催化,C_1化学与低碳醇的制取

一、引言以现代催化理论为基础研究合成气化学与甲醇化学,在两次世界性能源危机急迫感的推动下,有了飞速的发展。以一氧化碳加氢合成油品、低碳烯烃及低碳醇,以甲醇为基础原料合成油品、低碳烯烃及同系醇,成为引人关注的课题。这些反应能否带来工业化的前景,在原料     

F-T合成油品加工技术的研究进展

对近年F-T合成粗油品加工技术研究进行了综述。依据F T合成产物的特点,着重对F-T合成油品中烯烃叠合、含氧化合物的脱除以及F-T合成蜡的加氢精制、加氢裂化等的相关研究工作做一浅析,以期提高人们对F-T合成油品及其加工技术的认识,并对今后F-T合成油品的加工研究提出了建议。     

油页岩热解挥发分中轻油吸附回收工艺初探

将活性炭纤维吸附回收工艺应用于油页岩热解气轻质油品回收,自行建立了移动床油页岩连续热解实验装置及相应的油品回收系统。实验结果表明,冷凝冷却至室温的桦甸油页岩热解气中轻质油品含量可达20 g/m³以上。通过活性炭纤维吸附,可将煤气中的轻质油品完全回收。竞争吸附实验表明,"轻油"中的BTX、乙苯、C_10~13的烷烃、烯烃等更容易吸附,碳数相对较低的烯烃、烷烃、环烷烃吸附能力相对较弱。这将为油页岩热解气轻油高效回收工艺开发提供基础数据。     

气相色谱-原子发射光谱和溴加成法联合 测定含烯烃汽油中的单体烯烃 Ⅱ. 汽油的定量分析

采用气相色谱-原子发射光谱检测法对溴化处理后的汽油组成进行了定量分析,提出了烯烃定量回算算法,考察了溴通道比响应因子和分流失真等可能影响定量准确性的因素,并分析了可能造成该方法定量误差的原因,在此基础上提出了用分流失真校正因子修正分流进样造成的误差。方法的准确度实验表明,烯烃单体和混合烯烃的回收率均在96.5%-101%,说明该方法可用于汽油中烯烃含量的测定,同时应用该方法可对汽油中烯烃碳数、类型分布及含量有直观而清晰的认识,可为相关的催化剂及工艺研究提供丰富且准确的组成信息。     

N,N-双(α-氰乙基)甲酰胺键合硅胶涂层毛细管柱用于烷、烯烃中芳烃的分离

芳烃如苯、甲苯、二甲苯等是石油化工产品的重要原料,因此,分析油品中芳烃的含量是了解油品成分和芳烃资源的一个重要手段。此外在劳动保护职业病研究中也要求分析有关环境中烃类尤其是芳烃的含量。由于芳烃和其他烷、烯烃共存时组成的复杂性,同时迄今尚缺乏对烷、烯、芳烃有特殊选择性的高灵敏色谱检测器,因而发展高选择性、高效和快速地分离复杂烃类中芳烃的色谱柱和方法具有重要的实际意义。文献上曾有人采用Rohrsch-     

气相色谱-微波等离子体发射光谱的研究 I. 化合物结构对经验式测定的影响

本文以烯烃、芳烃、多核芳烃、烯烃-烷烃混合物、烯烃-多核芳烃混合物、氯代烃和溴代烃等类型的化合物为代表, 考察了化合物结构对气相色谱-微波等离子体发射光谱联用测定化合物经验式结果的影响。对属于同系物的烃类选其中任一种为参比物, 测定准确度不受化合物结构的影响; 对含有非同系物的混合物, 如烯烃-多核芳烃, 参比物和被测物的结构对测定结果准确度有一定的影响, 选择其中的非同系物作参比物时, 所测得的经验式准确度相对较差; 含卤素原子的化合物结构对经验式测定影响较大, 必须选择结构相近(碳架结构和卤素原子数相近)的化合物作为经验式测定的参比物。     

气相色谱-微波等离子体发射光谱的研究 Ⅰ.化合物结构对经验式测定的影响

本文以烯烃、芳烃、多核芳烃、烯烃-烷烃混合物、烯烃-多核芳烃混合物、氧代烃和溴代烃等类型的化合物为代表,考察了化合物结构对气相色谱-微波等离子体发射光谱联用测定化合物经验式结果的影响.对属于同系物的烃类选其中任一种为参比物,测定准确度不受化合物结构的影响;对含有非同系物的混合物,如烯烃-多核芳烃,参比物和被测物的结构对测定结果准确度有一定的影响,选择其中的非同系物作参比物时,所测得的经验式准确度相对较差;含卤素原子的化合物结构对经验式测定影响较大,必须选择结构相近(碳架结构和卤素原子数相近)的化合物作为经验式测定的参比物.     

气相色谱法和库仑法联合测定含烯汽油的烃族组成

在石油炼制操作控制和产品质量检查中都要分析油品的烃族组成。对含烯的催化裂化、热裂化、焦化及叠合汽油尤其要做饱和烃(S)、烯烃(O)、芳烃(A)的含量分析,简称SOA分析。传统方法为荧光指示剂吸附(FIA)法,近几年发展为多阀多柱的Packard PNA分析器,其扩展式可分析烯烃。前者分析时间长,受人为可变因素的干扰;后者烯烃采用可逆或不可逆吸附,误差较大。本文在普通气相色谱仪上,仪器不作任何改装,同库仑仪联合实现了汽油的SOA分析。 使用气相色谱仪,在极性固定液的不锈钢填充柱     

模拟轻质油品的氧化脱硫

以正庚烷为溶剂，苯并噻吩（BT）、二苯并噻吩（DBT）、4,6-二甲基二苯并噻吩（4,6-DMDBT）作为模型含硫化合物组成模拟轻质油品，在H2O2-HCOOH氧化体系中对模拟轻质油品氧化脱硫进行了研究。考察了氧化剂用量、氧化温度、氧化时间及芳烃、烯烃、含氮化合物的存在等因素对BT、DBT脱除的影响。实验结果表明：在反应温度60 ℃，H2O2∶S＝7∶1（mol/mol）,H2O2∶HCOOH＝1∶1（v/v）,反应时间在40 min的条件下，4,6-DMDBT能全部脱除, DBT、BT的脱除率分别为96% 、58%。向油品中添加芳烃、烯烃、含氮化合物等对BT、DBT的脱除均有不同程度的影响。     

气相色谱法测定催化裂化汽油的烃族组成

在国产仪器和设备上建立了气相色谱法分析催化裂化汽油烃族组成的分析方法。采用N,N-双(a-氰乙基)甲酰胺为固定液的色谱柱将样品中的非芳烃和芳烃分离。以水润湿氮气来稳定高氯酸-高氯酸汞吸收剂,这种吸收剂对烯烃显示了良好的吸收选择性。方法通过两次进样计算出饱和烃、烯烃、芳烃含量。一次进样的分离时间在10分钟左右。与荧光色谱法相比本方法有更好的准确度与重复性。     

气相色谱-场电离飞行时间质谱测定中间馏分油中链烷烃的形态分布

利用气相色谱-场电离飞行时间质谱技术( GC-FI TOF MS)建立了中间馏分油中不同异构程度链烷烃的碳数分布表征方法。首先利用GC-FI TOF MS技术对不同异构程度的链烷烃进行分离、鉴别,然后建立了中间馏分油沸点范围内正构烷烃、异构烷烃在GC-FI TOF MS测定时的相对响应因子算法及不同异构程度链烷烃的碳数分布算法,最后考察此定量方法的精密度和准确度。结果表明,GC-FI TOF MS可以将同碳数链烷烃区分为异构程度不同的3部分：多取代基异构烷烃、单取代基异构烷烃和正构烷烃;可利用GC-FI TOF MS对异构程度不同的链烷烃进行定量分析,精密度较好,相对偏差小于15%。此方法无需进行样品预分离,可直接进样分析,缩短了分析时间,且首次提供了不同异构程度异构烷烃的碳数分布信息。     

铋试金法测定高铋物料中的银

火法试金最常用的为铅试金,当物料中铋的质量百分含量15%时,铅试金分析方法测定银量结果精密度差,且结果偏低。实验中研究了铋试金测定高铋铅阳极泥中银量的方法、铋试金和铅试金方法过程对比、铋试金方法中杂质元素Sb,Cu,As,Ni,Pb的干扰、铋试金过程中铋扣直接溶解滴定和铋扣灰吹二次试金方法对比。通过多家单位对精密度和加标回收率的考察,相对标准偏差(RSD)在0.33%~0.84%,加标回收率在96.38%~100.62%,方法准确、可靠。     

Efficient binomial leap method for simulating chemical kinetics

The binomial tau-leaping method of simulating the stochastic time evolution in a reaction system uses a binomial random number to approximate the number of reaction events. Theory implies that this method can avoid negative molecular numbers in stochastic simulations when a larger time step tau is used. Presented here is a modified binomial leap method for improving the accuracy and application range of the binomial leap method. The maximum existing population is first defined in this approach in order to determine a better bound of the number reactions. To derive a general leap procedure in chemically reacting systems, in this method a new sampling procedure based on the species is also designed for the maximum bound of consumed molecules of a reactant species in reaction channel. Numerical results indicate that the modified binomial leap method can be applied to a wider application range of chemically reacting systems with much better accuracy than the existing binomial leap method.     

A new approach for development of rugged sample preparation of metabolites of albendazole in cow milk

Sample preparation is the critical step in analysis of residues in biological samples. The development of a ragged method is time-consuming, because a huge number of parameters must be checked. To reduce the number of experiments Taguchi's method was applied in the sample preparation of metabolites of albendazole. During the experiments 11 controllable and 7 noise factors were investigated. From the influence of controllable and noise factors on recovery and standard deviation, conditions for the sample preparation and recovery could be concluded with high accuracy and reliability.     

两点法确定混胺中两组分的电位滴定终点

利用两点法确定了液体推进剂混胺中两组分——三乙胺乖二甲苯胺的电位滴定终点,并与常规的弧切作图法乖二阶微分法确定的滴定终点进行了配对t检验,显示结果之间不存在显著差异,或可予校正。两点法简单快速,结果可靠,特别适宜于大量样品的快速分析。     

Thickness measurement of colloidal opal crystal growth by Bragg reflection

This study investigates a simple method for thickness estimation with single layer accuracy for self-assembling opal crystals prepared by the dip-coating method. The thickness (number of layers) of the opal crystals was estimated by an analysis of the optical reflectance from s-polarization incident light, and then verified with SEM. The opal crystals were considered as periodic dielectric layers and were analyzed with the transfer matrix method. The reflectance simulation showed a good agreement with the experimental results. The lattice constant and the thickness were determined at the peak position and by the fringes of the reflection spectra, respectively.     

Different approaches to proximate analysis by thermogravimetry analysis

The experimental optimization by the simplex method of the proximate analysis of coal and biomass by thermogravimetry analysis (TGA) is reported. Heating rate, final temperature, holding time, Ar flow rate and sample size were the control variables. The response function used was chosen to minimize the difference in percentage of volatile matter with the ASTM characterization. The relative accuracy of the method was demonstrated by determination of the volatile matter contents of a number of coals in parallel with the ASTM certified method. The method is successfully used with biomass samples.     

Direct configuration interaction with a reference state composed of many reference configurations

The configuration interaction method where a single reference state is composed of a linear combination of reference configurations is analyzed in detail. In this method single and double replacements are constructed by applying annihilation and creation operators on the reference state. The analysis is based on the recently derived factorization of the direct CI coupling coefficients into internal and external parts. Using the internal coupling coefficients the integrals are transformed to new entities which are used in the diagonalization step. This two-step procedure differs significantly from the usual straightforward one-step direct CI procedure. A number of operations analysis shows that calculations with the present method should be feasible even with a large number of reference configurations in the reference state. Based on first-order perturbation theory the accuracy of the method is predicted to be close to the accuracy obtained with the usual CI method with many reference configurations.     

The connection between the specific refraction,the dispersion and the structure of saturated hydrocarbon mixtures

The method of determining the number of rings in saturated hydrocarbon mixtures with sufficient accuracy from the specific refraction and the dispersion was indicated. With this method the molecular weight of the mixture need not be known.     

计算导数分光光度法的研究：Ⅰ.钨,钼的同时测定

本文以W、MO-SAF-CTMAB体系为例,选取二阶和三阶导数光谱的2个不同波长下的导数值,采用简单解联立方程组的方法即可同时测定钨和钼。本文从原理和实验上证实了计算导数光度法的可行性,提出了以方程组的系数矩阵条件数来指导测量点的选择。