Removal of Nickel and Vanadium from Crude Oil by Microwave-Chemical Method. I. Chemical Method

WY series demetalizers, some types of thiocarbamate, were synthesized by organic amine (diethylene triamine and triethylene tetramine), carbon disulfide, and sodium hydroxide and used to remove nickel and vanadium from crude oil. WY-1 demetallizer has excellent removal of nickel and vanadium efficiency for Shengli crude oil and Iran crude oil. The nickel and vanadium removal efficiency of Shengli crude oil reached 43.41 and 41.63% at the dosage of WY-1 500 mg/L, reaction time 30 min, and reaction temperature 70°C. With the dosage of WY-1 and increasing reaction time and reaction temperature, the nickel and vanadium removal efficiency of crude oil increased.     

Desulfurization of Simulated Oils by Microwave Chemical Methods

Abstract

Microwave technology was introduced for the desulfurization of sulfurous crude oil and the influence of microwave processes on removing benzothiophene sulfur and bi-benzothiophene sulfur in simulated oils was studied in this article. The results manifested that the desulfurization efficiencies of BBPV, formylhydroperoxide and peroxyacetic acid for an oil sample (simulated oil 2) containing bi-benzothiophene were better than for the oil sample (simulated oil 1) containing benzothiophene. When dosages of BBPV increased from 0.5% to 4%, the desulfurizing efficiencies of simulated oil 1 and 2 were raised from 19.8% to 53.7%, and 48.0% to 64.2%, respectively. With the increase of temperature, the reaction order desulfurization of the simulated oils by microwave increased, and the rate of the microwave reaction increased. The desulfurizing efficiency increases along with the temperature in the same time.     

微波技术对原油脱金属的影响研究

以北疆原油为原料油,以柠檬酸为脱金属剂,研究了微波参数对原油脱金属效果的影响及三种不同分离工艺对金属脱除率的影响。结果表明,在实验考察范围内,金属脱除率随微波辐射时间延长而提高,随着辐射功率的增大金属脱除率先升高后降低;分离工艺的分离效果取决于脱金属剂与金属反应产物的类型,微波脱金属与常规脱金属相比,金属脱除率可提高11%～20%。     

减二线馏分油微波辐射脱酸新方法的研究

以NaOH与去离子水为复合溶剂用微波辐射法对江苏减二线馏分油进行了脱酸精制研究。得到的最佳精制条件为 :V(复合溶剂 )∶V(油 ) =0 .2 2∶1、压力 0 .0 9MPa、恒压辐射时间 4min、微波功率 375W、静置时间 2 5min。馏分油的酸值 (KOH)由 0 .5 7mg/ g降至 0 .0 4 81mg/ g ,馏分油回收率为 99.3%。     

微波辅助络合萃取脱除柴油中碱性氮化物的工艺研究

依据萃取理论,运用正交实验设计方法,用95%乙醇和微量SnCl_2组成的复配剂在微波辐射条件下对催化裂化柴油进行精制工艺研究。结果表明,在复配剂中SnCl_2质量分数0．6%,压力0．3MPa,功率225W,剂油比1．0,辐射时间6min时,碱性氮脱除率为94．1%,回收率为94．8%。该方法与传统络合萃取相比节约了金属离子用量,提高了脱氮率,而且清洁无污染。     

Microwave Leaching of Vanadium From Petroleum Coke

The effects of microwave power, temperature, concentration of alkali and surfactant, sodium atoms ratio, liquid-solid ratio, and the leaching time on the leaching rate of vanadium were studied. Compared with microwave leaching and water bath heating leaching, the results showed that microwave heating can shorten the reaction time and improve the leaching efficiency. The reasons that microwave heating strengthened vanadium leaching from petroleum coke are discussed as well. The optimal conditions are determined: microwave power 500 W, leaching temperature 95°C, alkali concentration 125 g/L, sodium atom ratio of 3:1, surfactant concentration 400 mg/L, solid-liquid ratio 5:1, and leaching time 120 min. Under the best condition, the leaching rate of vanadium can be 89.54%.     

石油钻井废弃物微波单模谐振腔处理新工艺

 研究开发了对石油钻井废弃物的微波特殊工艺处理,考察了微波功率、停留时间、物质质量、N2流速以及压强等因素对石油钻井废弃物中所含油分脱除率的影响,探讨了可能的微波加热机理。结果表明,微波输入功率是影响微波处理石油钻井废弃物结果的最重要因素,其次是停留时间和物质质量影响。石油钻井废弃物中所含油分的脱除率在某种程度上与其初始水含量多少相关,水作为很好的微波吸收物质将吸收的能量传递给油。由于废弃物中存在一定的微孔结构,使得一部分水可以被加热成过热水,从而使油在较高的温度下气化,并在载气的作用下被脱除。     

油田井口称重计量微波加热技术研究

为了降低低产油井间歇产液对含水原油称重计量造成的误差,设计了一套带有微波加热源的含水原油称重计量装置,该装置可实现对井口来液进行高效、即时加热,减少油井间歇产液造成的原油挂壁、结蜡现象。通过室内实验发现,当控制单次称重的含水原油体积为20 L时,采用3个螺旋布置于称重装置底部总功率为3 kW的微波加热源,可以对不同含水率的原油进行高效加热。加热温升40℃的平均用时在10 min以内,同时能明显减少原油挂壁、结蜡的现象,使称重计量具有良好的准确度。与常规加热相比,微波加热即时、高效,对低产油井计量具有良好的适应性,同时还能有效地降低加热部分的投资费用,具有良好的经济效益。     

渣油的微波改质技术研究

以沙特中质渣油为原料,研究了微波辐射参数（温度、功率、时间）对油品降黏、脱硫、脱金属效果及族组成的影响,并研究了不同原料（沙特中质渣油、沙特轻质渣油、金陵渣油）性质对微波降黏效果的影响规律。结果表明:在实验考察范围内,油品黏度随辐射温度的升高先降低后升高,随功率的升高而降低,随时间的增长先降低后升高;硫含量随功率的增加逐渐降低;与渣油原料相比,经微波辐射后,渣油的饱和烃含量基本不变,芳烃含量略有增加,胶质、沥青质含量减少,金属（Ni、V）含量基本不变;原料中沥青质含量越高,降黏的效果越好。     

Microwave Demulsification in Removing Naphthenic Acids from Diesel Oil

Abstract

Emulsification is an undesired phenomenon in the refining of highly acidic oil by alkali-washing electro-refining. In this article, a novel microwave method is applied for demulsification in the removing of naphthenic acid from diesel oil. The internal heating is attributed to molecular rotation and ionic conduction. The decrease of interface zeta-potential and the viscosity of diesel oil are responsible for the demulsification with microwave irradiation. The results exhibited that the demulsification rate is maximized when the optimum microwave irradiation power, exposure time, and irradiation pressure for Anshan and Liaohe diesel oil are deemed to be 375 W, 5/6 min and 0.05 MPa, respectively.     

CATALYTIC HYDROTREATMENT OF PETROLEUM RESIDUE

ABSTRACT

Iraqi reduced crude (350°C+) with a sulfur content of 4.3 wt% and a total metal content (Ni+V) of 141 WPPM was n-heptane deasphalted at specified conditions. The deasphalted oil (97.2 wt% of original residue) contains 4.1 wt% of sulfur and 103 ppm of metal. The original reduced crude and deasphalted oil were hydrotreated on a commercial Ni-Mo-alumina catalyst presulfided at specified conditions in a laboratory trickle-bed reactor. The reaction temperatures varied from 300 to 420°C with the liquid hourly space velocity (LHSV) ranging from 0.37 to 2.6 h^?1. Hydrogen pressure was kept constant throughout the experiments at 6.1 MPa, with a hydrogen/oil ratio of about 300 NLL^?1 (normal liters of hydrogen per liter of feedstock). Analysis for sulfur, nickel, vanadium and n-pentane asphaltenes were carried out for hydrotreated products from both the original residue and the deasphalted oil. The comparison of the results obtained for the hydrotreatment of deasphalted oil and original reduced crude indicates that the removal of sulfur, nickel and vanadium was higher for the deasphalted oil than those obtained for the non-deasphalted residue over the entire range of conversion. The exclusion of extremely high molecular weight asphaltenes by n-heptane deasphalting seems to improve the access of oil into catalyst pores resulting in higher desulfurization and conversion of the lower molecular weight asphaltenes. The sulfur content of n-pentane precipitated asphaltenes remained unchaneed with LHSV for various temperature for hydrotreated products produced from both deasphalted oil and original reduced crude.     

水杨酸作用下微波辐射稠油破乳脱水的研究

以含水质量分数为50%的大庆稠油为原料,在水杨酸作用下对其进行微波辐射脱水,考察了水杨酸加入量(占稠油的质量分数)和微波辐射压力、时间、功率等条件对稠油脱水率的影响。结果表明,水杨酸作为特殊的催化剂可增强稠油乳状液对微波的吸收功能,对脱水具有明显的促进作用;在水杨酸加入量为5%,微波辐射功率为450 W,辐射压力为0.4 MPa,辐射时间为10 min的优化条件下,稠油脱水率达94.3%。     

Effects of Process Conditions on Desalting and Demetalization of Crude Oil

Abstract

The efficiency of desalting for six crude oils was studied with a SY-1 dynamic simulation experimental installation. The demulsifier DC2 was examined for 1#, 2#, and 4# crude oil and DC4 was used for 3#, 5#, and 6# crude oil. The effects of temperature, electric field gradient, dosage of demulsifier, and washing water on the desalting efficiency of six crude oils were investigated. The results showed that at the optimization process condition after desalting, the desalting efficiency and the salt content of 1# crude oil reached 89.17% and 1.92 mg/L; that of 2# crude oil reached 85.08% and 1.04 mg/L; that of 3# crude oil reached 91.06% and 1.35 mg/L; that of 4# crude oil reached 81.67% and 1.51 mg/L; that of 5# crude oil reached 81.03% and 2.32 mg/L; and that of 6# crude oil reached 86.64% and 2.67 mg/L. Different crude oils have different metal contents. Three assistants, ammonium nitrate (TJ1), nitric acid (TJ3), and polyamine carboxylate (TJ4), were used to improve the efficiencies of desalting and demetalization of six crude oils. TJ4 was more efficient in removing calcium and iron for 1# and 2# crude oil. TJ1 was more efficient in desalting and demetalizing 5# crude oil. The efficiencies for removal of calcium, iron, nickel, and vanadium respectively reached 99.89%, 98.33%, 20.58%, and 43.02%. TJ3 has better efficiency desalting and demetalizing for 6# crude oil. With the concentration of TJ3 increasing from 0 to 80 mg/L, the desalting efficiency increases from 31.22% to 73.54%, and the iron removal efficiency increases from 56.0% to 74.05%.     

响应面法优化固定化微生物降解石油污染物

从炼油厂活性污泥中筛选和驯化了1株石油降解菌SJ-1,以秸秆材料WT为固定化载体,采用表面吸附法制备固定化微生物;以胜利原油为反应底物,考察了温度、微生物接种量、原油质量浓度、pH值对原油降解率的影响;采用响应面法优化了降解条件,并在优化条件下进行了降解动力学实验。结果表明,单因素对降解率的影响程度从大到小的顺序为温度、pH值、原油质量浓度、接种量,其中pH值和原油质量浓度、原油质量浓度和温度的交互影响对原油降解率影响较显著;根据响应面模型计算得到的最佳降解条件为pH值7.0、原油质量浓度5000 mg/L、温度34℃、接种量46 g/L,此时原油降解率最高达68.3%;固定化微生物和游离微生物降解过程均符合一级动力学,且前者的降解速率是后者的3.67倍。     

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.     

微波消解-电感耦合等离子体发射光谱法测定管输原油中镍、钠、钒

建立了用微波消解试样,电感耦合等离子体发射光谱法测定管输原油中Ni、Na、V的检测方法。搅拌均匀的试样通过加入硝酸后经微波消解,制备成测试溶液,用电感耦合等离子体发射光谱仪(ICP-OES)测定其中Ni、Na、V的含量。方法回收率在93%～100%之间,相对标准偏差在3.08%～10.30%之间,方法满足口岸进口管输原油中Ni、Na、V快速测定的要求。     

盐-高分子联合作用下高蜡原油微波破乳研究

在考察了盐添加量与原油乳状液升温速率、脱水率、盐回收率关系的基础上,提出了盐-高分子联合作用对原油进行微波辐射破乳的方法。结果表明,利用SH9402微波反应系统,使含水质量分数为50％的大庆石蜡基高蜡原油乳状液在辐射功率为225W、系统压力为0．7MPa、恒压时间为12min、剂油质量比为0．05、乙酸钠／聚乙二醇2000质量比为3：7时,脱水率达95．97％,盐回收率达91．23％;与单一使用乙酸钠相比,脱水率提高了0．14个百分点,盐的用量降低了70％（质量分数）,盐回收率提高了29．29％。     

Introducing a New Method for Predicting PVT Properties of Iranian Crude Oils by Applying Artificial Neural Networks

Abstract

In this study artificial neural networks (ANNs) have been applied for the prediction of main pressure, volume, and temperature (PVT) properties, bubble point pressure (P_b), and bubble point oil formation volume factor (B_ob) of crude oil samples from different wells of Iranian oil reservoirs. Via a detailed comparison, the great power of ANNs with respect to traditional methods of predicting PVT properties, like Standing, Vasquez and Beggs, and Al-Marhoun, with higher prediction precision up to R² = 0.990 has been illustrated and the obtained parameters of ANNs for the application of prediction of other crude oil samples has been presented. The applied PVT data set in this study consists of 218 crude oil samples from Iranian reservoirs and for assurance of the applicability of the ANN model the PVT data set has been divided into 2 training (190 samples) and cross validation (28 samples) data sets and obtained ANNs from applying the training data set has been tested on the cross validation data set which has not been seen by the network during the training process. The obtained results for both training and cross validation data sets confirm the great prediction power of ANNs, for both data sets with respect to traditional PVT correlations.     

微波灰化等离子发射光谱法测定渣油中的铁、镍和钒

采用微波灰化技术对渣油试样进行处理,制备渣油水相测定溶液,用等离子发射光谱法对试样渣油中的铁、镍、钒进行测定,确定了微波灰化程序升温所需温度与时间,并进行精密度和准确度对比实验,结果表明各元素的相对标准偏差均小于5%,回收率在96%~105%。     

高蜡原油微波破乳乙酸钠-聚乙二醇添加剂的研究

采用乙酸钠和聚乙二醇2000复配添加剂对大庆高蜡原油破乳效果进行了研究。结果表明,利用SH9402微波反应系统,含水率为50%的大庆石蜡基高蜡原油乳状液在辐射功率为225 W、系统压力为0.7 MPa、恒压时间为7 min、剂油质量比为0.05、乙酸钠和聚乙二醇2000质量比为3：7时,脱水率达到96.39%,盐回收率达93.98%。与单一使用乙酸钠相比,不仅破乳效率高,而且乙酸钠用量降低,乙酸钠回收率提高,解决了乙酸钠残留的问题。