cm³·g^-1）,因而具有更好的催化活性。对比不同MMS催化剂对重质柴油、焦油等的加氢裂解、加氢脱硫和加氢脱氮性能,认为NiMoW三元复合金属硫化物催化剂(50%Ni25%Mo25%W)的活性最优。     

Phase-equilibrium modeling in the hydrogenation of vegetable oils and derivatives

The main tool needed to carry out phase-equilibrium engineering of a given process is an adequate thermodynamic model adjusted to the range of process operating conditions of the working system. In the present work the Group Contribution with Association Equation of State (GCA-EoS) is used to model the phase behavior of reacting mixtures typical of the hydrogenation of vegetable oils and derivatives at supercritical or high-pressure conditions.     

Thermal degradation of shale oils: 1. Kinetics of vapour phase oil degradation

As vertical modified in-situ retorts (VMIS) have been scaled up and tested, the overall oil yield has declined and is generally lower than that observed in an above-ground process. This reduced oil yield could adversely affect the economics of VMIS retorting. Diminished yields are attributed to a combination of factors associated with scale-up such as in complete rubblization, wide particle size distributions (large blocks of shale), and poor flow distributions. Additionally, oil losses can occur by comparatively long exposure of the oil vapours to high temperatures, by exposure to successive condensation and revaporization of the oil as it travels down the retort, and finally by long time thermal exposure of the condensed oil retained in the bottom portion of large VMIS retorts. To study such vapour phase degradation of shale oil using oil produced from Occidental Petroleum's No. 6 VMIS retort, a tubular continuous flow reactor, with an on-line gas chromatograph for gas composition monitoring was used to study thermal degradation of shale oil under retorting conditions. Oil and a combination of gases including steam were metered into the preheater and then the vapours passed into a quartz tubular reactor where the temperature and residence time of the gaseous mixture were controlled. Complete mass balances were performed giving the weight fraction of oil converted to noncondensable hydrocarbon gases and coke. This experimental design is novel because high temperature thermal degradation of shale oil was studied for the first time under steady state flow conditions with carefully controlled residence time and temperature. A range of temperatures (425–625 °C) and residence times (2–10 s) were used in a series of factorial-designed experiments (3²) to accurately determine the effects of these variables. Results of the study showed that the addition of steam to the carrier gas did not reduce oil degradation losses but did react with the coke thereby changing the product gas composition and quantity. A first-order oil degradation rate expression was used to model the rate of oil loss. The calculated activation energy was 17.3 kcal mol^?1. Chemical analyses of the product liquids and gases confirmed previously reported findings that the oil loss indices (alkene/alkane, ethylene/ethane, naphthalene/(C₁₁ + C₁₂), and gas/coke) increase with increasing oil degradation.