Review and Comprehensive Analysis of Composition and Origin of High Acidity Crude Oils

High acidity crude oils have an advantage over normal oils in terms of their price,but can cause corrosion and refinery problems.They are the so-called opportunity crudes and likely to be important reserved resources in the 21st century.Researches on high acidity crude oils are becoming more and more profound.Based on the existing research achievements,this article has given an overview of the chemical composition and acid distribution of high acidity oils,and also analyzed their origin types and potential influence factors.

Geochemical Characterization and Origin of High-Sulfur,Heavy Oils in Jiyang Sub-Basin,East China

High-sulfur,heavy petroleum is widely occurring in the Tertiary lacustrine Jiyang sub-basin, Bohai Bay Basin.They are differentiated into two families based on the bulk properties and biomarker compositions.Family 1 is characterized by high resins（40%-71%）and sulfur（2%-4%）,and low wax （l%-6%）,with n-alkanes removed by biodegradation,whereas family 2 is characterized by extremely abundant sulfur（3%-10%）,and high asphaltenes（7%-31%）and wax（2%-19%）,with no evidence of microbial attack.The oils of family 1 are distributed in the reservoir,lower than 1500 m throughout the sub-basin.Biomarker assemblages,such as low pristane/phytane ratios（1 Pr/Ph）and a high abundance of carotane,gammacerane,and dinosterane,suggest that they are derived from the calcareous mudstones and shales among the stratified,saline Es_4~u unit,in addition to the in situ biodegradation-concentrated sulfur content.However,the oils of family 2 are identified only in the western Zhanhua and eastern Chezhen depressions,with a depth deeper than 1700 m.Physical properties,together with biomarker ratios,including even-numbered n-alkanes,1 Pr/Ph,trace diasteranes,higher C35 homohopanes,and abundant dibenzothiophene series,with1 dibenzothiophene/phenanthrene,indicate an origin from carbonate source rocks.The X-ray diffraction analysis showed that the carbonate source rock is limited in the Es_4~u unit of the Bonan sag,which is different from most other source rocks in the same horizon.It is suggested that the high-sulfur,heavy oils are generated at the early stage of the oil window.Bacterial sulfate reduction might be responsible for the occurrence of sulfur species in the high-sulfur,heavy oils,while heavy biodegradation will enhance sulfur concentrations.

Flow Characteristics of Crude Oil with High Water Fraction during Non-heating Gathering and Transportation

In order to ensure the safety of the non-heating gathering and transportation processes for high water fraction crude oil,the effect of temperature,water fraction,and flow rate on the flow characteristics of crude oil with high water fraction was studied in a flow experimental system of the X Oilfield.Four distinct flow patterns were identified by the photographic and local sampling techniques.Especially,three new flow patterns were found to occur below the pour point of crude oil,including EW/O&W stratified flow with gel deposition,EW/O&W intermittent flow with gel deposition,and water single-phase flow with gel deposition.Moreover,two characteristic temperatures,at which the change rate of pressure drop had changed obviously,were found during the change of pressure drop.The characteristic temperature of the first congestion of gel deposition in the pipeline was determined to be the safe temperature for the non-heating gathering and transportation of high water cut crude oil,while the pressure drop reached the peak at this temperature.An empirical formula for the safe temperature was established for oil-water flow with high water fraction/low fluid production rate.The results can serve as a guide for the safe operation of the non-heating gathering and transportation of crude oil in high water fraction oilfields.

The Breeding of Hybrid Rape Variety Youyan 924 with Strong Heterosis and High Oil

The rape project of ＂Development and Application of Cabbage Type Rape Hybrids with Strong Heterosis＂ which belongs to National 863 Program aimed to breed the rape variety whose rapeseed yield or oil yield increased more than 10% compared with check （CK） variety, or oil yield increased more than 3 percentage points compared with CK. In the regional trial in the middle react,es of the Yangtze River for two years, the average rapeseed yield and oil yield of Youyan 924 which is a hybrid rape variety respectively reached 2 695.95 and 1 264.35 kg/hm2, which respectively increased by 5.22% and 13.4% compared with those of the other test- ing varieties in the same group, and respectively increased by 10.06% and 23.68% compared with those of Zhongyouza 2 which belongs to CK, thus reaching the standard of hybrid rape variety with strong heterosis; the average oil percentage of the variety in the two years was 46.63%,which increased by 3.44 percentage points compared with that of all the other testing varieties in the same group, and in- creased by 5.14 percentage points compared with that of Zhongyouza 2, and the oil percentage of it in the production testing reached 49.21%. Thus Youyan 924 is a variety with strong heterosis and high oil, moreover, its contents of erucic acid and glucosinolate are 0,25% and 20.27 μmol/g, respectively. From the data aggregation of national regional trial, it has the advantages of high oil yield, high yielding ability, reaching the standards of low erucic acid and low glucosinolate, strong lodging re- sistance, good disease resistance aqd moderate mature period.

Sulfuric acid leaching of high iron-bearing zinc calcine

Sulfuric acid leaching of high iron-bearing zinc calcine was investigated to assess the effects of sulfuric acid concentration, liquid-to-solid ratio, leaching time, leaching temperature, and the stirring speed on the leaching rates of zinc and iron. The results showed that the sulfuric acid concentration, liquid-to-solid ratio, leaching time, and leaching temperature strongly influenced the leaching of zinc and iron, whereas stirring speed had little influence. Zinc was mainly leached and the leaching rate of iron was low when the sulfuric acid concentration was less than 100 g/L. At sulfuric acid concentrations higher than 100 g/L, the leaching rate of iron increased quickly with increasing sulfuric acid concentration. This behavior is attributed to iron-bearing minerals such as zinc ferrite in zinc calcine dissolving at high temperatures and high sulfuric acid concentrations but not at low temperatures and low sulfuric acid concentrations.

Novel efficient procedure for biodiesel synthesis from waste oils with high acid value using 1-sulfobutyl-3-methylimidazolium hydrosulfate ionic liquid as the catalyst

Preparation of biodiesel from waste oils containing 72% of free fatty acids catalyzed by a novel Br?nsted acidic ionic liquid 1-sulfobutyl-3-methylimidazolium hydrosulfate([BHSO_3MIM][HSO_4]) was systematically investigated.The optimum molar ratio of methanol to waste oils,catalyst amount,reaction temperature and reaction time were 8/1,10%(based on the mass of waste oils),140°C and 6 h,respectively,under which the obtained yield of biodiesel reached 94.9%.Also,[BHSO_3MIM][HSO_4] as a catalyst still retained around 97% of its original catalytic activity after successive re-use of 5 batches(6 h per batch),showing the excellent operational stability.Moreover,the acidic IL [BHSO_3MIM][HSO_4] was able to ef ficiently catalyze conversions of waste oils with different amounts of FFAs(free fatty acids) into biodiesel,and showed tremendous application potential.Therefore,an ef ficient and environmentally friendly catalyst is provided for the synthesis of biodiesel from waste oils with high acid value.

Systemic treatment for severe concentrated sulfuric acid burns in an adult male at high altitude:A case report

BACKGROUND The aim of this study was to report a case of a patient who suffered from severe concentrated sulfuric acid burns while working at high altitude.This patient recovered after systemic treatment.We also provide a literature review for a better understanding of the disease.CASE SUMMARY A 30-year-old male,who was working in a local chemical plant in Xining at an altitude of 2261 m,suffered from 85%burns(Ⅲ°70%,deep Ⅱ°15%)after a tank containing 80%concentration of sulfuric acid exploded.The patient immediately received a series of first aid treatments,as well as rigorous wound managements after admission,which included protection for the whole body and organs,prevention and treatment of eye burns,and the appropriate oxygen therapy.After 65 d of treatment,the burn wounds had completely healed,and the patient was transferred to another specialized hospital for further eye treatment.The first aid before admission and the emergency treatment of wounds following admission were appropriate.No severe complications of sepsis,severe renal insufficiency,septic costal chondritis,corneal perforation or other burns occurred during the treatment.CONCLUSION The main causes of concentrated sulfuric acid burns consisted of accidental burns at work,accidents in the outside,factitious injuries and improper laboratory operations.The clinical manifestations were mostly deep Ⅱ°and Ⅲ°burns,with a formation of brown-black,leather-like eschar on the wound surface and locally embolized dendrite-like vessels.The clear cause of the injury and typical clinical manifestations in this case made it easy to diagnosis.However,adult cases with severe concentrated sulfuric acid burns in high altitude areas are rare,so the successful treatment of this case is of great significance.

Advance in germplasm innovation and gene mining of high-oil maize

As one of the 3 worldwide major grain crops, maize is the main source of food, feed and edible vegetable oil. High-oil maize has been selectively bred for many years due to its high oil content and nutritional quality. However, compared with normal maize, the progress of high-oil maize breeding is hindered nowadays. Main problems are scarce of high-oil maize germplasm, conventional breeding methods, and slow genetic research progress on oil content and fatty acid composition. In this study, germplasm innovation and gene mining of high-oil maize were reviewed to provide theoretical reference for genetic breeding and utilization. Several high-oil basic populations have been developed after more than 100 years of selection, which have served as the unique resources for high-oil maize breeding. They have also been used to dissect genetic architecture of oil biosynthesis in maize kernel. Using linkage and association analyses, many QTLs and loci associated with oil content and fatty acid composition have been identified and mapped. In addition, some candidate genes for QTLs have been validated to regulate maize grain oil content and fatty acid composition. Prospect for high-oil maize was also discussed to provide knowledge about genetic mechanism of oil biosynthesis and improvement of kernel quality in maize.

Thermal Treatment for Decreasing the Acidity of Crude Oil

Highly acidic crude oil is thermally soaked to investigate how the temperature and time involved affect the removal of organic acid in feedstock. Experimental results indicate that thermal treatment is an effective approach to decreasing acidity and the acid removal rate reaches 80%. Temperature is one of the main factors that determine the acid removal reaction. When the temperature ranges from 420oC to 440oC, the acid removal rate increases with the rise of the reaction temperature, but the increase slows down gradually. At the reaction temperature below 440oC, the long reaction time favors the acid removal. The cracking and polymerization of hydrocarbon molecules take place so that the properties of the crude oil change at the same time when the highly acidic crude is thermally treated.

Processing of Liaohe Highly Sour Crude

In order to solve the problems related with processing low-quality Liaohe highly sour crude, the Liaohe Petrochemical Company has explored the possibility in optimizing the processing of highly sour crude by adopting different process schemes depending upon the properties of the highly sour crude. The Liaohe naphthenic-base crude oil with low freezing point is earmarked for manufacture of naphthenic lube oils and heavy traffic paving asphalt, while the extra-heavy Liaohe crude with high acid number is routed directly to delayed coking unit coupled with corresponding corrosion preventing measures, resulting in tackling the problem of equipment corrosion arising from refining of Liaohe highly sour crude to obtain light distillates from Liaohe heavy crude through a short process scheme.

Preparation of boric acid from low-grade ascharite and recovery of magnesium sulfate

Boric acid and kieserite were prepared from low-grade ascharite by sulfuric acid method.This method results in the recovery of 71.06%and 45.03%for boric acid and kieserite,respectively.Meanwhile,the boric acid was precipitated from the filtrate at low temperature and the solution was recycled without discharging waste liquid in the whole process.The influence of amount of sulfuric acid,mass fraction of sulfuric acid,reaction temperature and reaction time on the leaching rate of boric acid were studied. The results show that the leaching rate of boric acid reaches 93.80%under the following conditions:the amount of sulfuric acid is 85%of theoretical dosage;the mass fraction of sulfuric acid is 25%;reaction temperature is 95℃;and the reaction time is 100 min. Meanwhile,the effects of mass fraction of magnesium sulfate,crystallization temperature and crystallization time on the crystallization of kieserite were investigated and the optimal crystallization conditions are obtained:the mass fraction of magnesium sulfate is 28%;the crystallization temperature is 180℃and the crystallization time is 4h.

Corrosion Rate of Hydrogenation to C110 Casing in High H_2S Environment

The corrosion behavior of C110 bushing at high temperature and high pressure with a high H2S / CO2 was studied, and a basis for the materials selection of sour gas well bushing was provided in H2S, CO2 and saline coexisting environment. Under acidic condiction, hydrogen atoms greatly entered into the material and caused the material properties changed. Weight loss method was used to study the corrosion rate of hydrogen charging samples and original untreated samples in simulated oil field environment. PAR2273 electrochemical workstation was used to examine the electrochemical performance of samples untreated, hydrogen charging after reacting in autoclave. The corrosion product film was observed through SEM. The experimental results show that sample with hydrogen charging has a much more obvious partial corrosion and pitting corrosion than the untreated blank sample even the downhole corrosion speed of bushing is increased after being used for a period of time. Polarization curve shows the corrosion tendency is the same between sample with or without hydrogen charging and corrosion tendency is reduced by corrosion product film. A layer of dense product film formed on the surface of samples provides a certain protective effect to the matrix, but cracked holes which will accelerate partial corrosion of the sample were also observed.

Development Situation and Future Tendency of Liaohe Oil Province

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碳同位素分馏效应对深层原油来源判识的影响

深层烃源岩演化程度高,随成熟度升高,原油中生物标志化合物含量大幅度减少,影响了利用常规生物标志化合物参数进行油源对比的可靠性。针对如何更好地利用δ^(13)C_(PDB)值进行深层原油来源判识,通过渤海湾盆地济阳坳陷东营凹陷烃源岩自然演化剖面中可溶有机质、烃源岩生排烃物理模拟实验产物4种族组分δ^(13)C_(PDB)值的分析,结合烷烃质量分数特征,探讨了深层烃源岩原油碳同位素分馏效应,提出利用δ^(13)C_(PDB)值进行深层原油来源判识的工作思路和方法。深层烃源岩因高热演化程度而产生的碳同位素分馏效应是明显的,烃源岩可溶有机质的烷烃、芳烃、非烃和沥青质4种族组分δ^(13)C_(PDB)值随埋深的增加均发生了明显增大现象,其中烷烃δ^(13)C_(PDB)值变化最明显,达5‰以上,芳烃δ^(13)C_(PDB)值约为4‰,非烃和沥青质δ^(13)C_(PDB)的变化相对较小,约为2‰~3‰。随埋深的增加可溶有机质中烷烃质量分数由40%左右增至80%以上,相应烷烃δ^(13)C_(PDB)值由-30‰左右增至-24‰以上,且烷烃质量分数与其δ^(13)C_(PDB)值的变化有很好相关性。同一类型烃源岩样品生排烃物理模拟产物族组分δ^(13)C_(PDB)值也显示了相似的结果,烷烃δ^(13)C_(PDB)值的变化幅度最大可达4‰,而芳烃、非烃、沥青质的δ^(13)C_(PDB)值变化相对较小,约为1‰~3‰。利用碳同位素进行深层原油来源判识时,首先根据烷烃质量分数与烷烃δ^(13)C_(PDB)值的相关性判断是否存在热演化造成的碳同位素分馏效应,并对烷烃δ^(13)C_(PDB)值进行合理恢复,然后再利用恢复后的δ^(13)C_(PDB)值进行原油来源的合理判识。依照上述方法对准噶尔盆地西缘车排子凸起轻质油来源进行了判识,轻质油的碳同位素明显存在热演化造成的分馏效应,轻质油源自深部二叠系高成熟烃源岩的可能性很大,这对该地区油气勘探目标评价部署工作具有重要实践意义。

825合金在含单质硫高温高酸性环境中的局部腐蚀行为

在132℃、H_(2)S分压4.8MPa、CO_(2)分压1.6MPa、氯离子质量浓度42750mg·L^(-1)的气田模拟地层水中,通过腐蚀挂片试验研究了825合金在含单质硫(每升地层水中包裹合金的单质硫质量为10g)与不含单质硫条件下的局部腐蚀行为。结果表明:在不含单质硫条件下825合金几乎不发生腐蚀,腐蚀6d时的腐蚀速率仅为0.0077mm·a^(-1);添加单质硫腐蚀3d时腐蚀速率达到0.0552mm·a^(-1),合金发生了严重的局部腐蚀,随腐蚀时间的延长,合金表面局部腐蚀坑面积、腐蚀坑最大深度和腐蚀速率增大。在不含单质硫条件下合金表面腐蚀产物极少,主要为FeCO_(3),在含单质硫条件下,随着腐蚀时间的延长,表面腐蚀产物增多,主要为FeCO_(3)与FeS;单质硫在高温下发生歧化反应产生H^(+)和S^(2-),使825合金表面腐蚀产物膜破裂,从而加剧了局部腐蚀。

基于NSGA-HVC算法的含高熔点原油单管道炼油系统短期调度优化

为了解决含高熔点原油的单管道短期调度优化问题,对调度过程中出现的目标函数和约束条件建立数学模型,并采用基于超体积贡献(HVC)的进化算法优化求解该问题。通过种群聚类获得唯一目标值集合,然后计算HVC,并根据目标价值优化参考点的选取,提出改进的基于HVC的非支配排序遗传算法(NSGA-HVC)对含高熔点原油的单管道短期调度问题进行多目标优化求解。实例分析表明,与其他算法相比,NSGA-HVC算法的求解性能更优,超体积(HV)指标高于其他算法10%左右,所得解集表现出更好的多样性和收敛性。将NSGA-HVC算法得到的调度结果与已有文献进行对比,结果表明所提算法在不同目标上的优化效果提升了3.1%~24.1%,整体上调度成本显著降低。

压力对原油流变性影响研究进展

鉴于低温下压力对含蜡原油的流变性具有较大影响,为分析与完善压力条件下含蜡原油的流变规律,对国内外在高压条件下含蜡原油流变性的相关研究成果进行系统归纳评述,具体包括压力对含蜡原油的屈服、黏度、析蜡点和触变等流变性质的影响,阐述了含蜡原油在压力作用下各种流变性质的微观机理和这些流变性质在压力下的不同实验研究方法及其优缺点。对目前高压条件下含蜡原油性质、微观机理和测量方法等进行总结,为今后深入展开相关研究提供必要的参考。

酿酒酵母耐受机制研究进展

酿酒酵母在工业生产中被广泛应用,却会受到多种应激源和抑制物的限制,因此,探究酿酒酵母应对环境中各种不利因素的耐受机制,进而利用遗传改造技术等多种育种手段提高其耐受能力,对于提高酿酒酵母在工业生产中的鲁棒性和发酵能力至关重要。本文综述了酿酒酵母对渗透压、乙醇、高温、有机酸、活性氧、二氧化硫等的耐受机制,分析了酿酒酵母中与环境胁迫有关的耐受基因,并总结了耐受机制的研究方向,未来可通过系统生物学和基因工程技术深入研究菌种适应环境的分子机制和功能网络,为提高酿酒酵母在工业生产中的抗逆性和发酵能力提供理论和实践指导。