A Comparative Study on the Hydrocracking for Atmospheric Residue of Mongolian Tamsagbulag Crude Oil and Other Crude Oils

Upgrading heavy and residual oils into valuable lighter fuels has attracted much attention due to growing worldwide demand for light petroleum product. This study focused on hydrocracking process for atmospheric residue (AR) of Mongolian crude oil in the first time compared to those of other countries. Residue samples were hydrocracked with a commercial catalyst at 450℃, 460℃, 470℃ for 2 hours under hydrogen pressure of 10 MPa. The AR conversion and yield of light fraction (LF) reached to 90.6 wt% and 53.9 wt%, at 470℃ by the hydrocracking for atmospheric residue of Tamsagbulag crude oil (TBAR). In each sample, the yield of MF was the highest at 460℃ temperature, which is valuable lighter fuel product. The polyaromatic, polar hydrocarbons and sulfur compounds were concentrated in the MF and HF because the large amount of light hydrocarbons produced from TBAR as the increasing of the hydrocracking temperature. The content of n-paraffinic hydrocarbons was decreased in HF of TBAR, on effect of hydrocracking temperature. This result suggests the longer molecules of n-paraffin (С20-С32) in HF were reacted better, than middle molecules of n-paraffin (С12-С20) in MF during the hydrocracking reaction. Because the hydrocarbon components of feed crude oils were various, the contents of n-paraffinic hydrocarbons in MF and HF of TBAR and DQAR were similar, but MEAR’s was around 2 times lower and the hydrogen consumption was the highest for the MEAR after hydrocracking.

中国炼油工业技术发展途径展望

我国炼油工业已形成完整配套的工业体系。2020年前我国油品需求将保持较高增长速度,但当前面临石油资源短缺、产品质量不高、化工轻油供需矛盾突出、环境治理等严峻形势。为此,炼油工业需结合我国实际,走发展深度加工道路,生产其他能源难以取代的运输燃料和化工原料;继续发挥催化裂化生产成品油的骨干作用;加快发展加氢裂化,实现油化一体化;采取原料预处理、催化裂化新工艺和产品后处理三者结合,提高成品油质量;污水实现回用,控制SOX对大气污染,加快我国炼油工业的发展。

Novel design of lubricant-type vacuum distillation process for lube base oils production from hydrocracking tail oil

Dividing-wall columns(DWCs)are widely used in the separation of ternary mixtures,but rarely seen in the separation of petroleum fractions.This work develops two novel and energy-efficient designs of lubricant-type vacuum distillation process(LVDP)for the separation of hydroisomerization fractions(HIF)of a hydrocracking tail oil(HTO).First,the HTO hydroisomerization reaction is investigated in an experimental fixed-bed reactor to achieve the optimum liquid HIF by analyzing the impact of the operating conditions.A LVDP used for HIF separation is proposed and optimized.Subsequently,two thermal coupling intensified technologies,including side-stream(SC)and dividing-wall column(DWC),are combined with the LVDP to develop side-stream vacuum distillation process(SC-LVDP)and dividing-wall column vacuum distillation process(DWC-LVDP).The performance of LVDP,SC-LVDP,and DWC-LVDP are evaluated in terms of energy consumption,capital cost,total annual cost,product yields,and stripping steam consumption.The results demonstrates that the intensified processes,SC-LVDP and DWC-LVDP significantly decreases the energy consumption and capital cost compared with LVDP.DWC-LVDP further decreases in capital cost due to the removal of the side stripper and narrows the overlap between the third lube oils and fourth lube oils.This study attempts to combine DWC structure into the separation of petroleum fractions,and the proposed approach and the results presented provide an incentive for the industrial implementation of high-quality utilization of HTO through intensified LVDP.

Hydrocracking diversity in n-dodecane isomerization on Pt/ZSM-22 and Pt/ZSM-23 catalysts and their catalytic performance for hydrodewaxing of lube base oil

Nobel metallic Pt/ZSM-22 and Pt/ZSM-23 catalysts were prepared for hydroisomerization of normal dodecane and hydrodewaxing of heavy waxy lube base oil.The hydroisomerization performance of n-dodecane indicated that the Pt/ZSM-23 catalyst preferred to crack the C-C bond near the middle of n-dodecane chain,while the Pt/ZSM-22 catalyst was favorable for breaking the carbon chain near the end of n-dodecane.As a result,more than 2%of light products(gas plus naphtha)and3%more of heavy lube base oil with low-pour point and high viscosity index were produced on Pt/ZSM-22 than those on Pt/ZSM-23 while using the heavy waxy vacuum distillate oil as feedstock.

Application of Hydrocracking Process for Upgrading Tail Oil Quality in 1.0 Mt/a Hydrocracker Unit at SINOPEC Yangzi Petrochemical Company

This article focuses on the hydrocracking technology for upgrading the quality of tail oil and the first commercial application of the RN-32V/RHC- 1 catalysts in the 1.0 Mt/a hydrocracker at the Yangzi Petrochemical Company, which was started up successfully in September 2008. One month after start-up of the hydrocracking unit, an evaluation opera- tion has been conducted fbr assessing the catalysts performance. The technical calibration results showed that the RN- 32V/RHC-1 catalysts had high activity, and the product yield distribution was reasonable. The hydrocracker can provide abundant feedstocks for the downstream aromatic production unit and ethylene production unit.

Application of Discrete Lumped Kinetic Modeling on Vacuum Gas Oil Hydrocracking

The kinetic model of vacuum gas oil （VGO） hydrocracking based on discrete lumped approach was investigated, and some improvement was put forward at the same time in this article. A parallel reaction scheme to describe the conver- sion of VGO into products （gases, gasoline, and diesel） proposed by Orochko was used. The different experimental data were analyzed statistically and then the product distribution and kinetic parameters were simulated by available data. Fur- thermore, the kinetic parameters were correlated based on the feed property, reaction temperature, and catalyst activity. An optimization code in Matlab 2011b was written to fine-me these parameters. The model had a favorable ability to predict the product distribution and there was a good agreement between the model predictions and experiment data. Hence, the ki- netic parameters indeed had something to do with feed properties, reaction temperature and catalyst activity.

Characterization and Modification of Indonesian Natural Zeolite for Hydrocracking of Waste Lubricant Oil into Liquid Fuel Fraction

Modification and characterization of natural zeolite under some various methods for hydrocracking catalyst of waste lubricant to gasoline and diesel fractions have been conducted. Natural zeolite from Klaten was activated using hydrothermal treatment at temperature 500 ℃ for 6 h （produced ZAAHd）, the ZA sample was treated with hydrothermal followed by Microwave （produced ZAAHdM）, the ZA sample was treated with HCI 3 N at temperature of 90 ℃ for 30 min （produced ZAAH）, the ZAAH sample was heated in to microwave （produced ZAAHM）, the ZAAHM was treated hydrothermal （produced ZAAHMHd）, the ZAAHMHd sample was heated in to microwave （produced ZAAHMHdM）, soaking of natural zeolit activated by HCl-microwave-hydrothermal-microwave in NH4NO3 1 N which was stirred using stirer at room temperature for 24 h （produced ZAAHMHdMN） and the ZAAHMHdMN sample was heated into microwave （ZAAHMHdMNM）. The heating process by microwave was conducted at 550 watt for 15 rain. Catalyst characterization involved determination of the number of total acid sites using gravimetric method with vapour adsorption of NH3 and pyridine, catalyst crystallinity by XRD （X-ray diffraction） and TO4 （T= Si and AI） site by infra red spectrophotometer （IR）. Hydrocracking of waste lubricants oil was performed in a fixed bed reactor of stainless steel at temperature of 450 ℃, H2 flow rate of 15 mL/min., feed/catalyst ratio of 5. Liquid products of the hydrocracking were analyzed using GC （gas chromatography）. The characterization results showed that various modification of natural zeolite increased acidity and dealumination degree of the catalysts. Products of the hydrocracking were liquid, coke, and gas fractions. Liquid products consisted of gasoline fraction （C5-C12）, diesel fraction （C12-C20）, and heavy oil fraction （〉 C20）.Thc conversion of liquid products was increased with the increase of catalyst acidity. The greatest liquid product conversion was produced by the ZAAHMHdMNM catalyst, i.e., 56.80%, with selectivity towards gasoline, diesel, and heavy oil fractions was 88.37%, 8.61% and 3.02%, respectively. The increase of catalyst acidity increased the selectivity of gasoline fraction.

Processing of tailings in Canadian oil sands industry

Vast amounts of tailings are produced daily in bitumen extraction from the Athabasca oil sands. The coarse sand from the tailings stream is used to build dykes around the containment basin. The run off slurry arrives at the water’s edge in the tailings pond at a solids concentration of about 3%～8% by mass. Settling of the solids takes place "relatively fast", over several days, creating a "free water zone" that contains little solids. When the fine mineral solids concentration has reached about 15% by mass, the suspension develops non Newtonian properties. After 2～3 years, the suspension concentration reaches a value of about 30% by mass at which the settling rate becomes extremely slow. Methods to handle the already created tailings ponds and new approaches to eliminate the creation of new ones will be discussed both from the industrial and fundamental prospective.

Bitumen Recovery from Indonesian Oil Sands Using ASP(Alkali, Surfactant and Polymer) Agent

A self-developed ASP agent was used to separate bitumen from Indonesia's oil sands by its comprehensive effect and the separation condition was well investigated. The bitumen extraction conditions for industrial application were recommended to cover a mixing temperature of 80℃, a mixing time of 40 min, a mass ratio of ASP agent to oil sands of 4:10, and a floating time of 10 min. Under the above conditions, the bitumen recovery was about 86% and the residual bitumen content in tailings was about 6%. The relationship between the residual bitumen content and the particle size of tailings was studied in order to find the way to reducing the residual bitumen content in tailings. The results showed that the residual bitumen content in tailings decreased with a decreasing tailings particle size. After being milled for 30 min with a mortar, the tailings was reprocessed via extraction by means of the ASP agent, and the residual bitumen content in tailings decreased from 5.47% to 1.25%, which could comply with the disposal requirements.

Uptake of Organic Contaminants by Plants from Oil Sands Fine Tailings

The objectives of this experiment were to evaluate the performance of different plant species growing in different kinds of oil sands fine tailings,and to estimate the uptake of organic contaminants by plants from the oil sands fine tailings.In general,total hydrocarbon in the plant could be ranked(beginning with the highest)as:unweathered plant 4 tailings (UWT),Freeze Thawtailings(FT),weathered plant 4 tailings(WT),and consolidated tailings(CT) for the willow,poplar and cattails.For grass,CT amended with tailings sand and muskeg had the highest hydrocarbon level in the field treatment,however,other three kinds of tailings(FT,WT and UWT) had lower but similar to each other hydrocarbon levels.

Modeling Effect of Bitumen Extraction Processes on Oil Sands Tailings Ponds

In the oil sands industry, high temperature with the addition of a caustic dispersing agent has formed the basis of the Clark hot water extraction process used successfully on a commercial scale to recover bitumen from surface mined oil sands ore since 1967. Processes different from the established Clark process （high temperature and caustic） have been developed to work at a range of temperatures with or without the use of sodium hydroxide. Large scale bitumen extraction pilot tests were performed with two different extraction processes and large strain consolidation tests were performed on the resulting different railings. These consolidation tests determined the compressibility and hydraulic conductivity relationships with void ratio which are engineering properties that influence the long-term disposal of the fine tailings. They were used in large strain consolidation numerical analyses of storage ponds to predict water release rates and changes to surface elevations that impact storage volumes and elevation of reclamation surfaces.

含硫渣油悬浮床加氢裂化性能釜式反应评定

在无外加硫化剂的情况下,在高压釜中对含硫常压渣油进行了悬浮床加氢裂化试验,得到了较优的加氢裂化条件。实验表明,由于原料本身含硫量较高,其中的硫作为硫化剂对所加入的催化剂进行了充分地硫化,在选定的实验条件下,可以得到较高的裂化转化率及相对较少的生焦量。

Improving Light Oil Yield, an Important Way to the Sustainable Development of Petroleum

Oil resources are non- renewable and the utilization of oil resources should be sustainable andrational. Oil processing industry must, to the maximum extent, produce liquid transportation fuel and chemi-cal feedstocks, which can hardly be replaced by other forms of energy. Restructuring oil refineries in China,developing hydrocracking technologies and improving light oil yield are the significant means to achievethe sustainable development of petroleum processing industry.

沸腾床渣油加氢裂化装置结焦情况分析与操作优化

分析了沸腾床渣油加氢裂化装置易结焦堵塞的原因,介绍了某炼化公司沸腾床渣油加氢裂化装置易结焦区域和结焦典型症状,从原料、催化剂、反应和分馏工况等方面进行了优化。通过将原料渣油引入脱固油浆减缓结焦,动态调整渣油转化率控制装置结焦:加工中东高硫低氮原油所产渣油时,转化率可控制在75%以上;加工低硫中东原油所产渣油时,转化率控制在不大于70%;加工低硫高氮原油所产渣油时,转化率控制在不大于65%。每吨渣油原料置换新鲜催化剂0.90~0.95 kg,低控减压塔塔底液位(25%~30%),提高塔底物料返混流量以减少沥青质在塔底器壁生焦。优化操作后,常压塔底油总沉积物质量分数稳定小于0.2%,确保了装置在渣油高转化率下的长周期稳定运行。

加氢裂化装置硫的腐蚀与防护

对加氢裂化装置加工高硫原油后的腐蚀情况进行了分析,重点分析了装置加工高含硫原料油后出现的分馏塔顶系统的设备、管线H2S腐蚀问题。进行了205B-1型缓蚀剂的应用试验,取得了良好的缓蚀效果。

PHT-01/PHC-05组合催化剂在加氢裂化装置的工业应用

在中国石油辽阳石化公司110万t/a加氢裂化装置中,以俄罗斯原油的二次油(减压蜡油和催化柴油的混合油,二者质量比10∶1)为原料,采用中国石油自主开发的PHT-01加氢精制催化剂、PHC-05加氢裂化催化剂及PHT系列加氢保护剂,为最大限度生产重石脑油进行了工业应用,考察了催化剂应用情况、产品性质及其分布。结果表明:催化剂运行中,可同时进行湿法硫化与钝化操作,精制反应器、裂化反应器的平均反应温度分别为367,363℃,比设计值分别低5,15℃,温升比设计值分别低3,4℃;目标产品重石脑油的含硫(氮)量均小于0.5μg/g、溴指数0.755 mg/g、芳潜质量分数47.3%、初馏点73℃、收率51.56%,精制油含氮量为7~9μg/g,主要产品收率为94.04%,满足下游重整装置进料要求。

加氢裂化装置原料轻质化对反应过程影响研究

在加氢裂化装置原料轻质化的背景下,考察了蜡油中掺炼不同比例直馏柴油对加氢裂化产品分布及产品性质的影响。当直馏柴油掺炼比例为45%(质量分数,下同)时,喷气燃料收率最高,达到26%。随着直馏柴油掺炼比例的增加,重石脑油的环烷烃、芳烃含量降低;喷气燃料烟点呈逐渐升高的趋势;尾油(大于260℃)的链烷烃含量呈逐渐升高的趋势,环烷烃、芳烃含量呈逐渐降低的趋势,BMCI值(芳烃指数)呈先升高后降低的趋势。当直馏柴油掺炼比例为75%时,喷气燃料烟点最高,为28.8 mm。以掺炼15%直馏柴油的蜡油为原料时,随着转化率的升高,尾油的BMCI值逐渐降低;当尾油收率为20%时,尾油的BMCI值低至7.2,链烷烃质量分数升至62.0%,环烷烃质量分数降至35.2%,芳烃质量分数仅为2.6%。

沸腾床渣油加氢裂化装置投产对重油制氢装置的影响

沸腾床渣油加氢裂化装置投产后,将溶剂脱沥青装置的原料由常减压装置洗涤油和减压渣油调整为渣油加氢裂化装置未转化油,作为重油制氢装置原料的脱油沥青性质由此发生变化。对比重油制氢装置原料油性质、主要操作参数、技术经济指标、气化炉运行周期等参数,结果表明,渣油加氢裂化装置投产后,以脱油沥青为原料的重油制氢装置气化炉油气分布更均匀,气化单元有效气含量提高2.12个百分点,有效气产率提高0.20个百分点,碳转化率提高0.18个百分点,氢气产率提高1.21个百分点,吨氢标油能耗下降140 kg,装置各项技术经济指标均有较大幅度提升,气化炉烧嘴运行周期明显延长。

异构降凝催化剂反应性能的研究

开发了一种适用于长链正构烷烃的异构化催化剂,它含有一种具有TON晶体结构的新型沸石分子筛,对该剂的反应性能进行了研究,无论采用润滑油原料或加氢裂化尾油,该催化剂都具有高的异构降凝活性,即使在深度降凝的条件下,润滑油收率仍高达82％。基础油质量优良,可用来制取APIⅡ或Ⅲ类的高档润滑油。

渣油及其悬浮床加氢裂化尾油中氮化物的转化趋势

以孤岛减压渣油为原料,在高压釜反应器中进行悬浮床加氢裂化反应,反应温度为415℃及430℃,对反应后产物进行常减压蒸馏,并对原料及悬浮床加氢尾油进行六组分分离,将得到的各馏分及各组分用非水电位滴定法测定碱性氮含量,用化学发光定氮法测定总氮含量,进行悬浮床加氢裂化尾油中氮化物分布的研究。结果表明:在渣油的悬浮床加氢裂化过程中,既有裂解反应,又有缩合反应,产物中的碱性氮和总氮主要集中在蜡油和尾油中。悬浮床加氢裂化反应后,在尾油六组分中随组分变重,氮含量增加。碱性氮化物在加氢裂化过程中含氮杂环会发生部分饱和,使非碱性氮化合物转化为碱性氮化合物。