固定床吸附柱放大效应考察─—理论板当量高度分析

从色谱塔板理论公式出发，推导出实测理论板公式及理论极当量高度和吸附热力学、吸附动力学参数之间的关系，并对模型的选择、优化操作线速的选取作了讨论。实验测定了ｄ＿ｐ／ｄ＿ｔ＝４．０／２０．０时，吸附柱内的轴向扩散系数及流体传质系数，并加以关联。对不同压力、流量下的理论板当量高度也进行了检验。     

变性羊毛对微量铋（Ⅲ）的吸附和洗脱性能的研究

本文研究了变性羊毛对微量铋（Ⅲ）的吸附和洗脱性能，实验表明，变性羊毛对微量铋（Ⅲ）具有良好的吸附性能，饱和吸附量为２．３ｍｇ／ｇ，吸附酸度为０．１０～０．３０ｍｏｌ／ＬＨＮＯ＿３，洗脱酸度为１．０～２．０ｍｏｌ／ＬＨＮＯ＿３。     

PLZT陶瓷的介电弛豫行为与A位有序

用传统粉末工艺合成了（Ｐｂ＿（０．８６５）Ｌａ＿（０．０９））（Ｚｒ＿（０．６５）Ｔｉ＿（０．３５））Ｏ＿３陶瓷（ＰＬＺＴ９／６５／３５）。Ｘ射线研究表明：试样中存在着Ａ位准体心立方有序超结构，有序畴的平均尺寸为１０～２０ｎｍ。测定了１０个频率下介电常数与温度的关系，并将介电常数最大值的温度Ｔ＿ｍ与对应的频率ｆ用Ｖｏｇｅｌ－Ｆｕｌｃｈｅｒ公式拟合，得到物理上合理的激活能及指数前项值，这表明试样的介电弛豫行为与自旋玻璃态类似。基于Ａ位有序超结构及类似于自旋玻璃态的极化行为，对试样的极化全过程进行了探讨。     

BaO－Gd2O_3－TiO_2体系相关系、相结构与电性质的研究

借助于固相合成、Ｘ射线衍射分析和交流阻抗法测定了ＢａＯ－Ｇｄ＿２Ｏ＿３－ＴｉＯ＿２体系的相关系、相结构与电性质。发现在研究的部分体系内有两个三元化合物新相：ＢａＧｄ２Ｔｉ＿４Ｏ＿（１２）属正交晶系，其晶胞参数为：ａ＝１．２１３７２ｎｍ，ｂ＝２．２３２６５ｎｍ，ｃ＝０．３８１９５ｎｍ，Ｖ＝１．０３４９７０ｎｍ￣３，Ｚ＝４；Ｂａ＿（１１）Ｇｄ＿４Ｔｉ＿７Ｏ＿（３１）属六方晶系，其晶胞参数为：ａ＝０．５９５４７ｎｍ，ｃ＝２．９７１９７ｎｍ，Ｖ＝０．９１２６３ｎｍ￣３，Ｚ＝１。在研究的部分体系内含有１３个单相区，２５个二相区，１３个三相区。测定了相关物相的电导和介电常数，发现ＢａＧｄ＿２Ｏ＿４与Ｇｄ＿２Ｔｉ＿２Ｏ＿７有很高的介电常数（ε’＞２００），是很有希望的功能材料。     

对苯二甲酸双羟丁酯合成过程中副产物四氢呋喃生成动力学的研究

对在工业生产条件下，以０．０５％（质量比）Ｔｉ（Ｏ－ｎ－Ｃ＿４Ｈ＿９Ｏ）＿４为催化剂，将对来二甲酸与１，４－丁二醇直接酯化，ＢＤ／ＴＰＡ＝１．７０（ｍｏｌ比），生成四氢呋喃（ＴＨＦ）的副反应动力学进行了研究，得出了ＴＨＦ生成的动力学方程ｄＦ／ｄｔ＝Ｋ（Ｍ＿Ｒ－Ｘ－Ｆ），反应速率常数ｋ＝１．７８×１０￣（１２）ｅｘｐ（－３２９００／ＲＴ）和ＴＨＦ生成的活化能Ｅ．＝１３７．５ｋＪ／ｍｏｌ，略高于酯化反应的活化能，表明以控制反应温度的方法抑制ＴＨＦ的生成是困难的。     

湿化学法制备0．95Pb（Mg_（1／3）Nb_（2／3））O_3－0．05PbTiO_3铁电陶瓷

用湿化学法制备了钙钛矿相的含量为９９％的０．９５Ｐｂ（Ｍｇ＿（１／３）Ｎｂ＿（２／３））Ｏ３－０．０５ＰｂＴｉＯ＿３（简称０．９５ＰＭＮ－０．０５ＰＴ）微粉，ＳＥＭ显示其粒度为０．２～０．３μｍ。通过ＸＲＤ确定了合成０．９５ＰＭＮ－０．０５ＰＴ前驱物的最佳条件为：溶液的ｐＨ值为１．５，反应温度为６０℃。制备０．９５ＰＭＮ－０．０５ＰＴ陶瓷时，预烧温度为８００℃（２ｈ），烧结温度为１２５０℃（１ｈ）。粉末烧结后制得纯钙钛矿相的０．９５ＰＭＮ－０．０５ＰＴ铁电陶瓷，其密度为理论密度的９５％，介电常数为１４８００（８００Ｈｚ）。     

TC－偶氮胂－高碘酸钾－钌（Ⅲ）退色反应在痕量钌的分光光度测定中的应用

在痕量钌（Ⅲ）的存在下，显色剂ＴＣ－偶氮胂与ＫＩＯ＿４在１．０ｍｏｌ／ＬＨ＿２ＳＯ＿４介质中加热至沸，退色反应在３ｍｉｎ内完成且与钌的含量具有良好的线性关系。在此基础上建立了痕量钌的催化分光光度分析法。其检出限可达０．０２μｇ／１０ｍＬ。钌含量在０．０４～０．４０μｇ／１０ｍＬ范围内符合朗－比定律。本文提出了退色反应的最佳条件及贵金属精矿中痕量钌的测定法。     

交联膨润土吸附磷行为研究

从热力学和动力学两方面讨论了交联膨润土吸附剂对磷的吸附特性。吸附等温式符合Ｌａｎｇｍｕｉｒ公式：Ｃ／ｑｅ＝０．１７Ｃ＋０．４１。吸附热力学模型为ｌｎＣ＝－４４０／Ｔ－０．１２６,吸附动力学特性可用下式描述：ｌｏｇ（ｑｅ－ｑ）＝ｌｏｇｑｅ－Ｋｔ／２．３０３,ｌｎ［１－（ｑ／ｑｅ）２］＝－Ｋｔ。其中,Ｋ＝（π／ｒ）２Ｄ,ｌｎＤ＝－２．５３－７４１．０７／Ｔ。扩散活化能为６．１６１ｋＪ／ｍｏｌ,表明吸附过程受扩散控制。     

高密度CaCO_3的制造

摘１４７４高密度ＣａＣＯ＿３的制造──Ｔｒｙｐｕｅ，Ｍｉｅｃｚｙｓｌａｗ等；波兰专利：１５８６７３。在２０～５０℃下把含有０．１～０．７ｍｏｌ／ｌＣａＣｌ＿２液体与索尔维制碱的碱液（含Ｎａ＿２ＣＯ＿３０．１～０．９ｍｏｌ／ｌ）反应。用缓倾法分离产生的...     

铅系复合钙钛矿Pb（Fe_（1／2）Ta_（1／2））O_3铁电陶瓷的介电弛豫

用普通合成法制备了纯钙钛矿结构相的Ｐｂ（Ｆｅ＿（１／２）＝Ｔａ＿（１／２））Ｏ＿３（ＰＦＴ）陶瓷，并进行了９００℃退火热处理。对其介电性质测试结果表明，未热处理与热处理过的ＰＦＴ陶瓷在０．１～１００ｋＨｚ频率下均表现出介电弥散性转变。未热处理的ＰＦＴ陶瓷最大介电常数对应的温度（Ｔ＿０）不随测量频率变化；热处理过的ＰＦＴ陶瓷在此频率范围Ｔ＿０值表现出明显的频率依赖性（频率色散），即ΔＴ＿０＝５℃。由此可以认为ＰＦＴ是弛豫铁电体。ＸＲＤ结果表明，未热处理的ＰＦＴ陶瓷无超晶格衍射；而热处理过的ＰＦＴ陶瓷则有较弱的（１１１）超晶格衍射。利用有序－无序转变理论及超顺电结构模型对其结构与性质进行了探讨。     

Steady-State Characteristics of Lithium Isotope Separation by a Circuit of Continuous Displacement Chromatography

Abstract

Height equivalent to a theoretical plate (HETP), which is an important factor to determine separation performance, is experimentally obtained for lithium isotope separation by a circuit of continuous displacement chromatography. The values of HETP are related to the flow rates and concentrations of the displacement reagents. A new equation to estimate HETP is derived and shows good agreement with the experimental data. Diffusion in the resin is found to be the major resistance for the isotope exchange reaction, and liquid mixing in the columns also strongly influences the value of HETP.     

Extruded monoliths for gas separation processes: Height equivalent to a theoretical plate and pressure drop correlations

Extruded monoliths are generally adopted in the chemical industry for the advantage of reduced pressure drops at high throughput, but a systematic procedure to evaluate their performance is not readily available. Key performance indicators for a monolith are the height equivalent to a theoretical plate (HETP) and the pressure drop of its channels. This contribution presents for the first time a systematic approach to the analysis of several extruded monoliths of industrial relevance. A procedure to derive the HETP correlation for an arbitrary extruded monolith is presented, and pressure drop correlations from literature are reviewed. The HETP correlations have been validated against three dimensional (3D) numerical simulations. A reduced-order model is derived from the HETP and is shown to capture the overall dynamics of the 3D simulations with high accuracy without adjustable parameters. Finally, a comparison between the extruded monoliths and packed beds is reported and includes pressure drops.     

同心圈式旋转床的精馏实验

同心圈式旋转床是一种新型超重力旋转床,其转子由一组多孔板同心圈构成,相邻同心圈之间无填料或填充填料。液体在同心圈上存在滑移效应,滑移效应能够增大气液比表面积和改善液体在同心圈上的周向分布。本文采用乙醇-水物系对转子直径为1.0m的大型同心圈式旋转床进行全回流常压精馏实验,实验选用无丝网填料同心圈和填充丝网填料同心圈两种转子。实验结果表明,本大型同心圈式旋转床具有较大的处理量,其等板高度（HETP）随F因子和超重力因子的增大先减小后增大。填充丝网填料同心圈转子的HETP小于无丝网填料同心圈转子。在超重力因子为563.4和F因子为5.5(m/s)(kg/m³)^0.5时,填充丝网填料同心圈转子的等板高度达到最小值51.5mm,每块理论板气相压降为1.5kPa。通过实验数据拟合得到了两种同心圈转子的HETP经验关联式。与折流式旋转床相比,同心圈式旋转床具有高通量和低压降的优点。     

A strategy for tailored design of efficient and low‐pressure drop packed column chromatography

Packed chromatographic column, with higher efficiency and lower pressure drop is designed by using inert core adsorbents as stationary phase. The analytical solutions for moments and height equivalent to a theoretical plate (HETP) are given under the conditions of linear adsorption kinetics by taking into account of the axial dispersion, film mass‐transfer resistance, intraparticle diffusion resistance, and the sorption rate for chromatographic column packed with inert core adsorbents. By minimizing HETP, a nonlinear algebraic equation was derived to predict the optimized value of the inert core radius. For a given adsorbent with the optimized inert core radius, a strategy was presented to tailor the design of new packed chromatographic column with higher efficiency and lower pressure drop. As an example for supercritical carbon dioxide chromatography, reduced equations in terms of dimensionless inert core radius were derived by “order of magnitude” analysis. The quantitative analysis shows that the major benefit of the inert core adsorbent is a shorter diffusion path compared to conventional fully porous particles. The shorter diffusion path reduces dispersion of solutes and minimizes peak broadening leading to lower pressure drop while maintaining high‐separation efficiency. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

填料塔精馏过程的建模与优化

通过对填料塔的等板高度的计算，将填料塔精馏过程的建模问题转化为一个理论筛板塔的建模问题，简化了建模过程的复杂性，并推算出灵敏板的位置和灵敏板温度，同时提出了优化操作的合理、可行的建议。     

Thermodynamic and Kinetic Study of Adsorption of R,S‐α‐Tetralol Enantiomers on the Chiral Adsorbent CHIRALPAK AD

Abstract

Experimental results for the separation of S,R‐α‐Tetralol enantiomers obtained on preparative columns packed with particle size 20 µm of chiral adsorbent CHIRALPAK AD are presented. The total porosity was measured by using the non‐retained compound 1,3,5‐Tri‐tert‐butylbenzene and was 0.61. The permeability of the bed packed with CHIRALPAK AD was calculated as 4.4×10^?13 m². The efficiency of columns was characterized by the height equivalent to a theoretical plate (HETP) and a linear dependency has been found over tested flow rates. The HETP of S‐α‐Tetralol and R‐α‐Tetralol calculated at the flow rate 5.0 cm³/min were 320 µm and 340 µm, respectively. Thermodynamic adsorption parameters enthalpy, ΔH and entropy, ΔS, have been calculated from van't Hoff plot. Equilibrium and kinetics of adsorption of single enantiomers and racemic mixture of α‐Tetralol on CHIRALPAK AD were evaluated as well. The parameters for multicomponent isotherm linear‐Langmuir model are presented. The breakthrough curves of α‐Tetralol enantiomers are simulated with a mathematical model that accounts for axial dispersion and linear driving force for the intraparticle mass transfer.     

Basic design of distillation columns filled with metallic structured packings

This paper reports a comparison of several available correlations to calculate flooding velocity and mass transfer efficiency by using the concept of height equivalent to a theoretical plate (HETP) for distillation columns filled with metallic structured packings. It is found that there are more correlations for pressure drop or gas velocity at flooding than correlations to predict HETP values, and that most of the correlations need empirical constants or exponents for their calculation. Nevertheless, these values are not reported for all the packings and all the sizes available. A case study is made for application of the proposed methods, and the results are presented and compared. A brief comment is made on each method and its ease of application.     

规整填料在加压精馏中的传质性能

高压精馏是现代过程工业中十分重要的分离过程 ,例如炼油工业中轻烃的分离 ,石油化工中乙烯、丙烯等低碳烃类的分离 ,都是经过高压精馏完成的 .高压精馏效率一般较在常压下有所降低 ,其中填料塔较板式塔下降更明显 ,故通常认为采用板式塔比较好 .但规整填料由于其大通量、低压降等优点 ,已经开始涉及高压领域 ,因此对规整填料在高压下的性能需进行测定和研究 .目前 ,对规整填料在高压下传质性能的研究 ,国外ＦＲＩ[1] 近年已开始进行 ,但其实验数据较少 ,在国内目前还属空白 .本文在国家重点精馏分离实验室高压热模精馏实验塔上进行了一系列…     

Separation of Nitrogen Isotopes by Displacement Band Chromatography

Abstract

A study of the separation of ¹⁴N and ¹⁵N isotopes via displacement band chronatography was conducted using sulfonated styrene-divinylbenzene resins. Starting with a feed solution of 0.5 N NH₄OH (containing 51% ¹⁵N), a band was developed that generated a concentration profile ranging from 11 to 85 % ¹⁵N. The separative power and HETP (height equivalent to a theoretical plate) were found to be dependent on the resin characteristics (size, crosslinkage) and operating parameters (superficial velocity, concentration). The use of a 7/10-microneter-size, high performance resin increased the separative power by a factor of 17 and decreased the HETP by a factor of 10, when compared to a 100/200 mesh Dowex 50W-X12 resin under similar process conditions. The HETP could further be reduced by lowering the superficial velocity and/or eluant concentration.