含硫原油的渣油ARDS与VRDS不同加工方案的技术经济比较

以80％的阿拉伯轻质原油和20％的阿拉伯重质原油的混合油为例，对一个原油加工能力为500万t／a的新建炼油厂采用ARDS（常压渣油加氢脱硫）和VRDS（减压渣油加氢脱硫）5种不同的加工方案进行了技术经济分析。表明在现行的价格和税制情况下，采用VRDS工艺比采用ARDS工艺在利润、投资效益率和柴汽比等方面占有优势。     

高硫含量原油加工

高硫含量原油加工路线的实质，主要是指常压渣油或减压渣油的加工方案。渣油加工有脱碳工艺、加氢工艺及沥青气化工艺。作者结合国内实际情况，重点介绍及推荐了沥青生产、减粘、延迟焦化、渣油加氢脱硫、溶剂脱沥青、沥青造气等渣油加工工艺，以及选择加氢裂化工艺的思路和原则。     

采用水溶性分散型催化剂的渣油悬浮床加氢工艺

抚顺石油化工研究院于９０年代开发的采用多金属水溶性分散型催化剂的渣油悬浮床加氢技术已完成了小型和中型运转试验。用研制的水溶性催化剂和悬浮床加氢工艺处理辽河、胜利、孤岛及沙特阿拉伯等原油的劣质常压渣油和减压渣油,单程通过得到的馏分油总收率可达６０％～８０％,过程基本不生焦。对辽河渣油悬浮床加氢尾油进行了延迟焦化和调合沥青试验,结果表明尾油可以得到充分利用。     

上流式反应器应用于固定床渣油加氢装置改造设计的体会

我国第一套渣油加氢装置——齐鲁石化公司０．８４Ｍｔ／ａ减压渣油加氢脱硫装置自１９９２年６月开工运转至今已６年。该装置采用美国Ｃｈｅｖｒｏｎ公司固定床减压渣油加氢脱硫（ＶＲＤＳ）工艺，原设计加工的原料油是孤岛原油的减压渣油。经加氢转化后所生产的减压瓦斯...     

渣油加氢脱硫拓宽了渣油催化裂化的应用

常压渣油加氢脱硫或减压渣油加氢脱硫与渣油催化裂化的组合工艺，提出了一个竞争力的加工燃料油的路线。在ＲＦＣＣ装置前采用ＲＤＳ或ＶＲＤＳ，可以使炼油厂加工的原油有更宽的选择范围、同时能经济地将渣油转化成动作用油田。     

焦炭沿渣油加氢催化剂径向的沉积规律

分别以胜利原油、沙特轻质原油和委内瑞拉原油的减压渣油为原料,采用渣油加氢脱硫、脱残炭催化剂,利用扫描电子显微电镜-能谱仪(SEM-EDS)联用技术对加氢后催化剂剖面径向不同部位的焦炭沉积情况进行了定性、定量分析。结果表明:在反应时间为2 h,反应温度为400℃,氢气初始压力为6 MPa,搅拌转速为500 r/min的条件下,焦炭沉积量沿催化剂剖面径向呈对称性分布,其分布规律受渣油平均相对分子质量、残炭质量分数、芳香性等因素的影响。     

沙特轻质原油的重油五种加工方案比较

以沙特轻质原油的重油为代表,介绍减压渣油延迟焦化、减压渣油加氢处理、常压渣油加氢处理、减压渣油溶剂深脱沥青（以生产重交通道路沥青为主）、减压渣油溶剂浅脱沥青（以大量生产脱沥青油为主）等五种重油加工方案,并进行技术经济分析。比较结果表明,五种加工方案各有其优缺点。其优点是：延迟焦化投资最低;两种加氢的轻油收率最高;深度脱沥青可解决含硫渣油的出路;而浅度脱沥青的经济效益最好。炼油厂应同时考虑它们的缺点,根据自身的需要选择合适的加工方案。     

我国含硫原油加工技术路线和技术进步

(1)渣油加氢处理／渣油催化裂化(RHT／RFCC)技术 中国加工进口含硫原油不断增多，使含硫渣油加工处理成为渣油加工的一大课题。将渣油加氢处理与RFCC相组合，可最大量提高轻质产品产率。这种联合技术的特点可使渣油脱金属、脱硫、脱氮，适用于加工高含金属、硫和残炭的中东渣油。高硫渣油加氢处理(RHT)可生产经加氢处理的常压渣油(或减压渣油)，     

渣油加工技术的研究Ⅲ.渣油加工方案及技术经济性的研究

介绍了减压渣油焦化（DC）、减压渣油脱硫（VRDS）、常压渣油脱硫（ARDS）、深脱沥青（SDA1）、浅脱沥青（SDA2）5种加工方案与炼油厂产品收率的关系，同时对不同产品方案的经济性进行了比较。综合考虑渣油加工5种路线的经济性和资源利用的有效性，以渣油VRDS和ARDS加氢脱硫方案为较佳，其次为SDA-2方案，焦化方案最差（尽管其装置投资较低）。     

5Mt／a加工高硫原油炼油厂开工经验

设计以沙特阿拉伯轻质、重质原油各５０％为原料,年加工能力５Ｍｔ,工艺流程以常减压蒸馏－重油加氢脱硫－重油催化裂化为主线,对目前国内唯一能单独全部加工高含硫原油炼油厂的两种开工方案进行了比较。确定全流程投料开车分两步实施：第一步选择低硫原油,先开成一个低硫炼油厂,重油不进行加氢精制;第二步低硫原油向高硫原油逐步切换,开重油加氢脱硫等加氢装置和硫磺回收装置。这样能很好地衔接原油硫含量,既可满足重油加氢脱硫等加氢装置的开车需要,又使重油催化裂化等装置正常生产。     

燃料型炼油厂提高轻质油收率加工方案的比较

在工艺路线经济技术评价模型系统的基础上,对沙特轻质、沙特重质原油各50％的混合原油进行提高轻质油收率加工方案的研究。对渣油脱碳型、渣油加氢型、渣油脱碳-渣油加氢组合型工艺13个不同加工方案进行研究的结果表明,轻质油收率由高到低的加工方案为：渣油加氢型方案≈渣油脱碳-渣油加氢组合型方案>渣油脱碳型方案;在高油价条件下,经济效益由高到低的加工方案为：渣油加氢型方案>渣油脱碳-渣油加氢组合型方案>渣油脱碳型方案。     

进口原油减压渣油生产优质建筑沥青试验

用沙中、科威特,阿曼及阿曼与胜利混合原油的减压渣油,进行了用各种氧化工艺条件生产优质建筑沥青的试验,试验结果表明,沙中、科威特减压渣油通过氧化可生产出符合GB/G494-1998标准的10号建筑沥青,用阿曼和75%阿曼与胜利混合原油的减压渣油可生产出10号、30号,40号优质建筑沥青。     

DEVELOPMENT OF HIGH-PERFORMANCE HEAVY OIL HYDROCRACK1NG CATALYSTS: CHARACTERIZATION OF ATMOSPHERIC RESIDUE FEED

ABSTRACT

The characterization results of the atmospheric residue obtained from Saudi Arabian Light crude oil show the complex nature and composition of this material. The distillation results showed that about 50 percent of Arab Light crude is the atmospheric residue. The elemental analysis of the residue showed that high amount of carbon, sulfur and nitrogen is present along with heavy metals such as nickel and vanadium. The determination of hydrocarbon types by HPLC exhibited that 12% polars and 27% aromatics are present along with 6% asphaltenes. Nuclear magnetic resonance study conducted on the residue and its fraction provides a detailed composition in terms of aliphatic and aromatic nature of the residue and its fractions. The results showed that the residue contains 21% aromatic and 79% aliphatic carbon. The aliphatic carbon is present in saturates and as side chains of aromatic and polar molecules whereas the aromatic carbons are those in the ring structure. Asphaltenes separated from the residue were characterized for their different properties to understand its complexity. The use of electron spin resonance spectroscopy provides determination of the free radicals present in the residue. Asphaltenes were analyzed using the state-of-the-art high temperature high pressure electron spin resonance (ESR) technique in the temperature range 20 to 625 °C and at 30 and 50 bar hydrogen pressure. The ESR determination at 30 bar shows that me pressure was not enough to prevent the boiling of the asphaltene and thus a decrease in the spin concentration was observed beyond 350 °C temperature. The data at 50 bar pressure showed the adequacy of this pressure for ESR measurement. The PMRTA analysis of asphaltene showed a decrease in residual hydrogen with increasing temperature.     

CATALYTIC HYDROTREATMENT OF PETROLEUM RESIDUE

Iraqi reduced crude (350°C+) with a sulfur content of 4.3 wt% and a total metal content (Ni+V) of 141 WPPM was n-heptane deasphalted at specified conditions. The deasphalted oil (97.2 wt% of original residue) contains 4.1 wt% of sulfur and 103 ppm of metal. The original reduced crude and deasphalted oil were hydrotreated on a commercial Ni-Mo-alumina catalyst presulfided at specified conditions in a laboratory trickle-bed reactor. The reaction temperatures varied from 300 to 420°C with the liquid hourly space velocity (LHSV) ranging from 0.37 to 2.6 h^-1. Hydrogen pressure was kept constant throughout the experiments at 6.1 MPa, with a hydrogen/oil ratio of about 300 NLL^-1 (normal liters of hydrogen per liter of feedstock). Analysis for sulfur, nickel, vanadium and n-pentane asphaltenes were carried out for hydrotreated products from both the original residue and the deasphalted oil. The comparison of the results obtained for the hydrotreatment of deasphalted oil and original reduced crude indicates that the removal of sulfur, nickel and vanadium was higher for the deasphalted oil than those obtained for the non-deasphalted residue over the entire range of conversion. The exclusion of extremely high molecular weight asphaltenes by n-heptane deasphalting seems to improve the access of oil into catalyst pores resulting in higher desulfurization and conversion of the lower molecular weight asphaltenes. The sulfur content of n-pentane precipitated asphaltenes remained unchaneed with LHSV for various temperature for hydrotreated products produced from both deasphalted oil and original reduced crude.     

CATALYTIC HYDROTREATMENT OF PETROLEUM RESIDUE

ABSTRACT

Iraqi reduced crude (350°C+) with a sulfur content of 4.3 wt% and a total metal content (Ni+V) of 141 WPPM was n-heptane deasphalted at specified conditions. The deasphalted oil (97.2 wt% of original residue) contains 4.1 wt% of sulfur and 103 ppm of metal. The original reduced crude and deasphalted oil were hydrotreated on a commercial Ni-Mo-alumina catalyst presulfided at specified conditions in a laboratory trickle-bed reactor. The reaction temperatures varied from 300 to 420°C with the liquid hourly space velocity (LHSV) ranging from 0.37 to 2.6 h^?1. Hydrogen pressure was kept constant throughout the experiments at 6.1 MPa, with a hydrogen/oil ratio of about 300 NLL^?1 (normal liters of hydrogen per liter of feedstock). Analysis for sulfur, nickel, vanadium and n-pentane asphaltenes were carried out for hydrotreated products from both the original residue and the deasphalted oil. The comparison of the results obtained for the hydrotreatment of deasphalted oil and original reduced crude indicates that the removal of sulfur, nickel and vanadium was higher for the deasphalted oil than those obtained for the non-deasphalted residue over the entire range of conversion. The exclusion of extremely high molecular weight asphaltenes by n-heptane deasphalting seems to improve the access of oil into catalyst pores resulting in higher desulfurization and conversion of the lower molecular weight asphaltenes. The sulfur content of n-pentane precipitated asphaltenes remained unchaneed with LHSV for various temperature for hydrotreated products produced from both deasphalted oil and original reduced crude.     

两种中东原油的减压渣油性质的研究

运用超临界流体萃取分馏技术，对两种中东原油（沙特轻质原油与阿曼原油）的减压渣油进行分离，测定与分析了窄馏分的折光指数、密度、粘度、残炭、平均相对分子质量、元素分析（C、H、S）、金属含量（Ni，V）、族组成（饱和烃、芳香烃和胶质含量）及结构组成。并与大庆、辽河原油的减压渣油分离结果进行了对比，为沙特轻质原油及阿曼原油的减压渣油的合理加工提供了重要的基础数据。     

催化裂化轻循环油生产高辛烷值汽油技术 LTAG 的工业应用

福建联合石油化工有限公司在蜡油加氢处理和催化裂化装置上采用LTAG技术，以催化裂化轻循环油（LCO）和蜡油生产高辛烷值汽油。对LCO和蜡油混合加氢后得到的加氢LCO和加氢蜡油分别在催化裂化提升管反应器下部不同位置分层顺序进料方式（LTAG技术）与在催化裂化反应器下部混合进料方式的生产数据进行了系统的分析和总结。结果表明：与混合加氢油进料的常规方式进行对比，LTAG技术的LCO催化裂化表观转化率提高5.17百分点，表观裂化率提高7.87百分点，表观缩合率降低2.01百分点，稳定汽油中烯烃和芳烃的体积分数分别增加1.2百分点和2.0百分点，汽油辛烷值RON和MON分别提高1.4个单位和0.8个单位。LTAG技术是将LCO高效转化为高辛烷值汽油的重要手段。     

减压渣油掺沥青减粘裂化工业试验

为了扩大减粘裂化装置的原料来源,解决脱油沥青的出路问题,进行了减压渣油掺沥青减粘裂化的实验室及工业应用试验,并对原０．４０ Ｍｔ／ａ减粘裂化装置进行了改造。试验采用大庆和涠洲混合减压渣油,掺入３０％和５０％的大庆丙烷脱油沥青,并在掺炼５０％沥青时加入４％～８％的高芳烃组分。工业试生产结果表明掺炼沥青后产品质量和能耗均达到改造设计要求,高芳烃组分有抑制结焦的作用,同时可提高沥青掺入量,减粘裂化装置掺炼沥青可取得良好的经济效益。     

渣油加工的经济性分析

分析了渣油加工的经济性,以三组原油和油品价格分析了油价对评估结果的影响。     

南阳减压渣油生产道路沥青的研究

针对南阳石蜡基原油其减压渣油不符合道路沥青标准要求,减压渣油经溶剂脱沥青后,也不能直接生产出合格的道路沥青的情况,利用减压渣油中掺入部分催化裂化油浆,经溶剂脱沥青可使脱油沥青的质量得到明显改善,当掺入的油浆量达到适当比例时,利用溶剂脱沥青工艺,可直接生产出各种牌号的道路沥青,并且利用溶剂脱沥青得到的高软化点脱油沥青与糠醛抽出油进行调合,也可以生产出合格的道路沥青。