羟基和酯基型Gemini双季铵盐表面活性剂在煤沥青表面的润湿特性

以自制的羟基和酯基型Gemini双季铵盐表面活性剂为研究对象,在考察其表面活性的基础上,进一步研究了表面活性剂在煤沥青表面的润湿性。研究表明,羟基型Gemini表面活性剂在煤沥青表面的接触角随疏水链长度的增长呈先减小后增大趋势,其中C₁₂-OH在煤沥青表面的润湿效果最好;对于m-n-m酯基型Gemini表面活性剂而言,接触角随疏水链长度的增长而降低。当疏水链长度一定时,m-6-m在煤沥青表面的润湿效果比m-2-m好。在一定浓度范围内,C₁₀-OH、C₁₂-OH和12-2-123种Gemini表面活性剂的表面张力与其在煤沥青表面黏附张力呈线性关系。煤沥青表面的Zeta电位随Gemini表面活性剂浓度的增大呈先增大后趋于平稳的趋势。     

含萘酰亚胺和烷基疏水基的新型表面活性剂合成及性能

为获得高效多功能表面活性剂,设计并合成了一系列萘酰亚胺和长链烷基为疏水基的新型季铵盐阳离子表面活性剂(C_nNDA,n=10,12,14,16代表长链烷基链长),并利用红外光谱(FT-IR)、核磁氢谱(¹H NMR)、核磁碳谱(¹³C NMR)和质谱(HRMS)对其结构进行了表征。研究了C_nNDA的表面活性、胶束性质、泡沫及抗菌性能。结果表明,C_nNDA具有优异的表面活性和泡沫性能。当疏水烷基链长碳数从10增加到16,其cmc值从1.01降至0.026 mmol/L;0.10 g/L的C₁₄NDA水溶液的泡沫半衰期可达16 h。同时C_nNDA具有良好的抗菌活性,C₁₆NDA对大肠杆菌和金黄色葡萄球菌的最低杀菌质量浓度分别为3.0和1.2μg/mL。另外,¹H NMR和荧光光谱研究表明,C_nNDA能够形成分子间氢键,且萘酰亚胺基团间形成了π-π堆积。C_n     

C16格尔伯特醇聚氧烷烯醚硫酸盐的制备及其界面性能研究

用C₁₆格尔伯特醇经共聚加成环氧丙烷(PO)和环氧乙烷(EO),再经氨基磺酸硫酸化合成了一种支链烷基醇醚硫酸盐(C₁₆GA-PES)。这种新型阴-非复合型表面活性剂具有优良的水溶性、耐盐性和表面活性。45℃下溶于大庆地层水,单独即可将大庆轻质原油/地层水界面张力降至超低;对稍重质的大庆三类油层油,使用该表面活性剂与少量亲油性更强的表面活性剂混合,亦可将界面张力降至超低。这种新型结构表面活性剂吸附在油/水界面形成的单分子层具有从强亲油到弱亲油-弱亲水再到强亲水的过渡结构,而双烷基链又赋予单分子层较高的烷基链密度,从而增强了单分子层与油分子的相互作用,易于将原油/水界面张力降至超低。与相应的嵌段中间体相比,共聚所得非离子中间体黏度显著降低,便于管道输送并且有利于采用SO₃气体降膜式硫酸化工艺制备硫酸盐。     

脂肪醇聚氧丙烯聚氧乙烯醚硫酸盐性能研究

研究了Extended表面活性剂C₁₂₁₄脂肪醇聚氧丙烯聚氧乙烯醚硫酸盐C₁₂₁₄P₁₂E₂S的物化性能,包括平衡表面张力、动态表面张力、泡沫性能、接触角、润湿性能以及乳化性能,并且与C₁₂₁₄脂肪醇聚氧乙烯醚硫酸钠(AE₂S)进行了比较,探究了PO基团的引入对表面活性剂性能的影响。结果表明,C₁₂₁₄P₁₂E₂S的临界胶束浓度(cmc)低于AE₂S,cmc时的表面张力高于AE₂S;C₁₂₁₄P₁₂E₂S降低表面张力速度高于AE₂S;C₁₂₁₄P₁₂E₂S的泡沫体积小于AE₂S;C₁₂₁₄P₁₂E₂S的润湿时间...     

可断键均三嗪脂肪磺酸盐型表面活性剂的合成与表面活性

以脂肪胺、三聚氯氰、氨基乙磺酸为原料合成了4种不同碳链长度均三嗪脂肪磺酸盐型表面活性剂[2-脂肪胺基-4-(2-磺基乙基)胺基-6-氯-1,3,5-均三嗪]。用元素分析、1HNMR、FTIR对中间体和目标产物的结构进行了表征。测定了25℃时4种表面活性剂的表面张力,研究了它们的表面活性。结果表明,疏水链长为C14时,该类表面活性剂的临界胶束浓度(cmc)和cmc下的表面张力(γcmc)达到最低值分别为:3.58×10-5mol/L和32.53 mN/m。与普通表面活性剂C12-LAS相比,疏水链长为C12~C16的该类表面活性剂的cmc均比C12-LAS低1~2个数量级,即它们降低水溶液表面张力的效率比C12-LAS高;疏水链长为C8、C12和C16时,其在溶液表面的饱和吸附量均比C12-LAS小,饱和吸附面积比C12-LAS大;疏水链长为C14时则相反。     

琥珀酸酯磺酸盐物化特性及其与甜菜碱复配体系界面性能（英文）

为满足低渗油藏注低矿化水开采原油的需要，研究了系列琥珀酸异酯磺酸盐表面活性剂(C₁₂EO₆-C_nMS,n=10,12,14和16)的泡沫特性以及溶液的表/界面活性，并研究了C₁₂EO₆-C_nMS与甜菜碱表面活性剂混合物的界面性能，得到了表面活性剂体系的最小烷烃碳数(N_min)。实验结果表明，C₁₂EO₆-C_nMS表面活性剂具有低泡性。C₁₂EO₆-C_nMS表面活性剂的临界胶束浓度(cmc)随着其脂肪醇碳链长度的增加而减小。同时，无机盐的加入使得C₁₂EO₆-C_nMS表面活性剂的cmc进一步降低，并且其降低程度随着无机盐浓度的增加而增大。脂肪醇碳链长度为10的C₁₂EO₆-C₁₀     

预成型高岭土干胶转化合成NaY型分子筛

通过干胶转化法制备了整体式NaY分子筛,采用XRD、SEM及XRF分析表征原料及产物,系统考察了合成体系的n（SiO₂）/n（Al₂O₃）、n（Na₂O）/n（SiO₂）、水量、晶化温度和晶化时间对整体式NaY分子筛制备的影响。结果表明,合成体系n（SiO₂）/n（Al₂O₃）=7.5时,骨架硅铝比（二氧化硅与氧化铝物质的量比）最大为6.12;n（Na₂O）/n（SiO₂）逐渐增大,整体式NaY分子筛结晶度逐渐升高,当n（Na₂O）/n（SiO₂）增至0.35时,会导致P型分子筛的生成;晶化温度从90 ℃逐渐增至120 ℃时,整体式NaY分子筛结晶度也随之升高;在110 ℃下晶化20 h,产物的结晶度达到98%并趋于稳定。干胶转化制备整体式NaY分子筛必须有水的参与,n（H₂O）/n（SiO₂）为4.2左右对反应物的成型及整体式NaY分子筛的晶化较为适宜。     

混合表面活性剂的表面活性与链长相关性

研究了一系列疏水链长度不同的混合表面活性剂的表面活性。总结了表面活性参数随表面活性剂疏水基链长变化的规律。混合表面活性剂形成胶团的能力和降低表面张力的效率主要取决于两表面活性剂的碳原子数,而降低水表面张力的能力则受总碳原子数影响不大。固定总碳原子数时,两表面活性剂链长相差越大临界胶团浓度越小,降低表面张力的效率越高,而降低表面张力的能力却反而越差。     

磺酸盐Gemini表面活性剂的合成与表面活性

以单链表面活性剂SCT及1,3-丙二胺为原料,通过一步取代反应,合成了4种含三嗪环的磺酸盐Gemini型表面活性剂Cn-3-Cn(n=6,8,12,14),测定了25℃时4种表面活性剂的临界胶束浓度CMC。结果表明,Cn-3-Cn的临界胶束浓度CMC均随着疏水烷基链长度的增加而减小,C12-3-C12(实际疏水基碳原子数为14)达到最小值7.23×10-5mol/L,当实际疏水基中碳原子数增加到16时,CMC有所增加。同传统单烷基离子型表面活性剂十二烷基硫酸钠(SDS)相比,该类表面活性剂的CMC值低1～2个数量级,显示出很高的表面活性。此外,表面张力随着疏水烷基链长度的增加呈现先减小后增大的趋势,最低γcmc为35.48 mN/m。     

双模板剂法SAPO-34分子筛的合成及其MTO催化性能调变

以四乙基氢氧化铵（TEAOH）和二乙铵（DEA）为混合模板剂，在低投料硅铝比[n (SiO₂) ∶n (Al₂O₃)=0.2]及低模板剂用量[n (模板剂) ∶n (Al₂O₃)=1.9]下，考察了两种模板剂比例的调变对合成的SAPO-34分子筛物化性能及其催化甲醇制烯烃反应（MTO）催化性能的影响。研究发现，通过改变两种模板剂比例，可以明显调变SAPO-34分子筛晶粒尺寸、硅分布（晶粒表面和体相的硅分布）、硅原子的配位环境，从而影响其MTO催化反应的效果。在低模板剂用量制备的SAPO-34产品中，晶粒尺寸是影响其催化寿命的最主要因素，小晶粒分子筛因其扩散路径短有利于延长催化寿命。此外，硅分布也是影响催化寿命的因素之一，表面富硅的分子筛导致外表面积炭程度大于晶内积炭，积炭趋势由外向内发展，加速分子筛“假性”失活。硅分布还影响MTO反应产物分布，表面富硅分子筛外表面更易发生非择形催化，显著提高C₄～C₆等产物的选择性，不利于目标产物双烯（乙烯+丙烯）选择性的提高。     

富勒烯对甲基苯胺衍生物的合成及其对硝化棉安定性的影响

以富勒烯(C₆₀)、溴素(Br₂)、八溴富勒烯(C₆₀Br₈)及对甲基苯胺(C₇H₉N)为原料,经两步反应合成了富勒烯对甲基苯胺衍生物C₆₀(NC₆H₄CH₃)_n;采用核磁共振碳谱(¹³C-NMR)、质谱(MS)、X射线光电子能谱(XPS)、傅里叶变换红外光谱仪(FT-IR)以及紫外-可见光分光光度计(UV-Vis)对合成得到的富勒烯对甲基苯胺衍生物结构进行了表征;采用差热分析(DTA)、真空安定性测试(VST)、热重分析(TGA)、甲基紫实验等热分析方法,并结合电子顺磁共振波谱法研究了富勒烯对甲基苯胺衍生物与硝化棉的相互作用规律和机理。结果表明,富勒烯对甲基苯胺衍生物将甲基紫试纸的变色时间由56min延长至95min;将单位质量硝化棉热分解释放的气体量由2.67mL/g降至1.46mL/g;将硝化棉的热失重率由17.17%降至5.46%;当富勒烯对甲基苯胺衍生物的质量浓度为0.76g/L时,其对氮氧自由基的清除率达到50%。表明富勒烯对甲基苯胺衍生物提高了硝化棉的安定性,且安定性能明显优于传统安定剂DPA和C2。     

Chemical Effects of CO2 Concentration on Soot Formation in Jet-stirred/Plug-flow Reactor

Soot formation was investigated numerically with CO2 addition in a jet-stirred/plug-flow reactor （JSR/PFR） C2H4/OJN2 reactor （C/O ratio of 2.2） at atmospheric pressure. An updated Kazakov mechanism empha- sizes the effect of the O2/CO2 atmosphere instead of an O2/N2 one in the premixed flame. The soot formation was taken into account in the JSR/PFR for C2H4/O2/N2. The effects of CO2 addition on soot formation in different C2H4/O2/CO2/N2 atmospheres were studied, with special emphasis on the chemical effect. The simulation shows that the endothermic reaction CO2 ＋ H - CO ＋ OH is responsible of the reduction of hydrocarbon intermediates in the CO2 added combustion through the supplementary formation of hydroxyl radicals. The competition of CO2 for H radical through the above forward reaction with the single most important chain branching reaction H ＋ O2, ＇ O ＋ OH reduces significantly the fuel burning rate. The chemical effects of CO2 cause a significant increase in residence time and mole fractions of CO and OH, significant decreases in some intermediates （H, C2H2）, polycyclic aromatic hydrocarbons （PAHs, C6H6 and CI6H10, etc.） and soot volume fraction. The CO2 addition will leads to a decrease by only about 5% to 20% of the maximum mole fractions of some C3 to Clo hydrocarbon intermediates. The sensitivity analysis and reaction-path analysis results show that C2H4 reaction path and products are altered due to the CO2 addition.     

氰化尾渣矿浆电解液中铁离子的萃取富集

采用二(2-乙基己基)磷酸酯(P204)-磺化煤油萃取体系从高硫酸氰化尾渣矿浆电解液中富集铁离子,重点研究了P204浓度、相比(O/A)、振荡时间、振荡频率及温度等对Fe³⁺萃取率的影响及其萃取过程。研究表明,在P204体积分数为25%、电解液pH为1.5、温度25℃、O/A=1∶1、振荡时间10 min、振荡频率180r/min的条件下,电解液中Fe³⁺的单级萃取率可达97.73%以上,饱和萃取容量可达到21.57g/L。Fe³⁺在有机相中的萃取富集主要归因于其与P204分子结构中羟基的阳离子交换反应以及磷酰基的配位反应,形成的配合物为FeSO₄A(HA)₃与FeA₃(HA)₃。在草酸1mol/L、O/A=1∶1、振荡时间10min、振荡频率190r/min的条件下,负载有机相中Fe³⁺的单级反萃率可达82.64%以上,反萃液中铁主要以[Fe(C₂O₄)_3<...     

OCM in a fixed-bed reactor: limits and perspectives

The oxidative coupling of methane (OCM) over a La₂O₃/CaO catalyst was studied in a poly tropic fixed-bed reactor (I.D. = 15 mm, W/F= 0.15 g · s/ml). Reaction conditions for stable operation were determined. (1) A minimum inlet temperature of 580°C was necessary to initiate the reaction. (2) The maximum hot-spot temperature of 1000°C limited the highest oxygen inlet concentration to 20%. The temperature gradients in the bed amounted to 250 K. The influence of the reaction conditions on the C₂₊ selectivity was investigated by testing the effects of temperature (T_inlet = 580–860°C), oxygen concentration (C_O2 = 5–20%) and particle diameter (d_p = 250–350 μm, and pellets of h_p = 4 mm and d_p = 4 mm). The C₂₊ selectivity ran through a maximum with increasing temperature and decreased with rising inlet oxygen concentration. Mass-transfer limitations, which occurred when applying pellets, resulted in a drop of C₂₊ selectivity. Highest C₂₊ yields amounted to 15.5% (X_CH4 = 31%, S ₂₊ = 51%). Distributed feed of oxygen was tested as a means to cope with the high temperature gradients and to increase C₂₊. selectivity. Upon applying this mode of operation, oxygen concentrations up to 30% could be converted. However, no improvement of C₂₊ selectivity and yield compared to cofeed operation was achieved.     

Synthesis of C2H4 by partial oxidation of CH4 over LiCl/NiO

Alkali halide added transition metal oxides produced ethylene selectively in oxidative coupling of methane. The role of alkali halides has been investigated for LiCl-added NiO (LiCl/NiO). In the absence of LiCl the reaction over NiO produced only carbon oxides (CO₂ + CO). However, addition of LiCl drastically improved the yield of C₂ compounds (C₂H₆ + C₂H₄). One of the roles of LiCl is to inhibit the catalytic activity of the host NiO for deep oxidation of CH₄. The reaction catalyzed by the LiCl/NiO proceeds stepwise from CH₄ to C₂H₄ through C₂H₆ (2CH₄ → C₂H₆ → C₂H₄). The study on the oxidation of C₂H₆ over the LiCl/NiO showed that the oxidative dehydrogenation of C₂H₆ to C₂H₄ occurs very selectively, which is the main reason why partial oxidation of CH₄ over LiCl/NiO gives C₂H₄ quite selectively. The other role of LiCl is to prevent the host oxide (NiO) from being reduced by CH₄. The catalyst model under working conditions was suggested to be the NiO covered with molten LiCl. XPS studies suggested that the catalytically active species on the LiCl/NiO is a surface compound oxide which has higher valent nickel cations (Ni^(2+δ)+ or Ni³⁺). The catalyst was deactivated at the temperatures>973 K due to vaporization of LiCl and consumption of chlorine during reaction. The kinetic and CH₄---CD₄ exchange studies suggested that the rate-determining step of the reaction is the abstraction of H from the vibrationally excited methane by the molecular oxygen adsorbed on the surface compound oxide.     

Approach by zeta-potential measurement on the surface change of hydrating C3S

The adsorption of Ca²⁺ on C₃S surface and the formation of C-S-H in the induction period of C₃S hydration were investigated by measuring zeta-potential, heat evolution change and by analyzing dissolved ions. Within 20 minutes, the dissolution of Ca²⁺ and silicate ions and the adsorption of Ca²⁺ on the surface of C₃S were alternately repeated. In the induction period (20 50 minutes), Ca²⁺ was adsorbed fairly strongly on C₃S surface giving positive zeta-potentials and the dissolution stopped for a time. In the hydration between 60 and 140 minutes, the C-S-H gel proceeded to crystallize and Ca²⁺ began to dissolve again, giving negative zeta-potentials by Si-O⁻. After 140 minutes, the second evolution was caused by the crystallization of C-S-H and Ca(OH)₂.     

载体对铁基整体式催化剂上丙烯催化还原NO的影响

以Al₂O₃、SiO₂和TiO₂为载体,采用凝胶-溶胶法和浸渍法制备铁基堇青石整体式催化剂,并对其丙烯选择性催化还原NO性能进行了研究。通过N₂物理吸附/脱附、XRD、SEM、H₂-TPR、Py-FTIR和原位DRIFTS技术对催化剂进行了表征。不同载体对催化剂的表面酸性、氧化还原性能、比表面积和表面形貌有显著影响,从而导致丙烯还原NO的催化活性明显差异。C₃H₆-SCR的催化活性按Fe/Al₂O₃/CM > Fe/SiO₂/CM > Fe/TiO₂/CM依次降低。在450℃的有氧条件下,在Fe/Al₂O₃/CM上催化C₃H₆还原NO效率可达到100%,这主要是因为较好的氧化还原性能和丰富的Lewis酸性位。基于原位的DRIFTS研究表明,Lewis酸性位的增加有助于促进形成NO₂/NO₃^-物种,从而提高了催化性能。     

2,6-二甲氧基苯酚在1-丁基-3-甲基咪唑四氟硼酸盐水溶液中溶解行为的红外光谱分析

利用衰减全反射红外光谱(ATR-IR)和二维相关红外技术研究2, 6-二甲氧基苯酚(2, 6-DMP)在1-丁基-3-甲基咪唑四氟硼酸盐([C₄mim]BF₄)水溶液(离子液体摩尔分数x_IL=1.0～0.02)中的溶解行为。随着水量增大, 2, 6-DMP溶解度先增大而后急剧减小, 对应的x_IL阈值为0.1。2, 6-DMP与[C₄mim]BF₄之间存在强相互作用, 2, 6-DMP上的甲氧基是重要作用位点之一;当少量的水加入[C₄mim]BF₄(x_IL=0.1～1.0), 致密的离子簇结构被解离, 2, 6-DMP容易与[C₄mim]BF₄作用, 溶解度增大;随着大量水加入(0.02IL<0.1), 离子簇完全解离为大分子水簇包围的离子对, 憎水的2, 6-DMP与[C₄mim]BF₄作用困难, 溶解度减小。这种由于水量改变引起的[C₄mim]BF₄水溶液微观结构变化影响2, 6-DMP溶解行为。     

The homogeneous gas phase oxidation of methane and the retarding effect of basic/inert surfaces

The homogeneous gas phase O₂-based oxidation of methane was studied in the temperature range, from 500°C to 750°C at methane partial pressures ranging from 3 bar to 40 bar. At the lower end of the temperature range methanol, formaldehyde, and CO represent the main products, while at temperatures exceeding 650° C/C-coupled products, C₂H₆, C₂H₄, C₃H₆ and C₃H₈ predominate. The change in selectivity as function of the temperature is well explained based on a free radical chain mechanism with degenerate branching, initiated by the gas phase reaction, CH₄+O₂→CH^·₃+HO^·₂. Bringing in basic catalysts known to catalyze the system at low methane partial pressures, in the reactor e.g. SrCO₃, BaCO₃, and 7% Li/MgO resulted in reduced rates of methane and oxygen conversions, and only minor changes in the selectivity to coupled products were observed.     

一株中度嗜盐菌Salinicola sp.在高盐环境中的烷烃降解特性

从青海油田附近被石油污染的土壤中分离得到一株可利用原油为唯一碳源的菌株,将其命名为X4菌株。经16SrDNA分析鉴定,该菌株与中度嗜盐菌Salinicola zeshunii strain N4^T（GenBank序列号为EU056581）同源性高达99%。X4菌株的最适温度为30℃,最适盐度为8%,最适pH为6.5,最佳碳源为甘油,最佳氮源为氯化铵。该菌可产生生物乳化剂,具有较强的细胞疏水性,对正辛烷、十六烷、二甲苯等典型烃类物质具有良好的乳化能力,细胞CSH值达到60%以上。在含5%盐度的无机盐培养基中,以3g/L的柴油为唯一碳源,采用GC-MS定量分析X4菌株的烃降解特征,结果表明菌株X4培养5天后柴油的总降解率达56%,菌株X4优先降解中长链烃类;C₇～C₁₃烃类的平均降解率为64.1%,C₁₄～C₂₀烃类的平均降解率为52.3%,C₂₁～C₃₁烃类的平均降解率约26.8%。离子型表面活性剂TTAB和SDS对X4菌株生长具有较强的毒性：在浓度达到100mg/L和400mg/L时能完全抑制菌体生长;在40mg/L的浓度下,使得菌株对柴油的降解率降低到20%。而X4菌株对非离子型表活剂——吐温80和生物表面活性剂——鼠李糖脂的耐受浓度均可达400mg/L。鼠李糖脂是嗜盐菌X4菌株的合适复配表活剂。