DEEP DESULPHURISATION OF A DIESEL BLEND IN A PILOT PLANT TRICKLE BED REACTOR

A pilot plant investigation was conducted to study the influence of hydrotreating conditions on conversion and characteristics of diesel blend and to determine the severity of operating conditions required to meet the proposed product specifications for diesel fuel in India. A typical diesel blend derived from various refinery streams with sulphur content of 2·06 wt% was hydrodesulphurised over a commercial NiO-MoO₃/Al₂O₃ catalyst in a pilot plant trickle bed reactor. The experiments were conducted at 300-370°C, 30-50 kg/cm², 2·0 3·0 hr^-1 liquid hourly space velocity and constant H₂/oil ratio of 185 m³/m³. The data showed that the diesel blend could be hydrotreated to meet revised product specifications of 0·25 wt% sulphur, 46 cetane number by increasing the severity of operation. The cetane number and aromatic saturation were limited by thermodynamic equilibrium at temperatures above 360°C. The influence of temperature was found to be more pronounced than that of pressure in the range of operating conditions studied.     

KINETICS OF HYDRODESULFURIZATION OF HEAVY GAS OIL DERIVED FROM OIL-SANDS BITUMEN

With gradual shortage in the supply of crude oil, the importance of producing synthetic crude oil from oil sands and shale oil is increasing day by day. In the present paper, the effects of various process variables such as temperature, liquid hourly space velocity and hydrogen/heavy gas oil volumetric ratio on the removal of sulfur compounds from oil sands derived heavy gas oil has been studied. The experiments have been carried out in a micro scale trickle bed reactor over a commercial Ni-Mo catalyst. The temperature, liquid hourly space velocity and hydrogen/heavy gas oil volumetric ratio have been varied from 365 to 415°C, 0.5 to 1.9 h^-1 and 400 to 1000 ml, respectively. Under optimum reaction conditions over 96% conversion of sulfur compounds was achieved. The kinetics of the rate of sulfur removal from the oil sands derived heavy gas oil has also been discussed in this article.     

环烷基变压器油精制过程中气体含量变化的研究

以中国海洋石油集团有限公司自产环烷基原油常二线馏分油为原料,考察了加氢脱酸-糠醛精制-液相脱氮和白土补充精制联合工艺各精制阶段对环烷基变压器油中气体含量的影响。结果表明：环烷基原油常二线馏分油经联合工艺精制生产变压器油时,液相脱氮电精制阶段会使变压器油中的氢气、二氧化碳、甲烷、乙烯及乙烷气体含量明显升高;通过调整电精制工艺条件和增设真空过滤装置进一步降低了变压器油产品中的气体含量,所生产的变压器油产品的气体含量均满足电力行业标准的技术要求。     

反应条件对沸腾床渣油加氢催化剂脱金属性能的影响

以高硫劣质渣油为原料,用自行研发的沸腾床渣油加氢微球催化剂,在STRONG沸腾床试验装置上进行了加氢脱金属试验,考察了温度、空速和氢油体积比对渣油脱金属率的影响。结果表明：在沸腾床全混流的状态下,在试验所考察的温度范围内,渣油加氢脱金属率随着反应温度的增加呈上升趋势,最适合的反应温度为380 ℃;在试验所考察的空速范围内,原料的脱金属率随着空速的增加呈下降趋势,且下降趋势明显,最适合的空速为1.6 h-1;在试验所考察的氢油体积比范围内,脱金属率先随氢油体积比的增大而提高,达到一个最佳反应区域（氢油体积比450~550）后,又随氢油体积比的增大而降低。     

渣油催化裂化生焦反应集总动力学模型的研究

在柴油馏分和重馏分油催化裂化生焦反应集总动力学模型研究的基础，通过生焦反应试验和动力学参数估计，建立渣油催化裂化生焦反应十集总动力学模型。结果表明，反应系统气相和液相均符合催化生焦机理的动力学模型，具有较好的拟合试验数据能力和良好的外推性，并符合催化裂化生焦反应规律。     

An Algorithm for Pseudocompound Delumping and Lumping into Homologous Groups

An algorithm for pseudocompound delumping and lumping into homologous groups is developed. This algorithm is useful for modeling refineries when using commercial simulators and detailed reactor models. Generally, commercial simulators represent petroleum fractions using pseudocompounds; however, reactor models and their kinetics are based on known compounds. This algorithm delumps the pseudocompounds into homologous groups that are represented by model compounds, which are then used by a detailed reactor model. After the reaction, the outlet stream is lumped again to pseudocompounds that are used in the remaining operations of the commercial simulator. The lumping operations are based on mass balance principles and fundamental properties of the hydrocarbon mixture. This algorithm is applied to the modeling of a hydrotreatment unit that belongs to the Mexican System of Refineries which uses a detailed three phase trickle bed reactor. The problem is to delump and lump the pseudocompounds, which represent light gas oil, into paraffins, naphthenes, and mono and polyaromatics. Results show a good agreement with industrial data.     

MILD HYDROCRACKING OF VACUUM GAS OILS TO IMPROVE FCC PERFORMANCE AND MAXIMIZE DISTILLATE YIELDS

A pilot plant study was conducted on mild hydrocracking of heavy vacuum gas oils derived from two different crude sources over a commercially available catalyst to determine the possibility of utilizing mild hydrocracker bottoms as fluidized catalytic cracking feedstock along with improved middle distillate yields. The mild hydrocracking experiments were conducted at 390°C, 60 kg/cm², 1.0/h liquid hourly space velocity and H₂/oil ratio of 390 l/l in a pilot plant trickle bed reactor using two catalyst beds for pretreatment and mild hydrocracking reactions. The experimental results showed that mild hydrocracking would result in valuable middle distillates with low sulphur and nitrogen content. With research octane number of 78, the naphtha obtained from mild hydrocracking was found to be a good blending stock for gasoline pool. The middle distillate fraction (140-370°C) obtained from mild hydrocracking product was found to have cetane number in the range of 48-54. The bottom product from mild hydrocracking of heavy vacuum gas oils was found to be a good feedstock for fluidized catalytic cracking unit because of its low sulphur, nitrogen and aromatic contents. The data obtained from pilot plant studies showed that the processing of mild cracker bottom in FCC unit would result in better quality fuels.     

KINETICS OF HYDRODESULFURIZATION OF HEAVY GAS OIL DERIVED FROM OIL-SANDS BITUMEN

ABSTRACT

With gradual shortage in the supply of crude oil, the importance of producing synthetic crude oil from oil sands and shale oil is increasing day by day. In the present paper, the effects of various process variables such as temperature, liquid hourly space velocity and hydrogen/heavy gas oil volumetric ratio on the removal of sulfur compounds from oil sands derived heavy gas oil has been studied. The experiments have been carried out in a micro scale trickle bed reactor over a commercial Ni–Mo catalyst. The temperature, liquid hourly space velocity and hydrogen/heavy gas oil volumetric ratio have been varied from 365 to 415°C, 0.5 to 1.9 h^?1 and 400 to 1000 ml, respectively. Under optimum reaction conditions over 96% conversion of sulfur compounds was achieved. The kinetics of the rate of sulfur removal from the oil sands derived heavy gas oil has also been discussed in this article.     

地层水对凝析气藏注CO_2相态的影响

常规的凝析气藏衰竭开发和注CO_2开发研究中均忽略了地层水的影响,这与真实情况存在偏差,有可能导致研究结果的不确定性加大。为此,基于CO_2—烃—水相平衡热力学模型,以一个实际近临界凝析气藏为例,通过相态模拟研究了地层水存在对凝析气藏反凝析相态特征和注CO_2相态的影响规律;计算了考虑地层水存在的凝析气定容衰竭反凝析液饱和度和剩余流体组成,以及注CO_2过程中凝析油气相体积分数和CO_2在凝析油气相中体积分数的变化规律。结果表明:1考虑地层水时定容衰竭的反凝析油饱和度更大,剩余流体重组分含量更高;2近临界凝析气藏压力衰竭过程中,由凝析气转变为挥发油的相变发生得更早;3在注CO_2过程中,地层水的存在使得CO_2对凝析油的反蒸发作用降低;4考虑地层水存在时凝析油相体积分数高约14%,CO_2在凝析油中溶解量比不考虑地层水大6%,CO_2含量高和压力较高时差异更明显,同时,地层水的存在也增强了CO_2的溶解封存能力。该研究成果对凝析气藏注CO_2提高采收率和温室气体CO_2埋存评价具有指导意义。     

固相萃取-气相色谱-质谱法测定费-托合成油中间馏分的烃类组成及碳数分布

采用SiO₂/Ag-Al₂O₃双柱固相萃取技术将费-托合成油中间馏分分离为饱和烃、烯烃、芳烃、氧化物等组分,利用气相色谱-质谱/氢火焰离子化检测器（GC-MS/FID）和气相色谱-场电离-飞行时间质谱（GC-FI TOF MS）表征各组分的类型和碳数分布。结果表明：低温费-托合成油中间馏分以正构烷烃、正构α-烯烃、正构醇为主,分别为41.0%,30.3%,8.8%,其他化合物基本为异构化合物;高温费-托合成油中间馏分组成复杂,正构化合物含量减少,异构化合物含量明显增加,其饱和烃中存在环烷烃,烯烃中出现双烯烃、三烯烃或环烯烃,芳烃以单环芳烃为主。     

REACTION KINETICS FOR OLEFIN HYDROGENATION OVER COBALT-MOLYBDENUM HYDROTREATING CATALYST AND MODEL STUDY OF CATALYST PROPERTIES

Intrinsic kinetic data for propylene hydrogenation over a CoMo / Al₂O₃ catalyst were measured in a plug-flow integral reactor at atmospheric pressure in the ranges of temperature and propylene concentration similar to industrial processes. The parameters of several Langmuir-Hinshelwood kinetic models derived from postulated corresponding reaction mechanisms were estimated by DFP variable measurement method. It was shown in view of physical meaning, variance and residue analysis that the data could be simulated satisfactorily by power law model and the models derived from the adsorption of only either molecular hydrogen or dissociated hydrogen. A kinetic optimization method which combined diffusion-reaction model, kinetic data, pore-size distribution and tortuosity factor was proposed in this paper to calculate the intraparticle reaction dead region and intraparticle concentration profiles. The method was used to treat hydrogenation reaction and the model values of tortuosity factor were justified by single pellet string reactor experiments. Research work showed that kinetic optimization method was effective for analysis of any reaction system over arbitrary shapes of catalysts.     

COMPARISON BETWEEN THE PERFORMANCE OF CONVENTIONAL AND HIGH-METAL Co-Mo AND Ni-Mo CATALYSTS IN DEEP DESULFURIZATION OF KUWAIT ATMOSPHERIC GAS OIL

Due to environmental constraints, sulfur content of diesel fuel has been restricted to very low levels (500 ppm maximum) in many countries. As a result, a greater emphasis has been placed in recent years on the development of catalysts and processes for deep desulfurization of diesel blending streams to produce low sulfur diesel fuel. In the present work we have compared the performance of a conventional Co-Mo catalyst with that of high metal loading Co-Mo and Ni-Mo catalysts in deep desulfurization of Kuwait atmospheric gas oil. The tests were carried out in a fixed bed reactor unit using 75 ml of catalyst under the conditions: P=32 bar; LHSV = 4h^-1; H₂/oil ratio = 100 ml/ml; temperature range = 330 - 390°C. HDS activity of the high molybdenum Co-Mo catalyst was superior to that of the conventional Co-Mo hydrotreating catalyst. High metal loading Co-Mo/Al₂O₃ catalyst also showed a substantially higher HDS activity than the Ni-Mo/Al₂O₃ catalyst containing a similar high metal loading. The unreacted sulfur compounds remaining in the product after high severity hydrotreating were identified as dibenzothiophenes with alkyl substituents next to the sulfur atom. The desulfiirization of such low reactive alkyl dibenzothiophenes was found to occur at a substantially lower temperature over the high metal loading Co-Mo catalyst compared with the conventional Co-Mo catalyst. The results have been explained on the basis of the stacking and dispersion of MoS₂ slabs as well as in terms of the nature of the sulfur vacancies in the MoS₂ layers in these catalyst systems.     

REACTION KINETICS FOR OLEFIN HYDROGENATION OVER COBALT-MOLYBDENUM HYDROTREATING CATALYST AND MODEL STUDY OF CATALYST PROPERTIES

Intrinsic kinetic data for propylene hydrogenation over a CoMof Al₂ O₃ catalyst were measured in a plug-flow integral reactor at atmospheric pressure in the ranges of temperature and propylene concentration similar to industrial processes. The parameters of several Langmuir-Hinshelwood kinetic models derived from postulated corresponding reaction mechanisms were estimated by DFP variable measurement method. It was shown in view of physical meaning, variance and residue analysis that the data could be simulated satisfactorily by power law model and the models derived from the adsorption of only either molecular hydrogen or dissociated hydrogen. A kinetic optimization method which combined diffusion-reaction model, kinetic data, pore-size distribution and tortuosity factor was proposed in this paper to calculate the intraparticle reaction dead region and intraparticle concentration profiles. The method was used to treat hydrogenation reaction and the model values of tortuosity factor were justified by single pellet string     

THE ROLES OF CARBON DIOXIDE IN METHANOL SYNTHESIS

The roles played by carbon dioxide in the chemistry of methanol synthesis over CuO/ZnO/A1₂O₃ catalysts have been experimentally investigated. It was concluded based on reaction rate measurements and thermodynamic considerations, that the two reactions that best describe the chemical system of methanol synthesis are the CO₂-hydrogenation and water-gas shift reactions. It was also found experimentally that the presence of CO₂ is vital for maintaining the catalytic activity. The significance of the study is enhanced by the fact that this was the first such investigation of the global chemistry of methanol synthesis to be based on the novel liquid phase process. It was also observed that the rates of methanol synthesis attained a maximum when the concentration of carbon dioxide in the reactor feed was controlled at a certain optimal value. The optimal CO₂ content was found to be a function of the operating temperature and syngas composition. The experimental data are especially important because the apparatus and the operating conditions have been well-defined and carefully chosen to closely simulate industrial reactors.     

棕榈油加氢脱氧反应的规律

模拟计算了棕榈油加氢脱氧反应中直接脱氧、加氢脱羧基和加氢脱羰基 3种脱氧路径的反应热,并在中型加氢装置上,采用浸渍法制备的Ni-Mo/Al₂O₃催化剂,考察了不同工艺条件下棕榈油加氢脱氧反应规律。结果表明,棕榈油的加氢饱和反应和3种脱氧反应均为放热反应,加氢饱和反应和直接脱氧反应放热量较大,加氢脱羧基反应次之,加氢脱羰基反应最低。提高反应温度,对脱羧基反应有利,不利于加氢直接脱氧和脱羰基反应的发生;提高反应压力,对加氢直接脱氧和脱羧基反应的促进作用大于加氢脱羰基反应;提高反应空速,加氢脱羰基反应所占比例增加,加氢直接脱氧和脱羧基反应所占比例降低。棕榈油加氢脱氧产物主要是C₁₅~C₁₈的正构烷烃。     

负载型催化剂的C10烯烃低聚性能

采用固定床反应器考察了HY分子筛、活性氧化铝以及活性白土3种不同载体,三氟甲烷磺酸、AlCl₃等不同活性组分及添加量,反应温度对C₁₀烯烃低聚反应的影响。选择浸渍法将质量分数5%AlCl₃负载到活性白土上,制得C₁₀烯烃低聚反应催化剂。吡啶红外光谱表征催化剂酸性,N₂吸附-脱附分析催化剂比表面积和孔径,采用气相色谱分析产物组成及含量。结果表明：在体积空速6 h^-1、反应温度190 ℃、反应压力1 MPa条件下进行反应,二聚产物收率为40.9%,三聚产物收率为21.7%。白土作为载体相比纯活性组分作催化剂提升了活性组分的利用率,减少污染,产物与催化剂更易分离,从而降低了催化剂分离的成本。     

常一线油管式固定床选择性液相加氢生产喷气燃料的研究

本文分析了中石油青海油田格尔木炼厂生产航煤产品的优势和紧迫性;以格尔木炼厂常一线油为原料,进行了FITS加氢生产航煤的工艺研究,结果表明采用该技术可在较为缓和的条件下（反应压力3.0MPa、反应温度260℃、反应空速8.0h-1、氢油比10v/v）生产出满足GB6537-2006国家标准的军用和民用航煤产品;进一步提高反应苛刻（反应压力4.0MPa、反应温度300℃、反应空速8.0h-1、氢油比40v/v）,可以生产出总硫含量小于10ppm的低硫清洁航煤产品;经过1000小时的稳定性试验,催化剂的活性保持平稳。以试验数据为基础设计的一套15万吨/年航煤FITS加氢工业装置的计算结果表明航煤FITS加氢装置在投资、占地和加工能耗等方面均低于现有同等规模加氢装置,具有良好的工业化前景。     

Pt-SO42-/ZrO2-Al2O3催化正己烷异构化反应动力学模型

采用共沉淀法制备SO₄^2-/ZrO₂-Al₂O₃,等体积浸渍法制备Pt-SO₄^2-/ZrO₂-Al₂O₃固体超强酸催化剂,采用5mL连续固定床反应装置评价了反应温度、反应压力、氢/油体积比和体积空速对Pt-SO₄^2-/ZrO₂-Al₂O₃催化剂催化正己烷临氢异构化反应活性的影响。进行拟一级动力学模型验证,建立正己烷异构化一级反应网络动力学模型。结果表明：增加反应压力和体积空速,正己烷转化率降低;随着氢/油体积比、反应温度的升高,正己烷转化率提高。在180～200℃范围内,正己烷在Pt-SO₄^2-/ZrO₂-Al₂O₃催化剂上的临氢异构化反应可以视为简单拟...     

SLHT连续液相加氢技术的工业应用

中海油东方石化有限责任公司采用SLHT连续液相加氢技术,新建一套600 kt/a柴油加氢装置。该技术采用配套新型超深度柴油加氢脱硫RS-2000催化剂,上流式反应器,并将热高压分离器整合进反应器,取消循环氢系统,使得工艺流程简化,投资省、占地少,耗能低。装置以直馏柴油和少量催化裂解柴油为混合原料,生产硫质量分数不大于10 μg/g、氮质量分数不大于5 μg/g、十六烷值60左右的满足国Ⅴ排放标准要求的超低硫柴油产品,装置能耗相比滴流床工艺降低了25%,具有良好的经济效益。     

碳四烃芳构化产物的综合利用研究

以大庆石化公司混合碳四为原料,在500 mL碳四芳构化模试装置上进行了碳四烃芳构化产物综合利用的研究。研究结果表明,在反应温度360～400 ℃、反应压力2.0 MPa、氢油体积比50:1、体积空速1.0 h-1的条件下,采用纳米分子筛为基础研制的碳四芳构化催化剂具有较高的活性,产品结构合理,芳构化产物中的C3～C4馏分可以作为乙烯裂解原料的一个补充,C5～C10馏分可以作为高辛烷值汽油调合组分。