Identification of petroleum acids in Liaohe super-heavy oil

In this study, petroleum acids were extracted from the super-heavy oil of Liaohe oilfield, North-east China, by using acetic acid, and their structural components and properties were investigated by using FT-IR and MS. Moreover, the trace metal contents in the super-heavy oil sample before and after acetic acid treatment were also measured in this work. The results showed that naphthenic acids were the main component of petroleum acids in Liaohe super-heavy oil, and the content of naphthenic acids with double rings was higher than that of other naphthenic acids. It can be concluded that petroleum acids in Liaohe super-heavy oil mainly consist of naphthenic acids, with a carbon number of around 11–69 and containing one to six naphthenic rings and/or one to two aromatic rings, and mainly exists in form of metal salts of petroleum acid. The molecular weight of petroleum acids is in the range of 190–1000.

Process for Separation of Petroleum Acids from Crude Oil

A new technique for separation of petroleum acids from crude oil was proposed. The method relates to processes for treating acidic oils or fractions thereof to reduce or eliminate their acidity by addition of effective amounts of crosslinked polymeric amines such as polypropylene amine and anionic exchange resins having amino-groups. Petroleum acids contained in the mixture can be extracted by a complex solvent. The results indicate that more than 80 % of the petroleum acids are removed and the process does not cause environmental pollution because all the solvents are recovered and reused in the test.

ANALYSIS OF PETROLEUM ACIDS IN DUSHANZI DISTILLATE

A method which involves conversion of carboxylic acids to corresponding hydrocarbons and determination of high-resoiution mass spectrometry has been applied to the analysis of petroleum acids in Dushanzi distillate and resulted in compound class identification of petroleum acids which have not been reported previously in Xinjiang petroleum.

石油酸含量对稠油流体性质影响实验

石油酸是稠油体系中的强极性组分,为研究石油酸对稠油流体类型、黏度及乳化特征的影响,以新疆风城油田SAGD井组超稠油油样为研究对象,采用高能质谱仪分析石油酸分子结构特征。通过实验研究石油酸含量对稠油黏温特性及剪切流变性的影响规律,分析含水率在不同石油酸含量条件下对稠油表观黏度的影响特征以及其相应的油水乳化特性。研究表明:超稠油样品酸值(以KOH计)为5.46 mg/g,样品中石油酸含量约为1.71%,以2~3环一元酸为主,碳数主要分布在15~35;稠油黏度随石油酸含量增加而降低;石油酸含量从0增至50%时,样品从牛顿流体转为非牛顿流体的拐点温度从120℃降至100℃;含水率升高时表观黏度先增加后降低,当石油酸含量从0增至50%时,反相点的含水率由30%~40%降至20%~30%,且不同含水率下的黏度均有大幅下降。该研究揭示了中国西部超稠油石油酸分子结构特征和石油酸含量对稠油流体性质的影响规律,可为降低稠油乳化、腐蚀程度,以及稠油资源高效开发提供借鉴。

酸热法提取黑水虻鲜幼虫油脂工艺研究

【目的】构建黑水虻油脂的快速、高效的新型提取工艺,解决传统提取工艺中因乳化作用和细胞破碎不足导致油脂提取率较低的问题,为黑水虻油脂的提取及黑水虻油脂的规模化发展提供新思路。【方法】使用酸热法提取黑水虻鲜幼虫油脂,通过控制变量法选取黑水虻鲜幼虫油脂的预处理方法和提取溶剂,经单因素试验和正交试验对提取工艺进行优化,分析黑水虻鲜幼虫油脂的理化指标,并通过高效气相色谱仪分析其脂肪酸组成。【结果】酸热法提取黑水虻鲜幼虫油脂的最佳预处理方法为添加质量分数5.0%的柠檬酸溶液匀浆破碎(m(鲜幼虫/g)∶V(溶液/mL)=1∶1),最佳提取溶剂为石油醚,提取工艺条件为柠檬酸溶液质量分数5.0%、料液比m(鲜幼虫/g)∶V(石油醚/mL)=1∶5、提取时间60 min和提取温度50℃。在此条件下,油脂提取率达到94.67%,且耗时4 h便可得到黑水虻鲜幼虫油脂。黑水虻鲜幼虫油脂的酸值为9.30 mg·g-1,过氧化值为1.74 mmol·kg^(-1),皂化值为227.23 mg·g-1。鲜幼虫油脂共检测出20种脂肪酸,其中,亚油酸与月桂酸的含量最高,分别为32.72%和30.75%。【结论】酸热法能快速、高效地提取黑水虻鲜幼虫油脂,既节省了干燥成本,又保证了油脂的品质和脂肪酸组成。

Study and Commercial Test on Technology for Deacidification of Distillate Oils

A new kind of solvent for deacidification of distillate oils was introduced in this paper. After successful laboratory study this technology had been applied in commercial scale successfully. Compared to traditional caustic wash of distillate oils, this technology has a lot of merits, such as the broad range of distillates to be processed, low caustic consumption, recycle of deacidifying agent, absence of waste caustic discharge, and low equipment revamp expenses, which can have promising perspectives for exploitation and application of this technology.

植物油酸值、过氧化值的测定方法研究

为解决国标法测定植物油酸值、过氧化值溶剂安全性问题,以核桃油为实验材料,建立以更安全且容易获取的石油醚、二氯甲烷分别代替GB 5009.229—2016和GB 5009.227—2016中乙醚、三氯甲烷,测定植物油的酸值和过氧化值的方法,考察方法的精密度,采用国标法和所建立方法测定4种植物油的酸值、过氧化值,并对结果进行t检验,考察方法的准确度。结果表明:所建立方法平行测定了6次核桃油的酸值、过氧化值,其相对标准偏差(RSD)分别为2.055%、1.318%;国标法和本实验方法同时测定4种植物油的酸值、过氧化值p值均大于0.05,两种方法不存在显著性差异。所建立的方法精密度和准确度均较好,并且提高了检测安全性,可用于植物油的酸值和过氧化值测定。

酸液作用下页岩力学参数变化规律

选取重庆市页岩气区区块露头页岩作为研究对象,开展酸压作用下页岩的物理特性及力学特性测试,揭示酸蚀作用下页岩的力学性质变化规律。结果表明:页岩中的方解石、白云石、黄铁矿与盐酸反应生成硫化氢、二氧化碳气体及三价铁离子等,并使其从无色变成黄色,从而造成页岩的溶蚀。同时,随酸液用量的增大及作用时间的延长,页岩抗压强度呈下降趋势。在同等条件下,随着层理角的增大,抗压强度逐渐增大。随着酸量的增大和作用时间的延长,页岩的抗拉强度呈下降趋势。在同等条件下,随着层理角的增大,拉伸强度降低。

A New Method for Determination of Naphthenic Acids in Crude Oil

The petroleum acids in crude oil were separated by extraction with column chromatogram and anion exchange resin. The separation effect and the related composition and structure of petroleum acids were obtained by using IR (Infra-Red) spectra techniques. The separated petroleum acids can under special conditions react with methanol to form corresponding esters, which can be analyzed by CI (chemical ionization)-MS (mass spectrometry). The characteristic ion peaks m/z (M+15)+ of naphthenic acid esters combined with z-series formula CnH2n+zO2 of naphthenic acids can be used to classify naphthenic acids into fatty acids, mono-cyclic, bi-cyclic, tri-cyclic, and higher polycyclic acids. The analytical results can give the molecular weight and the carbon number distribution of petroleum acids contained in crude oil. The results of study indicate that this method is simple, rapid and easy in operation.

Molecular Simulation of Naphthenic Acid Removal on Acidic Catalyst II. Experimental results of catalytic decarboxylation over acidic catalysts

The energy barriers of thermal decarboxylation reactions of petroleum acids and catalytic decarboxylation reactions of Bronsted acid and Lewis acid were analyzed using molecular simulation technology. Compared with thermal decarboxylation reactions of petroleum acids, the decarboxylation reactions by acid catalysts were easier to occur. The decarboxylaton effect by Lewis acid was better than Bronsted acid. The mechanisms of catalytic decarboxylation over acid catalyst were also verified by experiments on a fixed bed and a fluidized bed, the experimental results showed that the rate of acid removal could reach up to 97% over the acidic catalyst at a temperature above 400℃.

1,4-苯二甲醇交联改性石油树脂的制备

针对C9石油树脂用作包覆材料时存在软化温度与残炭率低的问题,选用甲基磺酸(MSA)为质子酸催化剂,1,4-苯二甲醇(PXG)为交联剂,对石油树脂进行交联改性。考察了反应温度、PXG用量(PXG占石油树脂的质量分数)、MSA用量(MSA占石油树脂的质量分数)对改性石油树脂软化温度与残炭率的影响,利用傅里叶变换红外光谱、凝胶渗透色谱、热重分析和扫描电子显微镜等对改性树脂进行表征。结果表明,最佳工艺条件为:反应温度220℃,PXG用量9%(w),MSA用量7%(w)。在此工艺条件下,改性石油树脂软化温度可提升到115.9℃,残炭率达19.84%(w),与改性前相比,改性石油树脂重均分子量、热稳定性均明显提升。

高酸原油选择适合破乳剂的实验分析研究

现有破乳剂均有一定的局限性,对于特高含水的水包油型乳状液,存在脱水率低、脱水温度高、脱水速度慢等缺点,因此,针对不同地区的不同原油选择适合的破乳剂有着重要意义。基于此,考察了影响破乳剂性能的各种反应条件,在实验温度90℃和用量为10×10^(-6)破乳剂的条件下,通过瓶试脱水法,考察评价石油磺酸盐对破乳剂的影响。研究表明,石油磺酸盐明显降低了破乳剂在高酸原油中破乳脱水作用。

Comparison of Carboxylic Acids in Some Crude Oils and Their Diesel Distillates and VGOs:Characterized by Negative-Ion Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (Negative-Ion ESI FT-ICR MS)

Three high-acidity crudes, Dar, SZ36-1, and QHD326, were separated through distillation into several fractions, including diesel distillates, and VGOs. Samples were characterized by negative-ion ESI FT-ICR MS. The O2 class species （petroleum carboxylic acids）, which have a close relationship with corrosion of equipment caused by high-acidity crudes, were put in the focus of attention and were discussed in this paper. Monocyclic, bicyclic, and tricyclic naphthenic acids are the main types of petroleum carboxylic acids in naphthenic-base crudes （SZ36-1 and QHD326）. But the main types of petroleum carboxylic acids in paraffinic-base crude （Dar） are aliphatic acids and monocyclic naphthenic acids. The O2 class species in SZ36-1 and QHD326 are distributed in a wider range and have bigger DBE value （double-bond equivalence value） and carbon number than Dar. Bicyclic naphthenic acids have the highest proportion among petroleum carboxylie acids in diesel distillates, but monocyclic and tricyclic naphthenic acids also occupy a high proportion. Particularly, aliphatic acids in the diesel distillate of Dar still have high proportion among petroleum carboxylic acids. The distribution of petroleum carboxylic acids in VGO is basically identical. The bicyclic naphthenic acids assume the first place （about 25 m%）, while the monocyclic and tricyclic naphthenic acids take the next place. The comparison of petroleum carboxylic acids in diesel distillates and VGOs has revealed that the molecules of carboxylic acids in VGOs are not only bigger but also more complicated.

多聚磷酸与SBS复配调合90号A级道路石油沥青研究

以高温性能、低温性能、老化后性能均不佳的90号沥青为基质沥青,通过添加多聚磷酸、SBS改性剂或多聚磷酸与SBS复配改性方式调合90号沥青,对调合后的样品进行针入度、延度、动力黏度、老化后性能等指标分析。结果表明,采用多聚磷酸与SBS复配改性方式调合的90号沥青各项指标完全满足JTGF40-2004道路石油沥青中90号A级道路石油沥青标准要求。并考察了储存温度和时间对沥青性能的影响,为基质沥青的质量提升提供了新的思路。

Distribution of Carboxylic Acids in Sudanese Dar Crude Oil: Characterized by Negative-Ion Electrospray Ionization Fou- rier Transform Ion Cyclotron Resonance Mass Spectrometry

The Dar crude oil produced in Sudan was distilled into several fractions. The heteroatom class species in crude and its fractions were characterized by the negative-ion ESI FT-ICR MS. The major emphasis was put upon the study on the O2 class species (petroleum carboxylic acids). The test results revealed that aliphatic acids and monocyclic naphthenic acids accounted for a large proportion in petroleum carboxylic acids of the Dar crude. The relative abundance of aliphatic acids and monocyclic naphthenic acids decreased with an increasing boiling point of fractions. Meanwhile, the relative abundance of bicyclic and tricyclic naphthenic acids increased at first and then decreased, whereas the relative abundance of petroleum carboxylic acids with higher double-bond equivalence (DBE) values increased. The high abundance of aliphatic acids in the Dar crude and its fractions covered the carbon numbers in a range of 16 to 18 which had important geochemical signifi- cance. The O2 class species were distributed in a broad range of DBE values and carbon numbers with increasing boiling points of fractions.

石油石化废水中环烷酸类特征污染物去除技术研究进展

我国石油与石油化工产业规模已稳居世界第二,是最大的工业废水来源。环烷酸(通式C_(n)H_(2n+z)O_(x))来自于原油中的酸性含氧化合物,是石油石化废水特有的一类高毒性难降解化合物,《石油化学工业污染物排放标准》(GB 31571—2015)对其最高排放浓度进行了专门限定。对环烷酸类污染物的高效去除一直是水污染控制领域重要的科研方向与工程热点。综述了近十年来国内外关于石油石化废水环烷酸去除方法及机理的研究进展,对环烷酸在强化分离(混凝和吸附)以及强化化学转化(高级氧化和生物降解)过程中的作用机制进行了归纳总结,并展望了强化环烷酸去除的技术发展方向,以期对提升石油石化行业废水治理技术水平、降低其有毒有害特征污染物排放强度提供参考。

Discussion on rheology in petroleum and nature gas teservoir stimulation

Petroleum and nature gas not only are important resources,but also are important strategic materials of our country.All methods the enhancing the producing degree of petroleum and natural gas reservoir,increasing single well production and extending the stimulation period of validity are important stratagem for petroleum and natural gas exploitation.Fracturing and acidizing are the main methods for stimulation as well as one of representative examples of rheology theory application in engineering.Based on analysis of low permeability reservoir characteristics,the fracturing and acidizing stimulation principles and main controlling factors were discussed.And the mechanical characteristics,chemical reaction and rheological behavior in the stimulation process were reviewed.Furthermore research trends afterwards including the material and fluid rheology in oil and natural gas production process,the deep rock fracture initiation and extension rheology,and the fracturing and acidizing application rheology were also proposed in this paper.

不同反应空速下渣油中铁、钙化合物形态转化行为研究

以不同空速下固定床加氢反应前后的油样为研究对象,考察了渣油中铁、钙化合物在固定床加氢反应过程中赋存形态的转化行为。使用酸解-醇碱法将石油酸盐中的石油酸部分萃取出来。通过红外光谱、元素分析、核磁共振氢谱、核磁共振碳谱、高分辨率质谱等方法对石油酸结构进行表征。为了研究石油酸在受热条件下的转化,将所得到的石油酸进行热重-质谱表征,分析石油酸在热反应中的转化行为,进而推断得到铁、钙化合物在热反应中的转化行为。结果表明,首先,相对于原料样品,反应样品酸值呈现显著下降,由原料的1.01 mg/g下降到0.08 mg/g以下,表明酸性物质形态发生了反应。固定床加氢反应前后渣油中石油酸的主要成分为环烷酸,且以多聚体的形式存在。渣油在固定床加氢反应前后,石油酸出现较为明显的分解,主要产物为CO_(2)、C_(3)H_(8)等物质;随着反应深度的增加,石油酸发生脱羧反应和断链反应的程度增大,使石油酸分解。

Benzene Monitoring and S-Phenylmercapturic Acid Determination of Workers at Oil Sites in Congo-Brazzaville

The toxicity of benzene is well known, and its leukemia effect has established. It is a natural constituent of crude oil and the diseases related to its exposure are recognized as occupational diseases. Objective: To assess occupational exposure of benzene to workers in an oil and gas production company. Materials and Methods: Firstly, it was a descriptive, cross-sectional study which consisted of benzene atmospheric quantification in a sample individual measurement of a homogeneous exposure group of workers. Secondly, urinary assays of S-phenylmercapturic acid have been performed at the end of the shift in the selected workers. Results: The study has included 79 (47.88%) workers, 17 atmospheric samples were usable and 79 urinary assays at the end of the shift were performed. The average benzene concentration for all sites was 10 times lower than the regulatory average exposure value (1 ppm = 3.2 mg/m3): average: 0.122 pp, median: 0.053 ppm and range: 0.019 - 1.448 ppm. All 79 urinary assays of S-phenylmercapturic acid with a biological exposure index of less than 25 μg/g creatinine: mean: 0.70 μg/g creatinine, median: 0.52 μg/g creatinine and extends: 0.23 to 6.7 μg/g creatinine. Conclusion: Exposure was below to the limit value for benzene in both atmospheric metrology and biometrology. Therefore it is an occupational group with low exposure to benzene. Thus, the medical supervision will be adapted according to the potentially exposing tasks.