复合驱用重烷基苯磺酸钠的鉴定及高分辨质谱分析

采用傅里叶变换红外光谱(FT-IR)分析和高效液相色谱(HPLC)分析相互佐证的方法快速准确地鉴定常用表面活性剂的类型。采用负离子电喷雾-傅里叶变换离子回旋共振高分辨质谱(ESI-FTMS)及傅里叶变换红外光谱仪(FT-IR)分析了驱油用重烷基苯磺酸钠(HABS)的相对分子质量分布及分子结构。结果表明,高分辨质谱分析得到HABS的相对分子质量分布为320~500;其分子通式为CnH2n-7SO3Na,碳数分布主要为C18~C24,其中C1 9含量最高,其次为C23、C18和C22。HABS红外光谱图在1 183.54、1 039.34 cm-1处有典型特征吸收峰,并且在1 183.54 cm-1和831.69 cm-1有较强的吸收,可知HABS主要为1,4-二取代苯环结构。     

重烷基苯磺酸盐组分分析

用电喷雾电离质谱(ESI/MS)法,分别在正、负离子模式下测定了几种重烷基苯磺酸盐(HABS)的组成.在负离子模式下,各组分主要以[M-Na]的形式被检测到,在正离子模式下,各组分主要以[M Na] 的形式被检测到.结果表明,两种模式分析结果基本相同,但正离子的响应灵敏度小于负离子的.谱图分析结果表明,HABS主要成分是一系列不同碳链长度的单烷基苯磺酸盐.金桐2#、金桐1#、南京1#重烷基苯磺酸盐以及ABS的最大组分是碳链长度分别为C17、C13、C13、C12的单烷基苯磺酸盐.根据谱图还可求出各组分的相对含量和摩尔质量,并据此计算出HABS的平均摩尔质量,其值小于由两相滴定法测定的结果.     

高效液相色谱法和质谱法分析重烷基苯磺酸钠的族组成

采用电喷雾质谱法得到了重烷基苯磺酸钠的相对分子质量分布,经过对质谱图解析确定了各组峰的族组成归属和烷基碳数分布;用高效液相色谱使重烷基苯磺酸钠各族组成得到分离,并结合质谱分析结果和族组成的极性规律判断出各组峰的族组成归属.用面积归一化法得出A段和B段重烷基苯磺酸钠的各族组成的质量分数,相对标准偏差0.58%～4.72%,各族组成质量浓度与峰面积呈良好的线性关系,证明了用面积归一化法的可行性.     

含硅烃基氯化锡的合成及其结构表征

用四（烃硅基亚甲基）锡和四氯化锡按不同的物质的量比进行反应,合成了相应的三烃基一氯化锡、二烃基二氯化锡和一烃基三氯化锡。讨论了影响反应的主要因素,并使用高效液相色谱对反应的进程进行跟踪检测。通过^1HNMR和元素分析,确定了这些化合物的结构。生物活性试验的初步结果显示,含硅二烃基二氯化锡对肺癌细胞SPC-A-1具有较好的体外抗癌活性。     

红外ATR光谱法与紫外光谱法研究高聚物老化

用红外ATR光谱法和紫外光谱法研究了聚丙烯酸酯类和丙烯酸丁酯—苯乙烯共聚物的老化过程。结果表明,这两种方法能有效地研究高聚物老化的动力学过程,在光、热、氧的作用下,高聚物的侧酯基和部分主链断裂,聚苯乙烯成分能延缓侧酯基的断裂。由试样经耐候试验机及氮分子激光两种老化处理的结果表明,后者导致高聚物的光降解速率比前者高9个数量级,因此,氮分子激光老化是一种研究高聚物光降解的好方法。     

重烷基苯磺酸的品质改善研究

采用硅胶吸附法和碳酸钡中和法,脱除重烷基苯磺酸（HABSA）中的硫酸。以石油醚和乙醇为洗脱剂,采用硅胶层析柱法洗脱分离HABSA与重烷基苯（HAB）。实验结果表明：硅胶吸附法虽然能脱除一定量的硫酸,但其HABSA回收效果差;与之相反,碳酸钡中和法可脱除70%以上的硫酸,且保持高的HABSA回收率。实验结果也表明,硅胶柱层析法是一种快速简便且高效的分析或工业分离HAB与HABSA的方法。碳酸钡中和法和硅胶柱层析法的联合运用可有效脱除HABSA中的杂质,达到品质改善的目的。     

重烷苯中二烷基苯和茚满萘满的分离与鉴定

通过柱层析的方法将重烷基苯大致分成了6个族组分,重点对第Ⅱ族组分、Ⅲ族组分进行了分析和鉴定。通过红外光谱的鉴定,大致确定第Ⅱ族组分主要为二烷基苯,第Ⅲ族组分主要为单烷基苯和少量的二烷基茚满、萘满(DT)。然后用紫外法求得了第Ⅱ族组分中邻、间二烷基苯之和与对二烷基苯的质量比约为1：4．09。第Ⅲ族组分中DTI的质量分数约为7．23％,DTI在重烷基苯中所占的质量分数约1．22％。     

重烷基苯磺酸盐表面活性剂对石油馏分的胶束增溶研究

表面活性剂提高采收率（EOR）的主要机制一直被认为是通过形成中间相微乳液在油和剥落流体之间的超低界面张力（IFT）。然而,现场试验发现油可以通过低浓缩表面活性剂驱油而不产生微乳液。本文选择了一种广泛使用的EOR表面活性剂,重烷基苯磺酸盐(HABS)来研究其对石油馏分、烷烃和芳烃的胶束增溶行为,利用紫外-可见光谱、动态光散射、透射电子显微镜、小角中子散射（SANS）和荧光显微镜。增加表面活性剂浓度导致增溶能力增加,胶束尺寸随着添加剂的加入而增加,伴随着最大前后外观从透明转变为不透明增溶能力。烷烃位于胶束核心,而芳烃位于栅栏层。一旦达到最大增溶能力,从胶束到乳液的演变已被证明是分散相突变。这些发现为胶束增溶对表面活性剂EOR过程的贡献提供了支持。     

煤化工产品为烯烃原料生产重烷基苯的研究

以煤化工产品为烯烃原料,通过与苯的烷基化反应,并在氢氟酸催化剂的作用下合成了重烷基苯。考察反应温度、压力和时间、苯烯摩尔比及催化剂用量对反应的影响。结果表明,在反应温度90℃,压力0.5 MPa,反应3.5 h,苯烯摩尔比8.33,催化剂用量9%条件下,液体收率84.3%,重烷基苯、饱和烷烃和副产物的产率分别为96.2%,17.4%和5.8%,82.4%的苯回收率说明苯可以循环利用。由此证明以煤化工产品为烯烃替代原料,与苯通过烷基化生成重烷基苯反应的可行性。     

Improvement on acid pyrolysis method for alkyl homolog and phenyl isomer distribution of alkylbenzene sulfonates

An acid pyrolysis method developed by H.L. Lew in 1967 has been further investigated and improved. Alkylbenzene sulfonates are pyrolyzed with phosphoric acid. This gives quantitative desulfonation. The resulting alkylbenzenes are online analyzed by gas chromatography. Lew's approach replaced the time-consuming reflux desulfonation gas chromatography methodology. While greatly reducing turnaround time, phosphoric acid used for acid pyrolysis in Lew's method resulted in deterioration of the gas chromatography column stationary phase and also corrosion of the pyrolysis tube. Improvement in these areas was studied. Column deterioration can be eliminated by using an acid trap, and pyrolysis tube corrosion can be minimized by using quartz wool to prevent phosphoric acid sputtering in the pyrolyzer. The method discussed in this paper produces results totally comparable with the reflux desulfonation gas chromatography and Lew's methods.     

重烷基苯磺酸合成超高碱值磺酸钙的研究

采用南京重烷基苯磺酸-甲醇-丁醇-氢氧化钙工艺,一步法制备磺酸钙。通过在反应过程中分别加入促进剂烷基酚钙和甲酸以及分批次加入氢氧化钙,中和反应最佳温度70-80℃,反应时间10 min,碳酸化反应最佳温度50℃。最后可制得总碱值(TBN)超过400 mg KOH/g的超高碱值磺酸钙产品,所得产品的理化指标、模拟评定结果都达到了国内外同类产品水平。     

碱对重烷基苯磺酸盐和无酸油相间界面张力的影响

以不含酸性物质的脱酸直馏柴油作为油相,研究了NaOH对重烷基苯磺酸盐/油体系界面张力的影响.结果表明,NaOH与原油中的石油酸反应生成自表面活性剂并不是油/水界面张力降低的主控因素.NaOH可以改变重烷基苯磺酸盐体系的最小烷烃碳数,从而影响界面张力,使界面张力达到超值.     

两种油溶性磺酸盐与重烷基苯磺酸盐复配体系的界面性能

以十二烷为油相,比较了二烷基苯磺酸盐（DAS）与α-烯烃磺酸钠（C2024AOS）两种不同结构的油溶性表面活性剂与重烷基苯磺酸盐（HABS）复配体系的界面张力.结果表明,具有苯环结构的DAS和直链型C2024AOS本身界面张力均较高.但与HABS/LAS二元体系复配之后,DAS与HABS之间在降低界面张力方面存在明显的协同效应（固定HABS与DAS质量比为3∶1,LAS含量为20％时,DAS/HABS/LAS三元体系界面张力可以达到3.28×10-3 mN/m;固定LAS含量为30％,DAS与HABS质量比为1∶1时,界面张力可以达到1.85×10-3 mN/m）,而C2024AOS与HABS之间不存在明显的协同效应.     

Chlorination of irradiated polyethylene single crystals: 1: Analysis of alkyl radical decay kinetics

The chlorination of electron beam-irradiated polyethylene (PE) single crystals was studied for a range of irradiation doses, temperatures and chlorine interaction times. The results of this work are presented in two parts: (1) Electron paramagnetic resonance (e.p.r.) analysis of irradiated PE without chlorination and (2) characterization of chlorine uptake in irradiated PE by use of X-ray energy of spectroscopy (XES) and electron spectroscopy for chemical analysis (e.s.c.a.). Spectra were obtained for 75 – 600 Mrad doses over 136 to 333 K temperature range. Alkyl radical concentrations and decay kinetics were derived from e.p.r. spectra and provided a basis for the chlorination analysis in Part II. A first-order alkyl radical decay constant of 4.3 × 10^?5s^?1 at 298 K was determined in agreement with previous research. Alkyl radical migration was modelled as a one, two or three-dimensional unsteady-state Fickian diffusion process. E.p.r. alkyl radical concentration data was used to estimate alkyl radical diffusion coefficients yielding values of 10 to 4 × 10^?18cm^2?1 at 298 K for the three models evaluated, respectively. These values are consistent with a diffusivity estimated by Seguchi and Tamura based on a 3-D model. A three-dimensional diffusion model seems to be the most realistic since it permits a zig-zag radical trajectory due to the staggered arrangement of ?CH₂- units in crystalline PE. Although a 3-D model would allow diffusion in all directions, it is still consistent with the observation that consecutive migration steps are most likely intermolecular.     

石油羧酸盐与重烷基苯磺酸盐复配体系性能研究

通过石油羧酸盐与重烷基苯磺酸盐复配后的体系在弱碱（Na₂CO₃）条件下分别与大庆采油三厂和大庆采油六厂的油水发生作用,对体系的界面张力性能和模拟驱油效率进行检测,同时进行了体系界面张力稳定性试验。结果表明,该复配体系具有优良的界面张力,模拟驱油效率达20%左右,稳定性良好,并且可大幅度提高原油采收率。     

Study on molecular structure and association behaviour of heavy subfractions of vacuum residue by an improved separation method

Vacuum residue (VR) is the most complex component of crude oil. Due to the special structure of heavy subfractions, physical aggregation and chemical coking reactions easily occur through molecular force, which affects the normal processing. Therefore, in-depth study and analysis of their composition, structure and association behaviours are particularly important. In view of the shortcomings of the traditional separation method in terms of separation accuracy, mainly including the purification of asphaltenes and the poor separation of resins. In this paper, a reasonably improved separation method is adopted, and the multi-stage asphaltene extraction and the multi-stage silica gel coupling separation are carried out innovatively, which achieves a high yield of 99% while ensuring the separation accuracy. The samples were characterized by elemental analysis (EA), gel permeation chromatography (GPC), Fourier-transform infrared spectroscopy (FT-IR), hydrogen nuclear magnetic resonance spectroscopy (¹H-NMR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscope (SEM) to study their structural characteristics and association behaviours. The results show that the main forms of heteroatoms in asphaltene and resin surface are C-O-C, C-OH, pyridine, pyrrole, and thiophene, and the content of these substances is higher in asphaltene. Compared with resins, asphaltenes contain a more peri-condensed aromatic structure and shorter alkyl substituent side chains. By studying the hydrogen bond and acid–base interaction, it is found that asphaltene and resin mainly contain OH-OH, OH-π, and OH-ether O, of which the content of OH-OH is the highest. Asphaltene and resin have more neutral and basic substances. These hydrogen bonds and acid–base interactions caused by heteroatoms are the main forces for the association of the heavy subfractions of the VR.     

烷基多苷的复配性能研究

用APG 0810、APG 0814和APG 1214同AES或BS 12进行复配,测定了复配样品的表面张力、润湿力、乳化力及发泡性能,并对复配规律进行了讨论。结果表明:APG+AES或APG+BS 12的表面张力呈现明显的协同效应;复配物中,APG 0814或APG 1214的质量分数为20%,就可使体系的表面张力由AES的39.9mN/m降至36.2mN/m;APG+BS 12或APG+AES两种复配体系的润湿力都显示协同效应,前者优于后者,以APG 0810+BS 12为最佳,复配物中当APG 0810质量分数为20%时,可将BS 12的润湿时间从11.2s降至6.2s;APG+AES体系的乳化力具有负的协同效应,而APG+BS 12体系显示正的协同效应,以APG 0810+BS 12为佳;APG+AES、APG+BS 12复配体系的发泡性能都显示协同效应,后者优于前者,尤以APG 1214+BS 12为佳,在复配物中当APG 1214的质量分数为20%时,体系的初始泡沫体积达494mL,5min时的泡沫达459mL。