A Study on Removing Naphthenic Acid From Diesel Oil by Salt

Abstract

Sodium carbonate as deacidification agent was used to remove naphthenic acid from diesel oil. The influence of affect factors about treating conditions on the acid removal of diesel oil was investigated, such as volume ratio of deacidification agent-to-oil (VRDO), reaction temperature, stirring time, and resting time. Orthogonal tests were done to conform the optimum process condition. The results showed that the optimum condition is that VRDO was 0.40, reaction temperature was 330 K, stirring time was 6 min, and resting time was 35 min. Under the optimum condition, acidity of diesel oil was reduced to 5.15 mgKOH/100 mL from 135.52 mgKOH/100 mL, and if deacidification rate of naphthenic acid reached 96.8%, diesel oil recovery could reach 92.6%. The quality index of diesel met the national standard.     

Removing Naphthenic Acids from Diesel Oil by Microwave Irradiation

Abstract

Microwave technology is introduced for removal of naphthenic acid from diesel oil. The decrease of Zeta-potential of interface and the viscosity of diesel oil are responsible for the acceleration of separation of naphthenic acid with microwave irradiation. It was observed that the separation percentage changed with the dosage of alkali compound solvent, irradiation pressure, irradiation time, irradiation power, settling time, and oil phase-to-solvent phase volume ratio (O/S). The removal rate of naphthenic acid was maximum when the optimum conditions were suggested to be M _p /M _T = 1.5, 0.05 MPa, 6 min, 375 W, 25 min, and O/S = 10, respectively.     

高酸值原油的成因与分布

原油酸值是表示原油中酸性物质总含量的参数,即中和1g原油所需要的KOH的数量。对世界大量原油酸值进行了调研,并根据酸值的大小将原油划分为正常原油、含酸原油、高酸值原油和特高酸值原油。其中将酸值高于1mg/g的原油称为高酸值原油。根据高酸值原油的成因,进一步划分出原生高酸值原油、次生生物降解型高酸值原油和混合型高酸值原油。研究发现,海相和湖相环境生成的原油,其酸值随生物降解程度的增加而增加的速率不同,湖相远高于海相。全球高酸值原油主要由生物降解作用形成,主要储量分布在前陆盆地的前缘地带,以大型地层圈闭油藏为主;其次分布在裂谷盆地、被动大陆边缘盆地和克拉通盆地含油气系统的边缘和浅层的各种背斜、断块和地层圈闭中。     

加工高酸值原油延迟焦化装置的选材

文章论述了国内外高酸值原油的酸分布,根据原油的酸分布结合环烷酸腐蚀的特征和延迟焦化的工艺流程,分析了环烷酸腐蚀对延迟焦化装置的影响,并对加工高酸值原油延迟焦化装置主要管道的选材提出实施意见。     

无机碱非水溶液脱除高酸原油中的环烷酸

以NaOH无水乙醇溶液为萃取剂,与高酸原油中的环烷酸进行一级萃取反应。通过界面张力分析和显微镜观察油相水滴分布情况表明,该脱酸方法不会引起油水乳化现象,要求醇的含水质量分数控制在4%以下。结果表明,小型混合澄清槽连续化操作的优化工艺条件为:NaOH用量3 200μg/g,反应温度55℃,反应时间5 min,溶剂/原料油(质量比)0.4,搅拌速率350 r/min。原油经脱酸反应后,酸值(KOH)可降低到0.28 mg/g,脱酸率达到94.2%。     

高酸原油溶剂脱酸前后酸分布研究

以蓬莱19-3高酸原油为原料进行溶剂脱酸,对脱酸前后原油进行了实沸点蒸馏,并对原油和各馏分进行性质分析,考察了高酸原油脱酸前后酸分布的变化规律和各馏分的脱酸效果,并对回收环烷酸进行分子量分布研究。     

Catalytic Neutralization Method for Naphthenic Acid Removal in Crude Oil by Alumina Supported Ca and Ba Catalysts

The presence of naphthenic acids in crude oils has caused a major corrosion problem to the production equipment, storage and transport facilities in the petroleum industry. To overcome this problem, catalytic neutralization method will be investigated on real petroleum crude oil sample with various parameters study such as the type of basic chemical used, dosing amount, type of catalyst, catalyst calcination temperature, and catalyst ratio of basic metal and dopant. Potential catalyst was characterized by XRD, NA, and TGA-DTA for its physical properties. Cu/Ca(10:90)/Al₂O₃ catalyst with calcination temperature of 1000°C was an effective catalyst for all three types of crude oil. In the presence of catalyst, all three types of crude oil samples showed enhancement in the removal of naphthenic acid.     

于离子液体的高酸原油脱酸效果研究

利用咪唑和环烷酸反应生成与原油极性差异大、易于分离的离子液体，脱除原油中的环烷酸。考察了咪唑含量、剂油比、反应时间、反应温度和搅拌速率对高酸原油一级脱酸效果的影响，并在所选的一级脱酸反应条件下，进一步考察了三级逆流萃取的脱酸效果。结果表明，在咪唑质量分数为30%、剂油质量比为0.4、反应时间5 min、反应温度30 ℃、搅拌速率300 r/min的条件下，北疆原油的一级脱酸率可达61.5%，酸值较低的蓬莱原油的一级脱酸率可达68.6%，酸值更低的1号和2号调和油一级脱酸率分别达到了70.6%和72.2%。试验所用的四种原油在剂油质量比为0.4时，三级逆流萃取的脱酸率可以提高到75%左右；当剂油质量比增大到0.6时，三级逆流萃取的脱酸率可达到84%以上。     

Reduction of the Total Acid Number of Crude Oil with Basic Solution

Abstract

Reduction of total acid number (TAN) of crude oil with sodium hydroxide and sodium carbonate solution was investigated. For emulsion emerging in an acid removal process by a sodium hydroxide solution, effects of the volume ratio of sodium hydroxide solution to crude oil and dosage of demulsifiers have been investigated. A model has been engaged to explain the interfacial behavior. When the volume ratio of sodium hydroxide solution (4 wt%) to crude oil exceeds 2, the formed emulsion is an unstable oil-in-water emulsion. When the volume ratio of 4 wt% sodium hydroxide to crude oil reaches 4:1, the total dosage of demulsifiers is 20 mg/l, the weight ratio of non-ion demulsifier LA42 to cationic demulsifier LGA is 1:1, the temperature reaches 40°C, most naphthenic acids were removed from crude oil and the emulsion separated quickly.     

柴油脱酸工艺研究新进展

综述了柴油脱酸工艺研究新进展,分析了传统脱酸工艺存在的各种问题,对新的脱酸方法作了介绍,着重介绍了目前已工业化的西南石油大学(SWPU)开发的馏分油脱酸剂技术,开发绿色脱酸工艺将是柴油脱酸研究的重点.     

DEACIDIFICATION OF DAGANG SECOND LUBRICATING OIL DISTILLATE BY COMBINED SOLVENT

A combined solvent was used for getting rid of the acid components of lubricating oil distillates. Data indicate that this solvent can remove most of the acid matters. The deacidified oil has better light stability than hydrodeacidified oils. This solvent can be reused and recovered. The reaction conditions are easy to be fulfilled. This deacidification method is an effective technology to remove the acid matters of high acid number feed stocks of lubricating oil distillates.     

DEACIDIFICATION OF DAGANG SECOND LUBRICATING OIL DISTILLATE BY COMBINED SOLVENT

A combined solvent was used for getting rid of the acid components of lubricating oil distillates. Data indicate that this solvent can remove most of the acid matters. The deacidified oil has better light stability than hydrodeacidified oils. This solvent can be reused and recovered. The reaction conditions are easy to be fulfilled. This deacidification method is an effective technology to remove the acid matters of high acid number feed stocks of lubricating oil distillates.     

聚乙烯胺用于直馏柴油脱酸的实验研究

采用以聚乙烯胺（PVAm）作主剂的脱酸剂对直馏柴油进行了脱酸实验,并考察了柴油脱酸过程中主要因素的影响。结果表明,在脱酸剂中PVAm与原料油中环烷酸的摩尔比为5.0、剂油体积比为0.02、反应温度和相分离温度均为50℃、反应时间20s、相分离时间为60min、萃取级数为3的操作条件下,脱酸剂可将苏丹柴油酸度从102.7 mgKOH/（100mL）降至6.0 mgKOH/（100mL）,脱酸率高达94.2%,精制油收率达到99.6%,精制油质量达到GB 252－2000产品质量指标。脱酸剂经高温水解再生,可以重复使用。此脱酸剂用于直馏柴油脱酸具有脱酸剂用量小、可循环利用、再生能耗低、绿色环保等优点。     

Inhibition and Promotion of Hydrolysis of Chloride Salts in Model Crude Oil and Heavy Oil

Abstract

The interactions of chloride salts with naphthenic acid and inhibitors during exposure to steam at 100–350°C were investigated in order to understand the release of hydrochloric acid in crude units. Naphthenic acid promoted the release of chlorine from calcium and sodium chlorides by a factor of up to 30 times, forming metal naphthenates in solution. Mitigation of the hydrolysis reactions was achieved with the use of chemical additives in both a model oil and in a Canadian heavy oil.     

The catalytic deacidification of acidic crude oil using Cu-doped alkaline earth metal oxide catalysts

Naphthenic acids (NAs) tend to cause operational problems that can lead to the deactivation of catalysts. To overcome the problem, catalytic deacidification was introduced utilizing an ammonia solution in ethylene glycol with the aids of alkaline earth metal catalyst with alumina as a support. The initial total acid number observed for NAs in n-dodecane was 4.21 mg KOH/g. In total, 1,000 mg/L of 0.4% NH₃-EG were used as the acid removal agent. Calcium, barium, and magnesium catalysts were tested in this study. The results showed Cu/Ca/Al₂O₃ was found to be the best catalyst that could be used to enhance the reaction.     

Separation and Characterization of Naphthenic Acids Contained in Penglai Crude Oil

Abstract

Naphthenic acids were separated from highly acidic Penglai crude oil by aqueous alkaline solution and analyzed by infrared spectrum (IR) and mass spectrum (MS). According to our results, the solution was composed of ethanolamine, alcohol, and water, the ratio being 0.1:7.9:10. When the solution and crude oil (ratio 0.4:1) were stirred at the speed of 300–400 r/min at 50°C for at least 10 min, more than 70% of the naphthenic acids in the crude oil could be removed. IR and MS results confirmed the presence of diversified naphthenic acids in Penglai crude oil and provided relative content information.     

The Removal of Naphthenic Acids from Beijiang Crude Oil With a Sodium Hydroxide Solution of Ethanol

Abstract

A new method is introduced in this article to separate naphthenic acids from Beijiang highly acidic crude oil with a sodium hydroxide solution of ethanol. The sodium hydroxide solution of ethanol was used as the acid removal reagent by mixing with the crude oil and then allowing the two phases to separate, with the naphthenic acids being extracted from the crude oil. Data indicated that the optimal content of sodium hydroxide in crude oil was 3,000 μg/g and the optimal extraction time was 5 min with the reagent/oil ratio being 0.4:1 (wt/wt). The suitable reaction temperature could be room temperature. The total acid number of the crude oil was lowered from 3.92 to 0.31 mg KOH/g and the acid removal could reach up to 92.1%.     

THE STUDY OF PRODUCING HEAVY TRAFFIC ASPHALT BY USING THE HIGH VISCOUS CRUDE FROM NO.l SHUGUANG ZONE OF LIAOHE OIL FIELD

ABSTRACT

The characteristics of the high viscous crude from No. 1 Shuguang Zone of Liaohe Oil Field are similar to those of residue distillates of general crude such as high density(ρ ₂₀=0·9977 g.cm^-3),high viscidity υ ₁₀₀= 1223·9 mm².s-¹) and high carbon/hydrogen ratio. This oil contains less wax, but rich in resin and asphalt, which belongs to low sulfur naphthene-base crude oil and can be used as feedstock to produce high paving asphalt. But now it is used as fuel after emulsificating. In order to make full use of this oil and resolve the problem of paving asphalt demand-supply, various paving asphalts conforming to GB50092-96 standard were produced by blending vacuum residue of the high viscous crude from No.l Shuguang Zone of Liaohe Oil Field and waste oil which is rich in aromatics and poor in wax. The laboratory test results show that modified paving asphalts have good low-temperature properties and antiaging feature.     

高酸度柴油微波辐射精制的研究

介绍了微波辐射法柴油脱酸的原理。采用正交设计法确定柴油微波脱酸的最佳工艺条件,研究了各因素对脱酸效果的影响。在最佳工艺条件下:碱性溶剂用量为理论用量的1.4倍,剂油体积比0.25:1,辐射压力0.06 MPa,恒压辐射时间5 min,辐射功率300 W,可将柴油酸度(KOH)由1 704 mg／L降至23.9 mg／L,达到国家规定的GB 252-2000质量标准,柴油回收率达99.3％。该精制过程无需破乳剂,具有清洁、高效、节能的优点。     

Treatment of oily sludge using solvent extraction

Baiji oil refineries produce 3000–3500?m³/year of oily sludge. This sludge is hard to be biodegraded, contains large quantities of crude oil, and hard to be transported into landfill sites. The aim of the present work is to treat this oily sludge by solvent extraction in order to separate this sludge to many components that are easy to deal with and recover the valuable crude oil. Different solvents types are used in this work: light naphtha, heavy naphtha, kerosene, gasoline, and methyle ethyle keton. The results show that methyle ethyle ketone gives crude oil extraction efficiency of 95%, solid separation of 24%, and water separation of 94% under 60?°C.