特稠油乳化降黏机理研究

研究了胜利油田罗家高硫特稠油的黏度及其极性四组分、有机杂原子、金属元素的关联。结果表明，该稠油的高黏度主要与三个因素有关：（1） 含有高分子量的胶质和沥青质组分；（2） 硫的质量分数很高；（3） 金属元素V、Fe、Ni形成配位络合物增加了沥青质的内聚力。同时考察了所筛选的降黏剂的效果，降黏剂明显降低了油水界面张力，使得稠油的黏度降低。比较了添加降黏剂前后沥青质的电子探针照片的变化，推测降黏剂分子借助强的形成氢键的能力和渗透、分散作用进入沥青质片状分子之间，破坏了沥青质分子平面重叠的聚集体，使聚集结构变得疏松，表明聚集有序性降低是稠油降黏的主要机理。     

电喷雾电离源结合傅立叶变换离子回旋共振质谱分析地下水中可溶性有机质分子组成

应用电喷雾电离源结合傅立叶变换离子回旋共振质谱(ESI FT-ICR MS)对地下水进行分析,基于高精确度的分子量检测结果,鉴定出O_x,N_1O_x和N_2O_x3大类,共计27小类含杂原子的化合物。杂原子化合物中O_x类化合物占绝大多数,而含N化合物则以结合大量氧原子的形式广泛存在。结合各类杂原子化合物的等效双键数(DBE)及碳数分布,发现O_x类化合物中存在大量的羧酸结构,推测含氮化合物可能来自于O_x类化合物的衍生反应。实验结果拓宽了对地下水中可溶性有机质的认识,为进一步确定其中杂原子化合物的结构类型奠定了基础。     

白石湖煤THF萃取物中硫、氮化合物赋存形态

采用四氢呋喃(THF)对白石湖煤进行索氏萃取,萃取液在四氟硼酸银存在下与碘甲烷反应,转化成甲基磺酸盐。采用电喷雾电离(ESI)傅里叶变换离子回旋共振质谱(FT-ICR MS)对甲基硫盐和含氮化合物进行了表征,结合硫、氮化学发光检测器(GC-SCD和GC-NCD)分析,研究THF萃取物中硫、氮化合物形态。结果表明,THF萃取物中主要是S_1、S_2、N_1、N_1O_1类化合物,含量较高的硫、氮化合物分别是二苯并噻吩类化合物及咔唑类化合物。     

先锋褐煤可溶有机质中含氮化合物的组成和结构特征（英文）

先锋褐煤在高压釜中用等体积的甲醇/甲苯溶剂300℃下热溶得到热溶物和热溶残渣,利用X射线光电子能谱(XPS)分析了先锋褐煤及其热溶残渣中氮的形态,利用气相色谱/质谱(GC/MS)和电喷雾傅里叶变换-离子回旋共振质谱(ESI FT-ICR MS)分析了热溶物中含氮化合物的组成和结构特征。研究表明,先锋褐煤中氮形态含量顺序为季氮吡啶氮吡咯氮,而季氮在热溶过程中更易溶出。GC/MS共检测出热溶物中20种含氮化合物,并且大部分为胺类化合物。ESI FT-ICR MS检测出热溶物中300多种含氮化合物,大部分含氮化合物含一个或三个氮原子。含一个氮原子的含氮化合物主要以N_1O_1、N_1O_2和N_1O_xS_(1-2)类化合物为主,而含三个氮原子的含氮化合物主要以N_3O_xS_(1-2)(x=1-12)类化合物为主。含一个氮原子的含氮化合物的等效双键数和碳数随氧原子数增加而增加。     

大港常压渣油各组分平均偶极矩的研究

将大港常压渣油利用液相色谱法分成六个组分，测定了各组分的平均偶极矩。结果表明，渣油分子具有极性，饱和分和轻芳烃组分、重芳烃、轻胶质、中胶质、重胶质、沥青质的偶极矩依次增大，分别为1.19、2.88、3.79、4.92、6.36、11.70 Debye。元素分析表明，从饱和分和轻芳烃组分到沥青质组分，H/C原子比逐渐下降，表明H/C原子比减小与平均偶极矩增大有关；从饱和分和轻芳烃组分到沥青质组分，S/C、N/C原子比总体呈现上升趋势，渣油组分的杂原子含量与其极性有一定的关系，但两者并不完全一致，渣油组分分子的平均偶极矩还受到其他因素的影响。     

低温煤焦油常渣C5沥青质的分离与表征

从低温煤焦油中蒸馏提取出大于350℃的常渣,以正戊烷、正戊烷+5%乙醇、正戊烷+5%异丙醇三种溶剂沉淀沥青质。通过1H-NMR、13C-NMR、傅里叶变换离子回旋共振质谱仪(FT-ICR MS)、元素分析和相对分子量测定等手段对重组分沥青质的结构参数、杂原子化合物的分布等方面进行了分析,构建含杂原子的平均分子结构模型。结果表明,乙醇和异丙醇的加入可以显著降低C5-沥青质的收率,所得沥青质的芳香性增强,平均分子量增大,为更高缩合度的具有较短侧链的结构;极性溶剂的加入没有改变沥青质中杂原子化合物的类型,但是O1和O2中一部分低缩合度的化合物转移到可溶质中,O3-O6化合物的相对丰度增大,表明混合溶剂有利于萃取低缩合度的化合物。     

塔河常压渣油沥青质含硫官能团形态与其性质的关系研究

以塔河常压渣油为原料,分离正庚烷沥青质,并将正庚烷沥青质分成三个极性不同的亚组分。测定沥青质亚组分的平均偶极矩,利用¹H-NMR谱关联得到沥青质平均结构参数以分析沥青质亚组分缔合性质,采用X射线吸收近边结构谱(XANES)表征沥青质亚组分中含硫官能团形态,分析硫原子存在形态对沥青质性质的影响。结果表明,随着沥青质亚组分极性降低,H/C原子比增大;沥青质极性增加,缔合性增强;沥青质中还原态硫主要以噻吩硫形式存在,其次为硫醚;亚砜、砜和磺酸盐是主要的含氧硫化物。噻吩、砜和磺酸盐等官能团的存在对沥青质性质具有影响,但对沥青质极性及缔合性的影响不明显,杂原子硫不是影响沥青质极性和缔合性的主导因素。     

大庆原油四组分分析及界面性质研究

采用四组分分离法将大庆原油分离成饱和分、芳香分、胶质和沥青质,用红外光谱、相对分子质量和元素分析等方法分析其结构组成,考察了化学结构与界面性质之间的关系.结果表明,大庆原油含饱和分最多,含氧官能团的羧酸类或酚类较多的胶质界面活性最大;相对分子质量较大的沥青质、胶质对油水界面膜的形成和稳定起决定作用;芳香分是油滴表面Zeta电位负值最大的组分.     

钼（VI）配合物催化氧化降解沥青砂中重组分过程研究

针对沥青砂的重组分，探讨了催化氧化沥青砂降解反应体系有机相和残余相中有机物的量随反应时间、催化剂及氧化降解体系的变化规律。结果表明，钼（VI）配合物［(MoO2)(C5H7O2)2］催化剂对沥青砂的氧化降解是非常有效的，催化降解反应与氧化剂、氢质子供体有关。在［(MoO2)( C5H7O2)2］/t-BuOOH/H3PO4体系中，沥青砂有机相中沥青质转化率为10.7%，残余相中沥青质转化率为20%。TLC-FID分析证明，沥青砂中沥青质的减少主要生成胶质和饱和烃，降解产物的得率为11.7%。     

卷烟烟气粒相物芳香核结构的研究

采用电喷雾电离(ESI)傅里叶变换离子回旋共振质谱(FT-ICR MS)以及碰撞诱导解离(CID)的方法对卷烟烟气粒相物的芳香核结构进行了研究。CID可以对质谱中储存的分子离子进行碰撞,将分子离子的烷基侧链打断,而芳香核结构得以保留。利用此方法,本研究对比了卷烟主流烟气和侧流烟气粒相物在CID前后质谱图及化合物类型的变化。在CID之前,在卷烟烟气总共发现了28类化合物:N_1O_(0-6)、N_2O_(0-6)、N_3O_(0-4)、N_4O_(0-2)、O_(1-5)及少量烃类,共近4 600个可鉴别分子组成的谱峰。主流烟气中化合物的氧含量明显高于侧流烟气。在CID之后,谱图中化合物的类型降为6种:N_(1-3)、N_1O_1、O_1和多环芳烃,可鉴别分子组成的谱峰降为近180个。主流烟气和侧流烟气的芳香核结构非常类似,主要为含有一个或两个氮原子的稠环结构,芳环数量为2～4个(由于仪器条件所限,本研究没有给出单环芳香核结构的结果)。     

龙口页岩油中含氧化合物的分析与鉴定

用酸碱分离和萃取色谱分离相结合的方法将龙口页岩油分离为酸性组分、碱性组分和五个中性组分(饱和烃、芳香烃、含氮化合物、含氧化合物1、含氧化合物2)。采用GC-MS和负离子ESI FT-ICR MS鉴定了龙口页岩油中酸性组分、中性组分4和中性组分5中含氧化合物的组成。GC-MS分析结果表明,龙口页岩油酸性组分含氧化合物主要包括苯酚类、茚满酚类、萘酚类、联苯酚类、芴酚类、菲酚类,以及C_5～16烷酸;龙口页岩油中性组分4和中性组分5中含氧化合物主要包括C_9～32脂肪酮和酯类化合物。FT-ICR MS分析结果表明,龙口页岩油中含氧化合物主要有O₁、O₂、O₃、N₁O₁、N₁O₂类化合物,其中,O₁和O₂类化合物种类较多。龙口页岩油重均相对分子质量集中在150～600 Da,说明龙口页岩油是由小分子化合物组成的。其表现出来的某些大分子化合物的性质,是由小分子化合物通过范德华力或氢键聚合在一起而形成的。龙口页岩油中O₁、O₂、O₃类化合物中DBE主要分布在1和4,说明龙口页岩油中O₁、O₂、O₃类化合物不饱和度和缩合度较低,因此,龙口页岩油是生物降解程度较低的油。     

Characterization of complex assemblages of organic acids in geological samples by negative electrospray ionization mass spectrometry using a double‐focusing magnetic sector field mass spectrometer

Four different geological sample types (a crude oil, a crude oil asphaltene, a reservoir core extract and a reservoir core asphaltene) have been characterized by negative ionization electrospray mass spectrometry at low and high mass resolution using a double‐focusing magnetic sector field mass spectrometer. The mass range, shape of the spectra and the signal distribution of the acidic constituents as well as the average molecular weights, the total ion abundance and signal intensity in the spectra were compared for the different sample types. Nominal mass classes have been evaluated and Kendrick mass plots were generated in order to identify homologous series. For the crude oil sample, accurate mass assignments were made by high‐resolution double‐focusing magnetic sector field mass spectrometry (DFMSFMS) and were compared with those obtained by negative ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). With both instrument types, compounds with the molecular composition C_nH_2n+zO₂, among which carboxylic acids predominated, were the main acidic compound class detectable in negative ESI mass spectra. Good agreement was achieved for the double bond class distribution and the carbon number distribution of the O₂ class. In addition, minor compound classes could be identified using FTICRMS. Copyright © 2010 John Wiley & Sons, Ltd.     

Separation and characterization of petroleum asphaltene fractions by ESI FT-ICR MS and UV-vis spectrometer

Using heptane, toluene, and tetrahydrofuran (THF) as eluant, asphaltenes were fractionated into five fractions based on their polarity and solubility. The molecular composition of polar heteroatom species in both asphaltene and its fractions were analyzed by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The application of UV-vis spectrometer in characterizing asphaltene composition and measuring asphaltene concentration was discussed. About 11.9 wt% asphaltene components adsorbed permanently on silica gel in the extrography column after excessive elution with various solvents. In negative FT-ICR MS, the mass spectra show that acidic and neutral nitrogen-containing compounds such as N1 and N1S1 mainly existe in the first three less polar fractions, while oxygen-containing compounds such as O2 , O2S, O2S2 , O3 , and O4 show high relative abundance in more polar fractions. These results suggest oxygen-containing compounds have stronger adsorption ability with silica gel. It was observed that the double bond equivalence (DBE) distribution of N1 class species in the fractions shifted to higher values while the carbon number shifted to smaller numbers as polarity of fractions increased. This indicates that acidic and neutral N1 compounds with longer carbon chain and less aromaticity have less polarity compared with those with shorter carbon chain and stronger aromaticity. UV-vis absorbance indicats that fractions containing the most aromatic and most polar asphaltene have better absorbance at long wavelength, while the fractions that consist of least aromatic and least polar asphatlenes show high absorbance at short wavelength.     

Multivariate Screening Analysis of Water-in-Oil Emulsions in High External Electric Fields as Studied by Means of Dielectric Time Domain Spectroscopy

The effect of crude oil resins with various polar characters on the stability of w/o model emulsions containing asphaltenes is investigated using a mixture design. The resins were extracted using an adsorption-desorption technique. One asphaltene fraction and four different resin fractions from one European crude oil were used. The stabilities are measured using time-domain dielectric spectroscopy in high external electric field. It is found that resins with different polar character have different effects on the emulsion stability. At asphaltene/resin ratios of 1 and 5 : 3 the resins in some cases lead to an emulsion stability higher than that of a similar emulsion stabilized by asphaltenes only, while at low asphaltene/resin ratios ( approximately 1 : 3) the emulsion stability is reduced by the resins. The effect on emulsion stability of combining two different resin fractions depended on the resin types combined as well as the relative amount of resins and asphaltenes. Also, an increase in the stability of some of the emulsions containing resins and asphaltenes for a period of 50-300 min after the emulsification was observed. This time-dependence of emulsion stability is attributed to the mobility of resins at the oil-water interface and the slow buildup of a stabilizing interfacial film consisting of resins and asphaltenes. Copyright 2000 Academic Press.     

胜利超稠油的乳化降黏机理研究

研究了胜利油田滨南超稠油单56-4X4高黏的内在原因。油品性质分析结果表明,影响其高黏度的主要因素有两个:胶质、沥青质的总含量超过30%;有机杂原子O、N、S及过渡金属Ni等形成的配位络合物增加了沥青质分子的内聚力。实验筛选出的降黏剂OP-10对该超稠油降黏率高达99.59%。通过FT-IR、SEM、分子量和偶极矩等分析对比了降黏剂作用前后胶质、沥青质的结构性质变化,结果表明,OP-10使胶质、沥青质的氢键缔合作用减弱,部分拆散沥青质的堆积结构,从而使胶质、沥青质的分子量和偶极矩减小,分析得到降黏剂分子能渗透及分散胶质、沥青质的堆砌聚集体。偏光显微镜对乳状液及蜡晶微观形态的分析表明,降黏剂OP-10使超稠油乳状液由W/O型反相为O/W型而起到降黏作用;使蜡晶的聚集形态由细小均匀转变为尺寸较大的絮凝体,破坏蜡晶的三维网络结构,促进稠油黏度的下降。     

双亲催化剂作用超稠油水热裂解降黏机理研究

合成双亲催化剂,200℃与超稠油反应后,降黏率达96.26%。通过气相色谱仪、元素分析仪、分子量测定仪、红外光谱仪及核磁共振波谱仪对反应前后稠油的物化性质进行分析。结果表明,反应后稠油胶质与沥青质含量减小,稠油分子量下降,沥青质分子量降低幅度最大;稠油及其重质组分的氢碳原子比增加,硫的含量减小。稠油发生水热裂解反应的同时,存在沥青质的聚合反应,沥青质的裂解在降黏反应中起到了关键的作用;双亲催化剂促进了水热裂解反应,同时抑制了聚合反应;双亲型催化降黏剂携带的具有活性催化功能的离子协同高温水作用于分子中的C-S、C-N、C-O、C-C及C=S、C=O、C=N、C=S等键,使其发生系列链的断裂、加氢、开环、成环、脱硫等反应,促进了稠油黏度的降低,稠油及其重质组分的氢碳原子比增加,稠油的品质得到一定程度的改善。     

Petroleum heteroatom compounds in various commercial delayed coking liquids: characterized by FT-ICR MS and GC techniques

Delayed coking is an important petroleum resid conversion process. The processability of coking liquids is known to be dependent on the heteroatom compounds present in the coking liquids. Eight commercial delayed coking liquids were characterized by electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) and gas chromatographic techniques. High relatively abundant heteroatom compounds in the coking liquids were 1–4 aromatic-ring pyridinic nitrogen compounds, carbazoles, benzocarbazoles, phenols, mercaptans, benzothiophenes, dibenzothiophenes, and naphthobenzothiophenes. Coking liquids derived from various feeds had similar compound class types, molecular weight distribution ranges, and double bond equivalents (DBE). However, the concentration of individual compounds and the distribution of DBE versus carbon number of heteroatom compounds varied. A comparison of heteroatom compounds in coker feeds and products revealed the various reaction mechanism of heteroatom compounds occurred during the coking process. The results suggested that molecular-level process models can be developed for optimization of unit operation to obtain desirable products that meet the environmental specifications and quality requirements.     

Mass spectral characterization of tetracyclines by electrospray ionization,H/D exchange,and multiple stage mass spectrometry

Electrospray ionization (ESI) and collisionally induced dissociation (CID) mass spectra were obtained for five tetracyclines and the corresponding compounds in which the labile hydrogens were replaced by deuterium by either gas phase or liquid phase exchange. The number of labile hydrogens, x, could easily be determined from a comparison of ESI spectra obtained with N2 and with ND3 as the nebulizer gas. CID mass spectra were obtained for [M + H]+ and [M - H]- ions and the exchanged analogs, [M(Dx) + D]+ and [M(Dx) - D]- , and produced by ESI using a Sciex API-III(plus) and a Finnigan LCQ ion trap mass spectrometer. Compositions of product ions and mechanisms of decomposition were determined by comparison of the MS(N) spectra of the un-deuterated and deuterated species. Protonated tetracyclines dissociate initially by loss of H2O (D2O) and NH3 (ND3) if there is a tertiary OH at C-6. The loss of H2O (D2O) is the lower energy process. Tetracyclines without the tertiary OH at C-6 lose only NH3 (ND3) initially. MSN experiments showed easily understandable losses of HDO, HN(CH3)2, CH3 - N=CH2, and CO from fragment ions. The major fragment ions do not come from cleavage reactions of the species protonated at the most basic site. Deprotonated tetracyclines had similar CID spectra, with less fragmentation than those observed for the protonated tetracyclines. The lowest energy decomposition paths for the deprotonated tetracyclines are the competitive loss of NH3 (ND3) or HNCO (DNCO). Product ions appear to be formed by charge remote decompositions of species de-protonated at the C-10 phenol.     

Effects of petroleum resins on asphaltene aggregation and water-in-oil emulsion formation

Asphaltenes from four crude oils were fractionated by precipitation in mixtures of heptane and toluene. Solubility profiles generated in the presence of resins (1:1 mass ratio) indicated the onset of asphaltene precipitation occurred at lower toluene volume fractions (0.1–0.2) than without resins. Small-angle neutron scattering (SANS) was performed on solutions of asphaltene fractions in mixtures of heptane and toluene with added resins to determine aggregate sizes. Water-in-oil emulsions of asphaltene–resin solutions were prepared and separated by a centrifuge method to determine the vol.% water resolved. In general, the addition of resins to asphaltenes reduced the aggregate size by disrupting the π–π and polar bonding interactions between asphaltene monomers. Interaction of resins with asphaltenic aggregates rendered the aggregates less interfacially active and thus reduced emulsion stability. The smallest aggregate sizes observed and the weakest emulsion stability at high resin to asphaltene (R/A) ratios presumably corresponded to asphaltenic monomers or small oligomers strongly interacting with resin molecules. It was often observed that, in the absence of resins, the more polar or higher molecular weight asphaltenes were insoluble in solutions of heptane and toluene. The addition of resins dissolved these insolubles and aggregate size by SANS increased until the solubility limit was reached. This corresponded approximately to the point of maximum emulsion stability. Asphaltene chemistry plays a vital role in dictating emulsion stability. The most polar species typically required significantly higher resin concentrations to disrupt asphaltene interactions and completely destabilize emulsions. Aggregation and film formation are likely driven by polar heteroatom interactions, such as hydrogen bonding, which allow asphaltenes to absorb, consolidate, and form cohesive films at the oil–water interface.