五种不同类型土壤中有机化合物土壤吸附系数的预测

为了验证土壤柱液相色谱法测定农药的土壤吸附系数的普遍适用性和预测的准确性,采用了5种组成及性质差异较大、具有一定代表性的土壤样品,对在甲醇 水流动相条件下测定的保留因子与土壤吸附系数间的相关性进行了研究。结果表明,土壤柱液相色谱法是预测农药的土壤吸附系数的一种有效方法,适于多种类型土壤中农药土壤吸附系数的预测。     

用色谱技术测定CO_2在合成甲醇催化剂上的传递和吸附系数

研究吸附质在催化剂固定床反应器上的传递和吸附系数,对研究非均相催化剂的性质,提高催化剂的效能,以及为反应器设计提供基本数据等方面,都是十分重要的。用传统的稳态方法求出传递和吸附系数,外推到工业条件下使用,一般是不太可靠的。如果用色谱技术,就能在比较接近工业操作的条件下获得传递和吸附系数,因而这种方法     

某极低放废物填埋场土壤特性及其锶阻滞性能研究

为了考察某极低放射性废物填埋场土壤对待填埋锶的阻滞性能,对拟建场址开挖土坑进行土壤取样,采用筛分法,静态(间歇)吸附和动态迁移法等方法对所取的土壤样品进行土壤粒径的分布及渗透系数测定,并进行拟建场址土壤对锶分配系数和阻滞系数的研究,结果表明拟建场址土壤为非均质介质特征;渗透系数,纵向弥散度和有效孔隙度表明该拟建场址土壤属于属于亚砂、亚粘土;静态吸附试验的吸附结果表明最大的分配系数值为765.5,动态吸附实验各实验点对锶的阻滞系数最高位300.0;实验结果表明场址需要做进一步的化学工程屏障阻滞锶的迁移以保障填埋场的安全。     

理想吸附混合物在二位不均匀模型表面上的活度系数

对理想吸附混合物在二位不均匀模型表面上的表面活度系数进行了系统的计算.结果表明,表面不均匀性将导致理想吸附混合物表观地呈现与Raoult定律的负偏差(表面活度系数小于1).但在与固-液界面相似的情况,即总覆盖度接近于1的条件下,算得的表面活度系数-吸附相成分关系皆呈现几乎完全对称的形状.因此实验测得的表面活度系数-吸附相成分关系所呈现的不对称性,可能是不同分子之间非理想的相互作用所引起,而不是表面不均匀所造成的.     

国产大孔吸附树脂浓集分离赤霉素

研究了７种国产大孔吸附树脂对赤霉素的吸附能力,其中Ｓ－８吸附效果较好,赤霉素固／液分配系数为１２．４４,动态吸附容量为４．０６ｍｇ／ｍｌ。８０％丙酮水地赤霉素的洗脱能力较强。用工业赤霉素发酵液进行吸附－解吸实验,分配系数可提高至２５．８８（ＰＨ＝２）,动态吸附容量可提高至１０．０２ｍｇ／ｍｌ,赤霉素收率可达９０％以上,且经吸附－解吸循环,可将发酵液中赤霉素浓缩７倍以上。     

液相色谱技术测定葡萄糖果糖在Ca型吸附剂上相平衡常数和总传质系数

]考虑轴向扩散的影响,导出液相色谱技术测定吸附相平衡常数和总数传质系数参数估值模型,测定葡萄糖果糖吸附相平衡常数和总传质系数,研究流速、温度对这些参数的影响。获得理论计算与色谱分离实验流出曲线相吻合结果。     

新型SGN螯合树脂吸附贵金属性能和机理的研究

本文首次研究自制的氨基胍基螫合树脂吸附贵金属的行为。测定了树脂在HCl及H_2SO_4介质吸附贵金属的分配系数和吸附百分率,并研究了各种贵金属的吸附速率、以及酸度和温度等对吸附过程的影响。并提出树脂对贵金属配阴离子的配位和交换共存的吸附历程。     

铅离子印迹聚合物选择性吸附特性的研究与应用

利用离子印迹技术以铅离子为模板,甲基丙烯酸为功能单体,偶氮二异丁腈为引发剂,乙二醇二甲基丙烯酸酯为交联剂,采用本体聚合法制备铅离子印迹聚合物。通过红外光谱和紫外光谱对该离子印迹聚合物进行表征,采用静态平衡吸附实验分析铅离子印迹聚合物的吸附性能和吸附选择性。实验结果表明:与非印迹聚合物相比较,Pb(II)印迹聚合物对Pb(II)具有较强的吸附能力和较好的吸附选择性,饱和吸附量为19.44mg/g,pH=6时吸附效果最好,达到吸附平衡的时间是7h;静态分配系数Kd和选择性系数k分别为1381ml/g和20.3。将该离子印迹聚合物应用于环境水样中铅离子测定时的预富集,结果满意。     

TP207树脂吸附La~(3+), Ca~(2+)及La~(3+)/Ca~(2+)分离系数测定研究

通过静态吸附和解吸试验系统研究了氯化体系中TP207树脂吸附La~(3+)和Ca~(2+)的规律,考察了吸附时间、吸附温度、吸附浓度和pH值对树脂吸附容量的影响,以及HCl浓度对负载树脂解吸率的影响,并得出了优化条件下的La~(3+)/Ca~(2+)分离系数。结果表明:在吸附时间5 h,吸附温度25℃和pH值为4.10的条件下, TP207树脂对La~(3+)和Ca~(2+)吸附容量分别为1.25和0.23 mmol·g~(-1)。在此条件下, La~(3+)/Ca~(2+)分离系数超过13,树脂循环利用20次后吸附容量下降10%,为工业生产中提La~(3+)除Ca~(2+)工艺提供了新的技术支持。     

低温变压分子筛动态分离CH_4/CO_2实验研究

在低温变压条件下测量了5A和13X沸石分子筛对CH_4/CO_2混合气体的分离能力。实验研究了CH_4/CO_2气体流量、吸附压力、填料高度和吸附温度对穿透曲线和分离能力的影响。研究结果表明,增大气体流量、增加吸附压力会降低分离效果,减小混合气体的分离系数;降低吸附温度、增加填料高度有利于CH_4/CO_2分离,提高混合气体的分离系数;在相同实验条件下,13X沸石分子筛对CH_4/CO_2混合气体吸附分离能力高于5A分子筛。     

Second virial coefficients of adsorption isotherms of organic molecules on porous polymers

The dependence of the specific retention volumes of sorbates on their concentration in the gas phase is investigated. It is shown that the slope tangent of the dependence is related to the second coefficient of the virial expansion of adsorption isotherm. It is established that the free energy of sorbate-sorbate interactions on the surface of porous polymer sorbents is constant for all investigated molecules. An equation for calculating retention volumes at different sorbate concentrations is proposed.     

用线性溶剂化能相关(LSERs)方法评价聚合物包覆钛胶固定相并与相关固定相比较

利用线性溶剂化能相关(LSERs)方法对聚(乙基苯乙烯-二乙烯基苯)包覆钛胶固定相(ES-DVB-TiO₂)的保留行为进行评价,并与聚丁二烯涂覆钛胶固定相(PBD-TiO₂),键合硅胶固定相(ODS)和树脂固定相(PR-1)作了比较,计算出各变最对logk'的百分方差数,发现V₂、Σα₂^H,和Σβ₂^H对logk'有较大的贡献,与聚合物固定相PRP-1近似,因此它们有相似的保留机理,即吸附机理大于分配机理.     

Retention of some monoamine oxidase inhibitory drugs on a β-cyclodextrin polymer-coated silica column

The retention of seventeen monoamine oxidase inhibitory drugs (mono- and disubstituted derivatives of propargylamine) was determined on a β- cyclodextrin polymer (β-CDP)-coated silica column using methanol-0.05 M K₂HPO₄ (6:4, v/v) as the eluent. The inclusion complex formation between the drugs and a water-soluble β-cyclodextrin polymer was studied by charge-transfer chromatography carried out on reversed- phase TLC layers. The capacity factors were correlated with the various physico-chemical parameters and with the inclusion complex-forming capacity of the monoamine oxidase inhibitory drugs. Calculations indicated that the inclusion complex-forming capacity of the drugs does not influence their retention on a β-CDP column, that is, the water-soluble and water-insoluble β-CDPs show different retention characteristics. The specific hydrophilic adsorption surface of the solutes significantly influences the retention in HPLC. The results suggest that the selectivity of the β-CDP-coated silica support may be different from that of the traditional alkyl-bonded reversed-phase columns.     

Joint use of cyclodextrin additives in chiral discrimination by reversed-phase high-performance liquid chromatography: temperature effects

The temperature dependence of chiral separations was investigated in combined system of reversed-phase (RP) liquid chromatography using two chiral additives: single or β native cyclodextrins and their permethylated derivatives. The model tested compounds of pharmaceutical interest were: methylphenobarbital, mephenytoin, morsuximide and camphor. Taking the localization of a complexation process as a criterion – the combined system with two selectors has been rationalized as occurring in three stages. The influence of temperature (in narrow range of 20°C) on retention and enantioselectivity was studied in; System I (complexation occurs in the mobile phase), in System II (complexation on the stationary phase) and in System III (complexation in both phases together). In System III (as for System I) it has been found that the model compounds could be classified into three groups based on their retention dependence on temperature: retention decrease with temperature decrease, retention increase with temperature decrease or no influence of temperature on retention. For all the compounds investigated, decrease in temperature increases the selectivity. Standard enthalpy (ΔH⁰) and entropy (ΔS⁰) changes of solute transfer between the mobile and the stationary phase and standard enthalpy (ΔH⁰_CD) and entropy (ΔS⁰_CD) changes of complex formation were also calculated. In Systems I and III, if the complexation in the mobile phase is favored process compared with interaction with the stationary phases (RP or covered by permethylated cyclodextrin), the shortest retention time and the best selectivity is observed at low temperature.     

模拟烟气气氛下矿物元素组分对砷的吸附特性研究

利用气相砷吸附反应实验装置,研究了300-900℃条件下CaO、Fe₂O₃、MgO、Al₂O₃、K₂SO₄及钙铁混合吸附剂在模拟烟气气氛下的As₂O₃（g）吸附特性。结果表明,在五种单元素吸附剂中,CaO的吸附能力最强,K₂SO₄最弱;随着温度升高,CaO的吸附量先增加,在700℃时略微下降后又增加,Fe₂O₃的吸附量先增加后减少,MgO、Al₂O₃、K₂SO₄的吸附量一直增加;三种比例的钙铁混合吸附剂的吸附效果的实验值相比计算值至少提高了92%,Ca：Fe比为3：1时,吸附效果最好,达到7.91 mg/g。混合后烧结反应导致表面结构改变是吸附效果提升的重要原因。     

K_2CO_3催化剂在煤焦热解中的形态转变及其对煤焦催化气化的影响

在固定床中考察了不同温度下神府煤焦催化热解中K2CO3的转变形态,以及在TG-DSC分析仪上研究了K2CO3添加方式和粒径对其气化速率的影响。结果表明,随着气化温度的升高,催化剂的添加方式对煤焦气化反应速率的影响减弱;对热解残渣的SEM/EDX谱图显示,随着温度升高,K催化剂在煤焦中能展现更好的分散性;在热解过程中,煤焦中的碳通过与K2CO3反应释放出CO2和CO,生成的气体量与温度相关;在较低温度650℃下,不同粒径对气化效果影响差别较大,粒径越小气化反应性越好。K2CO3的流动性随着温度升高而增强,催化活性也越强;低于700℃时,要考虑添加方式对气化反应性的影响。     

Iodide analysis by ion chromatography on a new stationary phase of polystyrene-divinylbenzene agglomerated with polymerized-epichlorohydrin-dimethylamine

A new stationary phase for iodide ion analysis has been developed. The cationic polymerepichlorohydrin-dimethylamine(PEPI-DMA) was served as modifier in synthesizing polyelectrolyte sorbents and the macroporous polystyrene-divinylbenzene(PS-DVB) resin was used as support. The positively charged polymer(PEPI-DMA) was electrostatically bonded to a negatively charged particle(PS-DVB sulfonated). The new stationary phase was characterized by scanning electron microscopy(SEM), Fourier transform infrared(FTIR), elemental analysis, chemical adsorption and desorption measurements. The chromatographic evaluation of the new stationary phase was performed using various anions with a conductivity detector. The new stationary phase was also applied to the determination of iodide directly with a DC amperometric detector using a platinum working electrode and an Ag/Ag Cl reference electrode. The chromatographic conditions were optimized and the eluent solution contained 5 mmol/L HNO3 and 15 mmol/L Na NO3 at a flow rate of 1.0 m L/min and column temperature of 30 8C. The applied voltage of the DC amperometric detector was 0.9 V. Under the optimum conditions, the linear range of the method was 0.2–50 mg/L for iodide ion with a correlation coefficient of 0.9990. The detection limit was 0.05 mg/L(calculated at S/N = 3) and the relative standard deviations(RSD, n = 6) were all less than 1% for retention time, peak area and peak height. This method was also utilized for the determination of iodide ions in samples of povidone iodine solution and kelp samples with satisfactory results.     

High-performance liquid chromatography of sulfonamides and quinolones on p-tert-butyl-calix[6]arene-bonded silica gel stationary phase

The high-performance liquid chromatographic behavior of some sulfonamides and quinolones was studied on a p-tert-butyl-calix[6]arene-bonded silica gel stationary phase. The effect of mobile phase variables such as methanol content, ionic strength and pH on their chromatographic behavior was investigated. The retention behavior of sulfonamides on the stationary phase was compared with that on both Zorbax C₁₈-bonded silica gel and γ-(ethylenediamino)propyltriethoxylsilane-bonded silica gel (diamino-bonded phase). The retention mechanism of sulfonamides and quinolones on the stationary phase was also discussed. The results indicate that the stationary phase behaves as a reversed-phase packing and its separation selectivity is much better than that of not only Zorbax C₁₈ phase but also diamino-bonded phase. Some sulfonamides and quinolones were separated on the stationary phase, but the separation of sulfonamides is far more successful.     

金属有机框架CPL-1填充柱气相色谱分析氢同位素

金属有机框架(MOFs)材料CPL-1的比表面积大、孔径均一,在低温条件下对氢同位素具有良好的量子筛分效应,是气相色谱固定相潜在的应用材料。采用CPL-1填充制备了长0.5 m、内径1 mm的微孔填充柱,借助单晶Al_2O_3颗粒间隙构建了色谱载气流通路径,在低温条件下探索研究了CPL-1填充柱的氢同位素分析性能。结果表明,在77 K时CPL-1对H_2和D_2的吸附量接近4 mmol/g,优于MnCl2/γ-Al_2O_3和γ-Al_2O_3,CPL-1填充柱在取样量0.25~2 mL范围内对低浓度氢同位素样品的检测具有良好的线性关系,检测的相对误差小于4%。CPL-1填充柱具有线性范围宽、重复性好、准确度高等优点,在氢同位素色谱分析中具有潜在的应用价值。