Evaluation of Effects of Selected Wax Inhibitors on Paraffin Deposition

Deposition from decane solutions of model paraffins such as n-C₂₄H₅₀ (C₂₄), and n-C₃₆H₇₄ (C₃₆), as well as a mixture of n-alkanes (C₂₁ to C₄₄) was examined with and without chemical wax deposition inhibitors. The device used to produce the deposits investigated was a “Cold Disk” Wax Deposition Apparatus (CoDWaD) capable of producing field like deposits with relatively small volumes of oil in minutes. It was found that most of commercial wax inhibitors tested could decrease the deposition of low molecular weight paraffins (C₃₄ and below), while having little effect on the wax deposition for high molecular weight paraffins (C₃₅-C₄₄). In many cases, although the total amount of wax formed on the cold plate was reduced, the absolute amount of deposition for high molecular wax was actually increased. Therefore, the net effect of many commercial inhibitors is to make even harder wax under the tests conditions studied here. One intriguing result was that the addition of an oleic imidazoline c rrosion inhibitor improved the performance of two wax inhibitors tested. It was also observed that there are subtle differences in inhibitor performance depending on whether the test solutions are binary mixtures, synthetic wax mixtures, or crude oil.     

AN EXPERIMENTAL STUDY OF THE EFFECT OF PARAFFINIC SOLVENTS ON THE ONSET AND BULK PRECIPITATION OF ASPHALTENES

Asphaltene onset concentration and bulk deposition were measured for a typical live reservoir oil titrated with n-C₆H₁₄, n-C₅H₁₂, n-C₄H₁₀, C₃H₈, C₂H₆, CH₄ and CO₂ at 100° C (212 ° F) and 29.9 MPa (4340 psia). The concentration of titrant at asphaltene onset was observed to decrease approximately in a linear fashion with decreasing molecular weight of the paraffinic solvent; CH₄ did not induce any asphaltene precipitation. Bulk deposition experiments were performed using a solvent: oil volume ratio of 10:1; the results indicated that the weight percent of asphaltenes precipitated increased exponentially with decreasing molecular weight of the paraffinic solvents. More importantly, the asphaltene molecular weight showed a maximum for n-C₄H₁₀ precipitated asphaltenes. Possible explanations for this unusual result are presented.     

New Generalized One-Parameter Vapor Pressure Formula of Homologous Pure Hydrocarbon Series

Generalized formula has been developed to calculate vapor pressure of pure hydrocarbon series (C_nH_2n+2) from C₁₁H₂₄ to C₃₅H₇₂ based on one parameter “carbon number” only. As a result this technique is considered to be useful for prediction of vapor pressure of pure hydrocarbons, since it is possible to use this formula depending on simple parameter “carbon number”.     

GEOCHEMICAL SIGNIFICANCE OF FATTY ACIDS IN CRUDE OILS AND RELATED SOURCE ROCKS FROM EGYPT

The acid fraction of crude oils and related source rocks of different stratigraphic units from the Gulf of Suez and Western Desert, Egypt were analyzed by GC and GC/MS. Normal alkanoic acids (n-C₉-n-C₃₀) were the dominant series (with the predominance of even-carbon numbers maximizing at n-C₁₆, n-C₁₈ or n-C₂₂while iso- and anteiso- branched acids were minor constituents. All samples showed a preference of short chain acids (n-C₁₀-n-C₁₉ with respect to long chain acids (n-C₂₀+) typical of marine oils and source rocks. The n-alkanoic acids distribution suggests a predominant algal and/or bacterial contribution. The presence of high relative abundance of mono and di-unsaturated carboxylic acids in a number of samples point to recent microbial activity. Distributions of n-alkanoic acids in the range (C₁₂-C₂₂) show striking similarities with the n-alkane distributions, indicating that both series may, at least in part, be diagenetically related by decarboxylation of the acids. Dehydroabietic acid has been identified in only one sample from Balaim Marine source rock. This resin-derived compound has probably been transported as pollen to the marine environment.     

注水开发过程中原油的生物降解与水洗作用

注水开发是提高原油采收率的常用方法。为了探索注水开发过程中原油遭受的次生蚀变作用和组分变化规律,对典型注水开发的济阳坳陷曲堤油田曲9油藏进行了动态跟踪和地球化学对比分析。研究结果表明,随着注水开发过程的推进,原油族组成中饱和烃相对含量呈升高趋势,而芳烃相对含量呈降低趋势,体现出典型的水洗作用效应。Pr/nC₁₇和Ph/nC₁₈比值呈现出先降低后升高,或先升高后降低的复杂变化,推测不仅受到水洗作用或生物降解的影响,还有类似地质色层效应的加入。C₁₅8β（H）-补身烷/C₁₆8β（H）-升补身烷逐渐升高,指向生物降解抑或水洗作用的蚀变,尚无法区分。三环萜烷/17α（H）-藿烷、C₂₇重排/C₂₇规则甾烷和甾烷/17α（H）-藿烷均呈现明显增高趋势,C₃₁藿烷22R/C₃₀藿烷（C₃₁R/C₃₀H）则呈现幅度较小的降低趋势,均指示生物降解作用的结果。甲基菲指数（MPI₁）、二苯并噻吩/菲（DBT/P）、C₂₆三芳甾烷20S/（20S+20R）与C₂₆/C₂₈三芳甾烷（20S）基本保持不变,表明水驱过程中三芳甾烷并不受影响,菲系列和二苯并噻吩系列未表现出显著的水溶性或抗生物降解能力差异。     

RECOVERY OF ASPHALTENES FROM TAR SAND BY SUPERCRITICAL FLUID EXTRACTION

Many non-oil producing countries are enriched with other sources of energy, for example tar sand, oil shale, coal, biomass, and uranium, that are not fully utilized. Supercritical fluid extraction (SFE) of tar sand was carried out in a batch autoclave at different temperatures. Extracts recovered from SFE were fractionated into oils, asphaltenes, preasphaltenes and gases by solvent extraction. The highest yield) of SFE (24.3 wt % dry basis) from tar sand was obtained with n-pentane/benzene (1/1, v/v') mixture at 655 K. Comparison of the amount of n-alkanes (C1-C4) evolved at 585 K and 685 K shows that the amount of methane is significantly increased at 685 K whereas the amount of C4 alkane is reduced. At 685 K, hydrogen and methane represent 45·1 vol % of the gases evolved from the SFE. The yields of C1-C3 alkane hydrocarbons were higher for supercritical fluid extracts at 685 K as compared to those obtained at 585 K. The quantity of olefines (C₂H₄ + C₃H₆) was found between 5·1 and 10·1 vol %.     

塔里木盆地塔河油田原油地球化学特征的化学计量学分析及应用

塔里木盆地塔河油田由于存在多期次原油充注导致其成因至今无法得到很好地解释。应用地球化学手段对塔河油田原油地球化学特征进行综合研究,结果显示：塔河油田奥陶系原油沉积于海相沉积环境,处于成熟—过成熟阶段,正构烷烃分布较完整、具有UCM鼓包、普遍存在25?降藿烷、伽马蜡烷含量低,C₂₉藿烷丰度高、规则甾烷呈现C₂₉>C₂₇>C₂₈分布、规则甾烷αββ构型丰度高于ααα构型等特征,表明塔河油田原油遭受过较强程度的微生物降解作用,存在至少2个期次的原油充注。利用主成分分析（PCA）和层序聚类分析（HCA）方法对原油生物标志化合物指标进行分析,将塔河油田原油分为3类：I类原油具有三环萜烷/五环萜烷、Ts/17αC₃₀藿烷、重排甾烷/规则甾烷、C₃₁/C₃₂藿烷、C₂₉/C₃₀藿烷、C₂₄/C₂₃三环萜烷、C₂₀₊₁₉/C₂₃₊₂₄三环萜烷、Ts/Tm高,Ph/nC₁₈低,正构烷烃分布完整,呈现出多期充注特征,但主要表现出早期生物降解原油的特征,早期生物降解原油的贡献高于后期充注正常原油的贡献;II类原油的nC₂₁^-/nC₂₂⁺值最低,部分样品正构烷烃缺失,UCM鼓包明显,主要代表早期经历过强烈微生物降解的原油; III类原油nC₂₁^-/nC₂₂⁺、αβC₃₁?22S/（22S+22R）、C₂₄四环/（C₂₄四环+C₂₆三环）值最高,正构烷烃受热成熟度的影响最大,高碳数正构烷烃大量热裂解导致低碳数正构烷烃相对富集,代表混合原油但正常原油的贡献较大。     

页岩中丙烷的降解特征及对页岩气组成的影响

为探讨高过成熟阶段页岩中小分子烃类的降解对页岩气组成的影响,选取了丙烷和页岩(取自四川盆地龙马溪组同一钻井、不同深度)开展不同系列的模拟实验。对C_3H_8、C_3H_8+页岩、C_3H_8+页岩+水在360℃、50 MPa条件下进行黄金管限定体系恒温热模拟实验,恒温时间包括72,216,360,720 h;同时为探讨更高演化程度条件下页岩中小分子烃类的降解特征,对C_3H_8、C_3H_8+页岩分别在400,450,500,550℃和50 MPa条件下恒温热模拟72 h。结果显示,360℃恒温实验条件下,C_3H_8+页岩体系中CH_4、C_2H_6生成量及CH_4/C_2H_6值比相应的C_3H_8对照实验高,且黏土矿物含量高的S1系列实验生成的CH_4、C_2H_6及CH_4/C_2H_6值基本较S2系列高。提高模拟实验温度后,丙烷的转化率显著提高,C_3H_8+页岩实验中的CH_4、C_2H_6产率均高于对照实验,且CH_4的产率高于C_2H_6。2个系列的模拟实验结果均说明黏土矿物能催化C_3H_8的裂解,且有利于CH_4的产生。含水体系中CH_4、C_2H_6生成量及CH_4/C_2H_6值比无水体系高,说明水能促进页岩中C_3H_8的裂解,且有利于CH_4的富集。页岩中黏土矿物和水对C_3H_8裂解的促进作用导致页岩气向干燥系数高的方向演化,页岩中小分子烃类的降解对高过成熟阶段页岩气的组成具有重要影响,在此过程中水分子起到重要作用,其对高过成熟页岩气资源的评价值得更多关注。     

分子筛类型对正戊烷催化裂解反应性能的影响

为了解决石脑油中正戊烷难以高效催化裂解为低碳烯烃的问题,先采用Aspen Plus模拟软件对正戊烷的催化裂解反应进行热力学平衡分析,然后考察分子筛类型对正戊烷催化裂解的低碳烯烃收率和选择性的影响规律。对正戊烷的催化裂解反应进行热力学分析的结果表明,当反应温度高于650 ℃时,丙烯和乙烯的质量比m(C₃H₆)/m(C₂H₄)<1,且低碳烯烃(C₂H₄+C₃H₆+C₄H₈)的收率开始增速缓慢。因此,综合考虑m(C₃H₆)/m(C₂H₄)和低碳烯烃收率,选择在反应温度650 ℃下考察正戊烷在不同类型分子筛上的催化裂解反应性能。结果表明：在MTT分子筛上催化裂解的低碳烯烃选择性较高,在温度为650 ℃、压力为0.1MPa、MHSV为540 h^-1的反应条件下,正戊烷在MTT分子筛上催化裂解的低碳烯烃(C₂H₄+C₃H₆+C₄H₈)选择性为55.21%。通过对催化裂解过程的裂解和氢转移反应的分析,表明小孔径的MTT分子筛能够抑制双分子反应,包括双分子裂解反应和双分子氢转移反应,从而提高低碳烯烃的选择性。     

Effect of Branched C8 Olefins Addition to Mexican Gasoline on Motor Vehicles Exhaust Emissions

Two groups of gasoline blends were prepared using a base-gasoline, containing 7.6% MTBE and added with either lower olefins (C₅-C₆) or butene's dimer (made up of 70% branched C₈-olefins). In each gasoline group, the olefin concentration was varied 5, 10, and 15 vol%. The dimer was produced in our pilot plant facilities from a mixture of n-butenes. An FTP-75 test procedure, performed on a 98 model year vehicle, was used to assess the effect of olefins type (C₅-C₆ or C₈) and their concentration in a gasoline blend on exhaust emissions; namely: CO, total hydrocarbons, NOx, and toxic compounds, such as aldehydes and ketones. Average CO emissions dropped 20-27%, when using 5-15 vol% C₈ olefins-gasoline, in comparison with those using C₅-C₆ olefins-gasolines. Total hydrocarbons emissions, on the other hand, remained practically unaffected either by the type of olefins or their concentrations (5-15 vol%). NOx emission factors decreased 10-14% when using the C₈ olefins-gasolines, relative to those containing lower olefins. Main toxic pollutants were formaldehyde, propanone, and acetaldehyde. In average, acetaldehyde emissions decreased 23-53% in the dimer-gasoline group, but formaldehyde emissions increased 5-39%, depending on the olefins content and in comparison with the lower olefins-gasolines.     

ALUMINA SUPPORTED Co-Mo OXIDES AS A CATALYST FOR HYDRODESULPHYRISATION OF ORGANIC SULFIDES AND DISULPHIDES (PART-I) USING STOPPED FLOW GAS CHROMATOGRAPHY

A model study on the hydrodesulphurization of dimethyl sulphide, di n-prophyl sulphide, di n-butyl sulphide and dimethyl disulphide on Co-Mo-A1₂O₃ surface was conducted using stopped-flow chromatographic technique. The plots for the rates of hydrocarbon formation agreed well with the first order reaction at the surface of the catalyst.

Activation energies for the hydrodesulphurization of (C₂H₅)₂S, (C₃H₇)₂S, n-(C₄H₉)₂S and (CH₃)₂S₂ are 57.55, 70.67, 72.74 and 37.80 Kj mole^-1 respectively.     

MOLECULAR SIEVE CARBON FROM COALS FOR AIR SEPARATION

Molecular Sieve Carbon (MSC) for air separation has been prepared from two Chineae coals ( anthracite and bituminous coal) by carbonization followed by activation and carbon deposition. The optimum experimental conditions have been obtained for each coal and the such made MSC could separate N₂ from air efficiently. Also investigated is the preparation of MSC by mixed coals of anthracite and bituminouscoal.

The adsorption of CO₂ and C₂H₆ on the MSC at 298K has been studied. Dubinin theory is used to interpret the isotherms. The predominating micropores of the MSC are those having the size of 0.33-0.40 nm in diameter.     

Studies on Carbon Number Distribution of High Melting Microcrystalline Waxes

Carbon number distribution of microcrystalline wax derived from tank sludges of Bombay High crude oil (India) and its various high melting fractions have been studied by High Temperature Gas Chromatography (HTGC). Binodal, Gaussian distribution and a wide range of alkanes, ranging from C₂₁-C₇₅, along with their many isomers with predominant alkanes being C₄₀ and C₆₇, have been observed in the microcrystalline wax. Higher melting wax fractions have Gaussian distribution.     

n-DIOCTADECYL FUMARATE-VINYL ACETATE COPOLYMER: SYNTHESIS, CHARACTERIZATION AND APPLICATION AS FLOW IMPROVER FOR OILS

Monomer n-dioctadecyl fumarate (DOF), and copolymers (C₁₈FVA) of DOF with vinyl acetate were synthesized. Monomer and copolymers were characterized by IR, ¹H-NMR, VPO and DSC. Due to the special structure of DOF, only copolymers containing 45.9%-97.8% (mol) DOF were obtained. The crystalline CH₂ numbers on polymer side chain χ were calculated from enthalpy determined by DSC, and it was found that χ slightly decreased with increasing vinyl acetate content. C₁₈FVA can be used as flow improver for viscous oil and residual oil, and the more the crystalline CH₂ number on the side chains, the better lattice match between copolymer and wax crystal structure of oils.     

热处理对添加防蜡剂长庆原油流动性及蜡沉积特性的影响研究

基于流变性测试和蜡沉积实验研究了热处理温度对添加EVA/PAMSQ复合防蜡剂的长庆原油的流动性和蜡沉积特性的影响。研究发现加剂原油依然具有热处理效果,50℃热处理条件下加剂原油的流动性改进效果较差,随着热处理温度升高至60、70和80℃,加剂原油的流动特性(如凝点、黏度、小振幅振荡剪切特性)显著改善。80℃热处理条件下,加剂原油的凝点已低于0℃,表明热处理与EVA/PAMSQ复合防蜡剂具有良好的协同效果。同时,随着热处理温度的升高,加剂原油的蜡沉积速率逐渐降低,但蜡沉积物的含蜡量逐渐升高,这可能不利于蜡沉积物的剥离。蜡沉积物呈现出非均质结构,表层蜡沉积物为凝油状,底层蜡沉积物具有比表层蜡沉积物更高的析蜡点和屈服强度。     

Experimental Investigations of the Mitigation of Paraffin Wax Deposition in Crude Oil Using Chemical Additives

Abstract

Wax deposition from crude oil is a very expensive problem for oil producers around the world. The objective of this study is to understand the characteristics of paraffin wax deposition and to test the effectiveness of solvents in the inhibition of the crystallization and subsequent precipitation of the paraffin wax and to test the most effective concentration of the solvent used. The oil used here is from the Dakota formation from the Fourteen Mile Field in the Big Horn Basin of Wyoming. Two paraffin inhibitors were tested for this crude oil on a horizontal flow system. The inhibitors are mixtures of solvents, pour point depressants, and wax crystal modifiers. These inhibitors were tested at different concentrations and temperatures and the deposition rates were obtained for each. One inhibitor especially designed for this crude oil was relatively successful, reducing the deposition by up to 59% depending on the temperature.     

水力空化场苯-甲醇低温烷基化制备二甲苯

基于文丘里型空化管的水力空化场强化,苯与甲醇在低温下进行烷基化反应;采用气相色谱 质谱联用分析反应产物,考察反应条件对反应效果的影响,并根据产物分布,推测并验证了反应历程。结果表明：在水力空化条件下,苯与甲醇在低温下发生了烷基化反应,其主要反应产物为甲苯、二甲苯和乙苯。最佳反应条件为：空化管入口压力0.4 MPa,反应终温40 ℃,苯摩尔分数20%,时间40 min。该反应历程为：在水力空化场强化下,苯与甲醇解离生成·C₆H₅、·H、·CH₃和·OH,继而·C₆H₅与·CH₃和·H发生自由基串联反应,依次生成烷基苯和烷基环烷烃,·OH与·C₆H₅或·H发生自由基反应,分别生成苯酚或水。     

成熟度与热模拟产物分步萃取对滞留油生物标志物的影响

明确抽提过程中不同极性有机溶剂对所获得的生物标志物参数的影响,对基于生物标志物的生烃母质研究具有重要意义。选用鄂尔多斯盆地延长组低熟富有机质泥页岩进行生、排烃热模拟实验,并结合热模拟固体残样的实测随机镜质体反射率(R_O)值,准确剖析热演化程度和溶剂极性对生源和沉积环境参数适用范围的影响。结果表明：有机溶剂极性的大小不仅会影响抽提物的产率和族组分特征,而且会显著影响抽提物中正构烷烃、三环萜烷的分布特征,但对甾烷的分布特征影响并不明显。溶剂极性和热演化的双重影响导致生物标志物参数的适用范围存在明显区别,∑C_21^-/∑C_22⁺和(nC₂₁+nC₂₂)/(nC₂₈+nC₂₉)仅在低熟—高成熟的中期阶段(R_O值介于0.70%～1.48%之间)可作为有效的生源参数,而沉积环境判识参数∑三环萜烷/∑藿烷值适用范围更窄,仅在低熟—高成熟早期阶段(RO值介于0.70%～1.34%之间)有...     

季铵盐类氯铝酸离子液体的表征及其催化苯与苯酐的酰基化反应

制备了多种季铵盐离子液体,考察了不同阴阳离子的离子液体对苯与苯酐酰基化合成邻苯甲酰苯甲酸(BBA)反应的催化性能.采用FTIR、紫外吸收光谱与Hammett酸强度函数联用的方法对离子液体进行表征,并借助量化计算分析反应路径.实验结果表明,不同阴离子的Et3NHCl离子液体催化活性的高低顺序为:Et3NHCl-2.5Al...     

环烷基变压器油精制过程中气体含量变化的研究

以中国海洋石油集团有限公司自产环烷基原油常二线馏分油为原料,考察了加氢脱酸-糠醛精制-液相脱氮和白土补充精制联合工艺各精制阶段对环烷基变压器油中气体含量的影响。结果表明：环烷基原油常二线馏分油经联合工艺精制生产变压器油时,液相脱氮电精制阶段会使变压器油中的氢气、二氧化碳、甲烷、乙烯及乙烷气体含量明显升高;通过调整电精制工艺条件和增设真空过滤装置进一步降低了变压器油产品中的气体含量,所生产的变压器油产品的气体含量均满足电力行业标准的技术要求。