金桥工程

我国重烷基苯资源如何更好地精细化利用将在全国第十二次工业表面活性剂研究与开发会议上展开讨论目前中国大陆烷基苯产能及重烷基苯资源状况如下:主要生产厂烷基苯产能(万t/a)2004年重烷基苯产量/t抚顺洗涤剂化学厂20 10343金陵石化烷基苯厂10 6455南京金桐化工有限责任公司10 5237江苏金桐化工有限责任公司10 5355总计40 27390重烷基苯由单烷基苯、二烷基苯、三烷基苯、多烷基苯、多苯烷、烷基茚满、萘满等组成。其芳烷质量分数约占9 5%以上。目前应用多限于生产油品添加剂,如用其合成重烷基苯磺酸盐(润滑油添加剂中增长最快、用量最大的…     

不同磺酸盐样品中活性组分鉴别及对比

以化学驱中常使用的3种不同来源磺酸盐样品为分析对象，将样品中可以产生超低界面张力(<1.0×10^-3mN·m^-1)的活性组分进行分离和鉴别，并对比分析不同磺酸盐中活性组分在结构组成上的差异。结果表明：3种磺酸盐样品中均可分离获得活性组分，活性组分的相对分子质量分布范围主要在380～460之间(不含Na⁺)，以单磺酸盐为主，几乎不含双磺酸盐。磺酸盐结构类型以烷基苯磺酸盐为主时，碳链长度为17～19的磺酸盐是活性组分中发挥界面活性的关键物质；磺酸盐结构类型以环烷基苯磺酸盐为主时，碳链长度分别在11～14、14～17的烷基苯并二环己烷、烷基茚满磺酸盐是活性组分中发挥界面活性的关键物质。对于不同来源磺酸盐而言，平均相对分子质量在417±5、相对分子质量分布区间小于80的组分具有较优界面活性。     

重烷基苯磺酸盐驱油体系配方设计

文章研究了重烷基苯磺酸盐(HABS)/QK-25原油间的界面张力(IFT)。探讨了HABS种类、复配比例和浓度,醇种类和含量,Na2CO3含量和非离子表面活性剂TX-10含量对IFT的影响。结果表明,当金桐2#/南京1#=5∶5时,体系界面张力最低;最优醇类为正丁醇,但醇种类和含量对界面张力影响不显著;TX-10含量、Na2CO3含量和HABS浓度对体系界面张力的影响依次减小。     

直链重烷基苯磺酸盐的驱油能力研究

研究了所合成的各种结构的直链烷基苯磺酸盐单剂及其复配体系在不同碱质量分数情况下对大庆四厂油／水界面张力情况。结果表明；对同一碳链长度的直链烷基苯磺酸盐，带甲基的比带乙基、异丙基和苯环上不带取代基的烷基苯磺酸盐降低界面张力的能力强；同样结构的十六碳链长的烷基苯磺酸盐又较其他碳链长度的烷基苯磺酸盐效果更优；长、短碳链的带甲基的直链烷基苯磺酸盐按一定比例复配，协同效应显著；与支链烷基苯磺酸盐复配后，体系的驱油能力、抗稀释性和抗Ca^2 、Mg^2 能力明显增加。直链与支链按一定比例复配将是烷基苯磺酸盐作为驱油用主剂的发展方向。     

两种重烷基苯磺酸盐的制备及界面性能研究

以苯、C_(16)~C_(19)重烷/烯烃为原料,以氢氟酸为催化剂,在烷基化中试装置上合成了C_(16)~C_(19)重烷基苯;分别以C_(16)~C_(19)重烷基苯、工业重烷基苯(烷基苯装置副产物)为原料,在磺化中试装置上合成了两种重烷基苯磺酸盐(C_(1619)HABS、工业HABS)。经测定,发现二者界面性能相近。     

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.     

ESI-MS法对重烷基苯烃基结构的研究

采用多种分析手段,其中以电喷雾质谱为主的方法研究了重烷基苯的烃基结构。首先通过柱色谱法对重烷基苯进行分离,将其分成了六个族组分。通过各族组分的红外、紫外鉴定,确定它们各自的归属,用电喷雾质谱测定Ⅱ～Ⅴ族组分磺酸盐的相对分子量分布,结合红外、紫外测定的结果及每族物质的不饱和度和通式,推算出了烷基芳烃部分的相对分子质量和烷基的碳数分布。重烷基苯中几个主要成分的碳数分布为:其中二烷基苯的碳数分布在10～25之间,单烷基苯的碳数分布在10～25之间,烷基萘的碳数分布在5～20之间,烷基二联苯的碳数分布在4～19之间。     

重烷基苯磺酸盐复配体系获得超低油水界面张力

将阴离子表面活性剂窄馏分重烷基苯磺酸盐(HABS 3#)与不同类型的表面活性剂复配,并测定复配体系对十二烷/水溶液的界面张力。结果表明,阴离子HABS 3#与非离子脂肪醇聚氧乙烯醚(AEO-9)、两性离子椰油酰胺甜菜碱(CAB-35)、阴离子窄馏分重烷基苯磺酸盐(HABS 1#)复配后,均能在总浓度为0.01%时,在一定的复配比例下,使得油水界面张力降至超低(10~(-3)mN/m),而与阳离子十六烷基三甲基溴化铵(CTAB)复配后,体系对油水界面张力反而升高。获得最低油水界面张力时的复配比例分别为AEO-9含量15%,CAB-35含量40%,HABS 1#含量10%,CTAB含量0。     

重烷基苯磺酸盐复配体系获得超低油水界面张力

将阴离子表面活性剂窄馏分重烷基苯磺酸盐(HABS 3#)与不同类型的表面活性剂复配,并测定复配体系对十二烷/水溶液的界面张力。结果表明,阴离子HABS 3#与非离子脂肪醇聚氧乙烯醚(AEO-9)、两性离子椰油酰胺甜菜碱(CAB-35)、阴离子窄馏分重烷基苯磺酸盐(HABS 1#)复配后,均能在总浓度为0.01%时,在一定的复配比例下,使得油水界面张力降至超低(10^(-3)mN/m),而与阳离子十六烷基三甲基溴化铵(CTAB)复配后,体系对油水界面张力反而升高。获得最低油水界面张力时的复配比例分别为AEO-9含量15%,CAB-35含量40%,HABS 1#含量10%,CTAB含量0。     

二烷基苯磺酸盐表面活性剂的合成、表征及性能研究

据国际能源机构（IEA）预测,2030年我国石油消费量的80％需要依靠进口。在世界原油价格大幅攀升的局势下,大量的石油进口无疑成为我国经济发展的沉重负担,必须加大石油开采力度。目前,大庆油田所用的较好的三次采油用表面活性剂是进口的石油磺酸盐ORS-41,这种表面活性剂价格昂贵,迭2万～2.5万元／t。经分析,这种进口石油磺酸盐的主要成分是各种炕基苯磺酸盐的混合物,其中单烷基苯磺酸盐占18％,二烷基苯磺酸盐占16％,因此,研究二烷基苯磺酸盐表面活性剂的性质,可为三次采油用重烷基苯磺酸盐表面活性剂的复配提供理论依据。为了研究不同结构的二烷基苯磺酸盐分子结构与其表面活性的关系,以烷基苯为原料。经过酰化、格氏反应、碘与红磷还原、磺化、中和等步骤,合成了6种二烷基苯磺酸盐,并用’麒豫对产品进行了表征,用Wilhelmy-Plate法在20℃下测定了二烷基苯磺酸盐水溶液的表面性能,结果表明,苯环在烷基链的位置影响产品的表面张力和表面吸附性能。     

Rapid complexing of oxoacylglycerols with amino acids peptides and aminophospholipids

We prepared model Schiff bases from 2-[9-oxo]nonanoyl glycerol (2-MAG-ALD) and various amino compounds. 2-MAG-ALD was obtained by pancreatic lipase hydrolysis of trioleoyl glycerol and reductive ozonolysis of the resulting 2-monooleoyl glycerol. The reaction products were purified by thin-layer chromatography. Schiff bases were synthesized in greater than 50% yield by reacting 2-MAG-ALD with twofold molar excess of valine, Nα-acetyl-l-lysine methyl ester and the tripeptides glycyl-glycyl-glycine, glycyl-glycyl-histidine, and glycyl-histidyl-lysine in aqueous methanol and with 1-palmitoyl-2-stearoyl glycerophosphoethanolamine (PE) in chloroform.methanol for 16 h at room temperature. Prior to analysis the bases were reduced with sodium cyanoborohydride in methanol for 30 min at 4°C. Reaction products were analyzed by high-performance liquid chromatography/electrospray ionization/mass spectrometry (HPLC/ESI/MS). Reduced Schiff bases of 2-MAG-ALD with PF and amino acids were analyzed by normal-phase HPLC/ESI/MS and those with peptides by reversed-phase HPLC/ESI/MS. Single adducts were obtained in all cases and both the α-amino group of valine and the ε-amino group of Nα-acetyl-l-lysine methyl ester were reactive. Molecular ions of reaction products were the only detected ions in the negative ionization mode, whereas in the positive ion mode sodiated molecular ions were also detected. The present study suggests that 2-MAG-ALD may form Schiff base adducts with amino compounds in other aqueous media, such as the intestinal lumen and in the hydrophobic environment of cell membranes.     

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.     

耐高温重烷基苯磺酸盐的合成及表征

在对萃取技术进行了改进的基础上,以重烷基苯（HAB）为原料,经发烟硫酸磺化、分酸、中和和萃取等步骤,合成了重烷基苯磺酸钠（nABS）表面活性临界剂。利用红外吸收光谱（IR）对HAB和合成的HABS进行了表征,并通过测定HABS的表面张力、泡沫性能和热失重等性能,考察了HABS的热稳定性。结果表明,只用热乙醇萃取的方法简化了以往的萃取步骤,节省原料,操作简单。合成的HABS的临界胶束浓度（cmc）为0．045％,临界胶束浓度下的表面张力（‰）为33．423mN／m。在1500r／min下,起始发泡体积为450mL,半衰期为230min。TGA曲线表明,加热到300％,HABS热失重5．48％。说明这种表面活性剂耐高温性能良好。     

Sensitivity of positive ion mode electrospray ionization mass spectrometry (ESI MS) in the analysis of purine bases in ESI MS and on-line electrochemistry ESI MS (EC/ESI MS)

A cone-shaped MS inlet and on-line electrochemistry (EC) were used to enhance the ionization efficiency in electrospray ionization mass spectrometry (ESI MS) of purine bases. A pathway of positive ion mode ESI may involve oxidation of purine bases, guanine, adenine, xanthine and hypoxanthine, by 1e⁻, 1H⁺ processes. The electrospray process generates dimers of purine bases that are detected in ESI MS as protonated ions, except for xanthine, for which a protonated radical dimer is detected. Thus electrochemical oxidation of purine bases during ESI may generate reactive radicals that can subsequently dimerize. Dimer formation is facilitated in ESI MS when the carrier solution pH is high. The positive ion mode ESI MS ionization is consistent with the reactivity of the bases toward oxidation. Furthermore, the formation of the protonated ions, and Na⁺ and K⁺ adducts of the bases, expected in positive ion ESI MS, are observed. In addition, unusual H-bonding of purine bases guanine and xanthine is confirmed by ESI MS. Application of low EC voltage to the on-line EC cell in EC/ESI MS improves the sensitivity and correlates with the decrease of the intensity of the dimers, possibly as a result of their further oxidation.     

Detection of hydroxy fatty acids in biological samples using capillary gas chromatography in combination with positive and negative chemical ionization mass spectrometry

The most common method for use in the structural analysis of hydroxy fatty acids in biological samples is the gas chromatography-mass spectrometry (GC-MS) analysis of trimethylsilyl ethers of the methyl esters using electron impact ionization. A comparison of electron impact (EI) with chemical ionization mass spectrometry (CI-MS) shows that CI-MS is the superior technique. All ions necessary for structural analysis are observed at sufficiently high levels of intensity when methane or isobutane are used as reactant gases. The molecular weight can be determined from the ion group M+H, M-15 and M+H−90. The ionic series M+H−n×90 enables one to determine the number of hydroxyl groups. The position of the hydroxyl groups can be derived from the fragments of the α-cleavage of the fatty acid chain. The application of heptafluorobutyrates as derivatives for hydroxy fatty acid methyl esters shows advantages in the trace analysis of these compounds. Heptafluorobutyrates exhibit useful mass fragmentation patterns in the positive as well as in the negative CI mode. With methane as the reactant gas, M+H usually is base peak in positive mass spectra. The ionic series M+H−n×214 leads to the number of hydroxy groups in the molecule. In the negative mass spectra, M and M-20 are indicative for the molecular weight. The ion group m/z 213, 194 and 178 at high levels of intensity is typical for heptafluorobutyrates. The advantage of the application of heptafluorobutyrates is the high sensitivity which can be obtained in trace analysis using negative MS. Heptafluorobutyrates of hydroxy fatty acids gave a 20-fold higher response in the negative scan mode compared to that of the positive. The detection limit for heptafluorobutyrates in negative CI-MS was on the order of 1 fg (10⁻¹⁵ g).     

Characterization of polyisobutylene succinic anhydride chemistries using mass spectrometry

Representative Polyisobutylene succinic anhydride (PIBSA) samples have been studied by different MS techniques including Electrospray Ionization Fourier Transform Ion Cyclotron Resonance MS (ESI‐FTMS) (positive and negative modes), Atmospheric Pressure Chemical Ionization Fourier Transform Ion Cyclotron Resonance MS (negative mode), and Matrix‐Assisted Laser Desorption/Ionization Time‐of‐Flight (positive and negative modes). Negative ion ESI‐FTMS produces the best results. Differences between “mono‐succan” and “di‐succan” content can readily be observed. The source of the PIBSA (PIBSA‐I and PIBSA‐II processes) can be easily distinguished and the formation of methyl esters and amide derivatives can provide complementary data. The experiments have demonstrated the capabilities of mass spectrometry to detect and characterize such polymers samples. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

超高效液相色谱-串联质谱法测定化妆品中的9种性激素成分

采用超高效液相色谱-串联质谱（UPLC-MS/MS）检测技术,建立了化妆品中睾酮等9种性激素成分的检测方法。样品经质量分数50%乙腈提取,经流动相（水+乙腈）提取过滤后,采用C18柱（100 mm×2.1 mm×3.0μm）进行分离,用电喷雾离子源、正负离子模式进行扫描,在多反应离子监测模式下检测,基质匹配标准曲线外标法定量。结果表明,9种性激素在5～115 ng/mL范围内线性关系良好,相关系数大于0.999;加标回收率为80%～120%,RSD小于5%(n=3),检出限均低于0.03μg/g。该方法简单、快速、灵敏,能够满足化妆品中睾酮等9种性激素的检测需求。     

高效液相色谱串联质谱法分析水和饮料中13种常见农药

[目的]建立利用液相色谱串联质谱法检测水和6种饮料中13种常见农药的分析方法.[方法]空白检材加入内标和13种农药混标后用乙腈提取,离心后取上清液直接进样分析.液相色谱采用C18色谱柱,流动相用含甲酸铵和甲酸的水、乙腈梯度洗脱,质谱采用电喷雾离子源(ESI),正离子多反应监测(MRM)模式扫描.[结果]13种农药的检测限为0.1～50 μg/L;日内及日间精密度均在15％以下.[结论]方法简便、快速、灵敏、选择性高,可应用于实际案例的分析.