高酸值原油的脱酸

原油的腐蚀性主要由原油总酸值（Total Acid Number,以下简作TAN）决定，而总酸值则主要取决于石油中的环烷酸（也叫石油酸）含量，总酸值的测定一般用ASTMD664方法，以完全中和1g含酸原油所消耗的IOH毫克数表示，通常总酸值在0.5mgKOH/g 以下认为是低酸原油，而TAN在1．5以上则认为是高酸原油，由于环烷酸可在60－420℃的大范围内给石油运输和加工设备带来腐蚀，其中210－420℃时腐蚀剧烈，因此一般石油公司都要求原油总酸值在0.5mgKOH/g以下，减少或避免环烷酸腐蚀的方法主要有。     

进口原油酸值情况调查及环境风险探讨

文章针对进口原油中存在的酸性物质,通过电位滴定法进行酸值测试,对世界各地原油的酸值进行分析。探讨进口原油的酸值分布情况、酸性物质组成和危害及对环境的影响,为加工高酸原油装置建设和运行、开展高酸值原油防腐对策研究及环境风险评估提供参考。     

高酸值原油加工探讨

阐述了高酸值原油中石油酸的分布规律以及加工过程中存在的主要问题,介绍了国内外高酸值原油加工工艺技术以及加工高酸值原油时的设备防腐蚀技术.重点在于解决加工高酸值原油的炼油装置目前存在的设备腐蚀严重问题,对保障炼化企业安拿生产、提高炼化企业经济效益具有参考价值.     

电位滴定法测定原油酸值的不确定度评定

利用电位滴定法对原油中的酸值进行测定,对酸值试验结果进行了不确定度评定,建立酸值不确定度评定的计算模型,分析和计算了试验过程中影响酸值测量结果的不确定度分量,进而给出原油酸值的不确定度,原油酸值的测定结果为0.63 mg/g,其扩展不确定度为0.01 mg/g(置信因子k=2),原油酸值重复性试验是影响该方法不确定度的主要因素,重视原油试样及氢氧化钾异丙醇的滴定过程对不确定度产生的影响,原油酸值测定中,应重点从这两个方面加以改进,提高酸值测量结果的准确性。     

试论我厂加工高酸值原油的技术措施

介绍了加工高酸值原油面临的主要问题、腐蚀状况、腐蚀机理及防护措施，通过国内炼制高酸值原油炼厂和我厂的实际经验，采用材质升级、碳钢掺铝、加注高温缓蚀剂和完善“一脱三注”等措施，可以有效缓解高酸值原油对设备的腐蚀问题。     

环烷酸缓蚀剂的缓蚀性能评价研究

存在于石油中的酸性物质统称为石油酸,其中环烷酸的含量又占90％以上。当原油酸值超过0．5mgKOH／g时．就会在200～400℃下产生环烷酸腐蚀：在270～280℃时产生环烷酸腐蚀的第一个高峰：在340～350℃出现第二个腐蚀高峰：在400℃以上观察不到环烷酸腐蚀．此时环烷酸已经完全分解。环烷酸在高温下对设备的腐蚀一直威胁着相关炼油厂的生产安全。我国的辽河、孤岛、大港、中原等原油及蓬莱、流花、秦皇岛等海上原油均属于高酸值原油,近年来相当多的进口原油酸值也很高．因此,相关炼厂迫切需要解决环烷酸的高温防腐问题。     

不同原油界面活性组分的分离及表征

用极性分离法将胜利油田孤东1#、孤东4#原油和大庆原油分离为饱和分、芳香分、胶质、沥青质组分(S、Ar、R、As)。孤东1#和孤东4#沥青质组分质量分数(14.43%、11.35%)明显高于大庆原油沥青质组分质量分数(0.09%),而饱和分组分质量分数(47.08%、46.54%)低于大庆原油饱和分质量分数(68.08%)。孤东1#和孤东4#原油的原油组分(S、Ar、R、As)氧的质量分数、酸值由大到小的排序为:沥青质>胶质Ⅰ>芳香分>饱和分。而大庆原油的原油组分酸值由大到小的排序为:胶质Ⅰ>沥青质>芳香分>饱和分;大庆原油的饱和分组分中氧质量分数较低,饱和分中氧质量分数在原油氧中所占比例最高(0.375%),饱和分中的氧化物对大庆原油的界面活性影响不可忽视。在3种原油所有原油组分中,孤东1#原油沥青质的酸值最大(16.45 mg KOH/g沥青质),说明孤东1#原油沥青质组分含有较多酸性基团,反应活性较强。色-质分析结果表明,孤东原油饱和分正构烷烃在C10-C37呈双正态分布,大庆原油饱和分正构烷烃主要分布在C10-C38,基本呈正态分布。     

高酸原油酸值测定的探讨

介绍了国内外测定石油及石油产品酸值的主要标准方法,比较了它们的特点、差别。以环烷基的高酸原油绥中36-1和石蜡基的高酸原油达尔原油为测定对象,用GB/T263(颜色法)与GB/T7304(电位滴定法)进行了对比试验,得出电位滴定法更加适合测定原油、渣油和其它石油产品的酸值。并在GB/T263(颜色法)的基础上进行了改进,改进后的方法用来测定环烷基高酸原油,测得的酸值结果与电位滴定基本一致,改进后的方法具有快速、简便、易操作的特点,有利于在实验室应用。     

高酸原油脱钙技术进展

介绍了高酸原油酸值与钙含量之间的关联和钙在原油中的赋存状态、危害。综合国内外原油脱钙方法及应用背景,指出当前脱钙技术及脱钙剂存在的不足;针对现有的高酸值高钙原油的特点,提出螯合、沉淀脱钙法有较好的应用前景,提出研制开发新型、高效、环境友好、廉价的脱钙剂是主要的发展方向。     

基于逐步回归分析的原油酸值预测方法

以渤海DL油田不同区块的75个原油样品的酸值和其它9项物性参数为研究对象,利用社会科学统计SPSS软件,研究原油酸值与其它物性参数之间关系,建立了原油酸值与其它物性的数学模型y=0.106x1-0.323x4＋0.296x5-0.020 x8-90.506,该模型计算得到的实测值与预测值的相对误差满足标准规定的再现性要求。研究结果表明,采用多次回归数学方法建立的预测模型,其误差仅为0.07%,可据此快速获取原油酸值,反映原油所受生物降解的程度。     

Effects of additives on oxidation characteristics of palm oil‐based trimethylolpropane ester in hydraulics applications

Hydraulic fluids represent one of the most important groups of industrial lubricants. Increasing attention to environmental issues drives the lubricant industry to choose vegetable‐based hydraulic fluids which are biodegradable as compared to mineral‐based fluids. However, the lubricating properties of vegetable oil, such as poor oxidative stability and high pour point, have hindered their use. In this study, trimethylolpropane ester, which was derived from palm‐based methyl ester, was used as the base hydraulic fluid. The purpose of the study was to determine the optimum formulation for palm oil‐based synthetic lubricants by using suitable additives that can improve the oxidative stability and viscosity in accordance with the standard regulations for hydraulic fluid applications. The oxidative stability of the oil was evaluated by total acid number (TAN) and viscosity tests. In general, base oil without additive began to degrade after 200 h. The formulated oil, on the other hand, was quite stable even after 800 h of operation. The best formulation was obtained using 1.0% of either additive A or additive B. Both TAN and viscosity values were found to increase with increasing heating temperature. Meanwhile, the results have also shown that additive A performs better than additive B. After 800 h of exposure, the final TAN value for the formulated oil was only at 0.32 as compared to 4.88 mg KOH/g for the oil without additive. However, the kinematic viscosity of the oil at 40 and 100 °C was almost unchanged as compared to the oil without additive.     

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。     

石油产品酸性含氧化合物测定实验的教学改革

针对中国石油大学(华东)化学综合实验拟开设的"石油产品酸性含氧化合物测定"的实验项目,进行教学改革。选取克拉玛依加氢蜡油为原料,改进深色石油产品酸值测定法,筛选酸值测定所需的溶剂,研究表明:改进深色油品酸值测定法较好的溶剂为甲苯-异丙醇,溶剂比甲苯:异丙醇(V/V)为1:2,溶剂量为60 mL。选取汽油1、汽油2、汽油3、柴油为原料,改进浅色油品酸度测定法,省略中和95%无水乙醇步骤,加做空白。实验证明,无论是测定深色油品还是浅色油品的酸值,改进后的方法可行、简便,减少污染。     

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。     

广西石油与天然气管道发展技术分析

长久以来,广西少油无气,更无石油和天然气管道,能源和相应的基础设施均严重不足,制约着广西的能源供应和经济社会发展。自中石化的西南成品油管道后,广西陆续建成西气东输二线广南支线、中缅天然气管道、中石油钦州-南宁-柳州成品油管道等一批石油与天然气管道,这将大大缓解广西能源短缺的压力,并能促进能源消费结构调整。这些管道建成之后,要加快完善配套设施以及管道运营维护技术,进行管网优化以及储备调峰,保障广西管道能源通道源源不断地充足供应,为广西经济社会发展提供强劲能源动力。     

A study of rice bran oil refining

Examination of a number of rice bran oils revealed the presence of monoglycerides (0.5–1.4%) and other hydroxylated compounds such as diglycerides and glucosides. The hydroxyl numbers of the samples ranged from 8.5 to 27, depending on their acidity. On the assumption that the inordinately high refining losses of rice bran oil are due, along with the acidity, to the presence of hydroxylated compounds, the hydroxyl numbers of several samples of that oil were reduced by progressive acetylation with acetic anhydride. This was accompanied by gradual reduction of the refining losses, which seems to support the above mentioned assumption.     

加工高酸原油常减压装置高温腐蚀分析及对策

惠州炼油项目拟加工蓬莱19-3原油,该原油属于高酸低硫中间环烷基原油,文章根据环烷酸腐蚀的特点及其影响因素,提出了环烷酸腐蚀环境的选材建议,并依据惠州炼油项目常减压工艺流程图分析了惠州炼油项目常减压装置环烷酸腐蚀的重点部位。     

Stabilization of bio-oil over a low cost dolomite catalyst

A low cost alkaline catalyst of dolomite (CaMg(CO₃)₂) was used to stabilize acacia sawdust bio-oil mixed with methanol. The upgrading efficiency was evaluated in terms of the total acid number (TAN) and viscosity. A change in the dolomite calcination temperature from 700 to 900 °C led to a significant change in the TAN and viscosity of the methanol-added bio-oil. Dolomite activated at higher temperatures had larger amounts of active CaO and MgO species due to the enhanced decarboxylation of calcium and magnesium carbonates. An increase in the dolomite content (1-5 wt%) decreased the TAN value of bio-oil remarkably. A thermal aging test of the methanol-added bio-oil upgraded using dolomite (calcined at 900 °C) at 50 °C for 24 h was carried out by storing the bio-oil at 80 °C for one week. Although the TAN value increased after the aging process, it was still lower than the TAN of raw bio-oil. In addition, increasing the methanol content (10-30 wt%) decreased the TAN and viscosity of the bio-oil significantly.     

磷改性高岭土型流化催化裂化催化剂的表面酸性及裂化性能的研究

采用磷元素改性高岭土型流化床催化裂化(FCC)催化剂,热重-程序升温脱附(TG-TPD)和红外(IR)酸性测试结果表明,磷改性的催化剂,能够降低催化剂总酸量,弱酸量和强酸量,可增加中强酸的酸量,可以降低催化剂的B酸强度和L酸中心数。在微反活性和小型固定流化床装置上评价了磷改性催化剂的反应性能,经过磷改性的催化剂,可提高催化活性,增强重油转化能力,改善焦炭和汽油选择性。     

In situ infrared attenuated total reflectance spectroelectrochemical study of lubricant degradation

An attenuated total reflectance (ATR) infrared (IR) cell was designed using a boron-doped silicon wafer as the optically transparent electrode to simultaneously perform ATR-IR spectroscopic and electrochemical impedance measurements. The degradation of industrial lubricants was investigated by monitoring the near-surface concentration of hydrocarbons, detergents and anti-wear additives and the formation of degradation products, while polarizing the cell using electrochemical impedance spectroscopy (EIS). The detergent and the anti-wear agent concentration on and near the silicon surface, based on the IR spectra, and the sum of bulk solution and charge transfer resistance, based on the impedance spectra, were all at a maximum for 30 h drain oil, and then decreased for later drain oils. These results agree with other independent measurements, such as oil viscosity, total acid number (TAN), and total base number (TBN) to indicate that the lubricant is significantly degraded after 30 h in the engine test. These data demonstrate the potential use of the ATR silicon-based electrochemical cell as a monitoring device for lubricant degradation, and as an effective analytical tool capable of studying interfacial kinetics, surface interactions of the additives, and performance of silicon-based spectroelectrochemical devices.