苏丹高酸原油两段催化裂化初步研究

在小型提升管催化裂化实验装置上进行了苏丹高酸原油两段提升管催化裂化的实验研究,考察了LTB-2催化剂和ZC-7300催化剂对苏丹高酸原油的催化裂化效果.结果表明苏丹高酸原油虽然性质较差,但是很容易催化裂化.苏丹高酸原油在ZC-7300催化剂上的转化率很高,但产物分布较差,尤其是柴油的收率太低;采用LTB-2催化剂时,苏丹高酸原油的转化率较低,但柴油和低碳烯烃的收率较高,同时可以完全脱除其中的石油酸.在丙烯产率高达20.18%的情况下,柴油收率可以达到21.63%,而且汽油的烯烃含量非常低.由于原料的残炭很高,焦炭的产率非常高,将增加烧焦负荷.     

不同基属高酸原油催化裂化反应

以石蜡基的苏丹达尔原油和环烷基的绥中36-1原油为原料,在固定流化床装置上进行了催化裂化实验,考察了反应温度、剂油比和重时空速对重油转化率和汽柴油产率的影响。结果表明,虽然基属不同,两种高酸原油催化裂化脱酸率都在99%以上,但是重油转化率和产物分布有明显区别。达尔原油裂化性能好,转化率高,但柴油产率较低,焦炭产率太高;绥中原油裂化性能差,重油转化率只有72.78%,但柴油收率较高。反应条件对两种高酸原油催化裂化的影响差别较大,反应温度和剂油比的改变对石蜡基的达尔原油影响较大,而重时空速对环烷基的绥中原油影响较大。     

高酸原油直接催化裂化反应规律研究

在实验室XTL-5型提升管中试装置上考察了反应温度、剂油质量比和停留时间对苏丹高酸原油催化裂化反应的影响。实验结果表明,在反应温度460℃、停留时间1.15 s、剂油比为6左右的缓和条件下,苏丹高酸原油的重油转化率在90%以上,液收可以达到80%以上。由于原料的残炭质量分数大于8%,导致苏丹达尔原油的直接催化裂化焦炭产率较高。随反应温度的升高和停留时间的延长,转化率不断提高,但汽柴油收率不断下降。随剂油比的增大,汽油产率先升高后降低,柴油收率则不断下降。     

催化裂化装置加工高酸原油后设备腐蚀问题探讨

加工高酸原油后,催化裂化装置分馏塔低温位腐蚀严重,采用扫描电镜等分析手段进行分析,得出腐蚀原因可能是脱后原油含盐量超标,在塔顶形成HCl-H2S-H2O强酸性腐蚀环境,发生H2S与HCl含水体系的交互腐蚀。通过采取多种有效措施,将脱后原油盐含量从大于3mg/L降至3mg/L以下,解决了催化装置腐蚀问题。     

原油及馏分油脱酸技术进展

石油酸是原油和馏分油中普遍存在的腐蚀性物质,其主要成分为环烷酸并且含量可以高达90%以上。环烷酸具有羧酸的所有化学性质,所以常常造成严重的腐蚀,从而影响原油加工设备及油品使用设备的正常运行和使用寿命。随着近年来世界范围内高酸原油产量的逐渐增加,高原油及各种高酸值馏分油所带来的腐蚀与产品质量问题显得愈发严重,因此迫切需要开发出经济高效的脱酸技术与工艺路线。本文较为全面而详细地总结并评述了国内外原油及油品的各种脱酸技术方法。分析表明：目前所报道的各类脱酸工艺较多,其中工业应用的加氢脱酸效果虽好但是成本较高,而其他大多数脱酸方法都存在较多的缺点或不足,因此探寻一种绿色环保、经济高效并且具有较好普适性的油品脱酸工艺显得非常迫切而必要。酯化法脱酸具有加工工艺简单、不需要复杂的后继处理,几乎可以降低所有的高酸值原油和油品（轻质、重质馏分油以及渣油）的酸值,为原料油的进一步加工提供了方便。酯化脱酸工艺的关键在于高效催化剂的选择,而目前的催化酯化体系虽然脱酸率较高,但仍存在着反应时间较长的不足,相信通过反应过程强化等手段解决该问题以后,催化酯化脱酸工艺会被很快投入到原油及油品的脱酸实际工业生产中去。     

高酸原油脱酸技术研究

考察了热处理条件对高酸值达布朗原油的脱酸效果的影响,通过一系列的实验,发现温度和时间是影响脱酸效果的主要因素,找到了针对达布朗原油较好的热处理条件。考虑到高温热处理会使原油的物理化学性质发生改变,还在较低温度下考察了在原油中加入氧化镁能否有效的提高脱酸率,结果表明,在较低温度下氧化镁能显著的改善脱酸效果。     

国内外高酸原油脱酸发展现状

近年来,随着常规原油资源日益减少和原油开采技术的提高,非常规原油的产量逐年增加。非常规原油的酸值一般较高,基本都属于高酸原油,高酸原油在加工的过程中会对设备造成严重的腐蚀,而且对石油产品的使用性能产生较大影响,因此,解决高酸原油加工问题具有重大的意义。介绍了国内外高酸原油脱酸的几种工艺,如碱洗脱酸、醇氨法脱酸、酯化脱酸、加氢法、热分解法等方法,并对各种方法进行了对比。     

高酸原油加工模式研究

针对高酸原油加工的四种类型,进行了经济性计算和分析,对各自的特点和存在问题进行了剖析;国际油价高低对高酸原油加工效益的影响较小,而高酸原油与基准原油的价差则是影响加工效益的关键因素。     

高酸原油催化脱酸效果试验研究

对高酸原油的催化脱酸效果进行了试验,分别进行了不同温度下的脱酸效果,不同空速下的脱酸效果,不同催化剂下的脱酸效果以及不同种类的有机酸的脱酸效果的试验研究。通过研究可知Mg对于催化剂的脱酸效果有重要的影响,浸镁的ML-16B催化剂效果明显高于不浸镁的催化剂,且脱酸效果随温度的升高而增加;在重时空速方面,当空速低于18 h-1时,如果继续降低空速不但不能有效的提高脱酸率还会增加脱酸成本;比较了不同酸种类的脱酸效果可以发现,有机酸的碳链越长,脱酸效果越差。     

高酸原油润滑油馏分加氢脱酸研究

环烷基原油润滑油馏分适合作变压器油、冷冻机油以及橡胶填充油等特种油,但其酸值较高,必须经脱酸处理才能满足使用要求。选用加氢脱酸催化剂A和催化剂B对高酸原油润滑油馏分（常二线油、减二线油和减三线油）进行加氢脱酸研究,结果表明,常二线油在较缓和的反应条件下,可达到预期脱酸效果,而减二线油和减三线油加氢脱酸难度增大,反应温度需相应提高（40～50） ℃,催化剂B比催化剂A具有更高的加氢脱酸活性。     

Kinetic study of crude oil-to-chemicals via steam-enhanced catalytic cracking in a fixed-bed reactor

This study presents new experimental results on the direct conversion of crude oil to chemicals via steam-enhanced catalytic cracking. We have organized the experimental results with a kinetics model using crude oil and steam co-feed in a fixed-bed flow reactor at reaction temperatures of 625, 650, and 675°C over the Ce-Fe/ZSM-5 catalyst. The model let us find optimum conditions for crude oil conversion, and the order of the steam cracking reaction was 2.0 for heavy oil fractions and 1.0 for light oil fractions. The estimated activation energies for the steam cracking reactions ranged between 20 and 200 kJ/mol. Interestingly, the results from kinetic modelling helped in identifying a maximum yield of light olefins at an optimized residence time in the reactor at each temperature level. An equal propylene and ethylene yield was observed between 650 and 670°C, indicating a transition from dominating catalytic cracking at a lower temperature to a dominating thermal cracking at a higher temperature. The results illustrate that steam-enhanced catalytic cracking can be utilized to effectively convert crude oil into basic chemicals (52.1% C2-C4 light olefins and naphtha) at a moderate severity (650°C) as compared to the conventional high-temperature steam cracking process.     

CDOS催化剂的重油裂化性能

通过对某炼油厂减四线油和减四线抽出油的性能对比,选择更难裂化的减四线抽出油在小型固定流化床装置上,对以DOSY为活性组元的CDOS催化剂和常规REY重油裂化降烯烃催化剂进行对比实验,考察已工业应用的CDOS催化剂在实验室条件下,对催化剂的重油转化及降烯烃的能力。结果表明,在相同剂油比下,CDOS催化剂作催化材料时,具有更好的产物分布,可获得较高的转化率和轻质油收率以及较低的焦炭和重油收率。CDOS催化剂降低汽油中烯烃的能力高于常规REY类型重油裂化降烯烃催化剂。     

长庆原油不同馏分的催化裂化性能研究

在固定流化床装置上进行了长庆原油的常压渣油、脱沥青油和减压渣油的催化裂化反应,考察了反应温度对产物分布、氢转移反应及柴汽比的影响。结果表明:常压渣油的裂化性能最好,脱沥青油次之,减压渣油的裂化性能最差。相同的反应条件下,脱沥青油的转化率比减压渣油高约6百分点,总液收高20百分点以上,而焦炭产率则只有减压渣油的2/3。对不同的原料,反应温度对氢转移反应和柴汽比的影响趋势不同。减压渣油的氢转移和柴汽比受反应温度的影响较大。     

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。     

Recovery of phytosterols from sunflower oil deodorizer distillates

Phytosterols are usually recovered by crystallization from the deodorizer distillate (DD) of vegetable oils. In this work, the impact of the principal process variables (viz., solvents and cosolvents, cooling rate, crystallization temperature, and ripening time) on the quality and yield of the recovered phytosterols was studied by using a sunflower oil DD “enriched” (i.e., preconcentrated) via transesterification with ethanol (EDD) as a feedstock and commercial hexane as solvent (S), with S/EDD mass ratios of 3 to 5. Water (0 to 4.5 wt%) and ethanol (0 to 10 wt%) were used as cosovents, with crystallization temperatures between 0 and −20°C and crystallization times from 4 to 96 h. The cooling rate was either −20°C/h or “brisk chilling” from 40 to −5°C. The nature and composition of the EDD solvent and cosolvent composite arose as the most important process variable, strongly influencing both the percentage of sterol yield and the purity of the crystals, as well as their filterability and washability. Water-saturated hexane sufficed to give good crystallization, yet the beneficial effect of adding water as the single cosolvent was enhanced by adding small and precise amounts of ethanol. A recovery of sterols as high as 84% (with 36% purity) was achieved by using a single-stage batch crystallization of the S/EDD mixture (S/EDD=mass ratio 4).     

Photocatalyzed oxidation of crude oil residue by beach sand

Crude-oil residue in contact with beach sand and air was observed to undergo photocatalytic oxidation on exposure to light from a high pressure mercury vapor lamp. The kinetics of the heterogeneous reaction were of zero order in the mass of organic material present. Carbon dioxide was the oxidation product. No dark reaction occurred. The beach sand used contained magnetite and ilmenite as minor constituents. These materials are known to have catalytic properties for hydrocarbon oxidation. The results point to a self-cleaning process provided by the natural environment for the photocatalytic removal of crude-oil contamination from sandy beaches.     

Review of processes for downhole catalytic upgrading of heavy crude oil

Unlike conventional refinery processing, downhole upgrading involves implementing catalytic processes in oil-bearing geologic formations. In this way impurities contained in heavy crude oil can possibly be left in the ground or easily separated during oil production, providing an improved crude oil feed for refineries. Additionally, value or viability can be added to an otherwise uneconomic or remote heavy oil deposit. In order to successfully produce improved quality oil via a downhole upgrading project, several processing steps are anticipated: placement of catalysts into an appropriate downhole location, mobilization of reactants over the catalyst bed, and creation of processing conditions necessary to achieve a reasonable degree of catalytic upgrading. Each of these steps has been proven by past application; their combination into a unified below-ground process remains problematic. Downhole processing differs from surface processing in that brine, high steam partial pressures and low hydrogen partial pressures need to be accommodated in the downhole setting. There are no reports of significant downhole catalytic upgrading of crude oil, although examples of thermal upgrading are noted. However, available technology should be amenable to conducting a successful process. Upgrading of heavy crude oil at anticipated downhole processing conditions has been successfully proven in the laboratory. Recently published literature with immediate pertinence to the problems of downhole catalytic upgrading is reviewed with the goal of stimulating research and providing directions for future investigations.     

参考油在催化裂化生成油模拟蒸馏分析中的重要性

本文简述了参考油在催化裂化生成油模拟蒸馏分析中的作用及重要性,通过实验证明参考油在跟踪色谱柱漂移、检验色谱进样、检测系统是否正常、判断色谱柱失效等方面有重要作用。