催化裂化轻汽油及其醚化产品的分析

采用气相色谱-质谱、气相色谱-红外、色谱保留值法、化学法、转化率计算法等技术对催化裂化轻汽油中的组分特别是活性烯烃及其醚化产物进行了结构确定,用色谱峰面积校正归一法测定醚化产品中醚的含量;方法被用于催化裂化轻汽油的醚化催化剂评价和工艺研究。     

用气相色谱/质谱法分析醚化后催化裂化轻汽油中的醚及相关烯烃

用气相色谱／质谱联用仪对醚化工艺过程中醚化前后的催化裂化轻汽油组成进行了定性定量分析。由定性结果分析汽油中的活泼烯烃和生成醚的类型,由定量结果分析活泼烯烃转化成醚后的量的变化情况及生成醚的多少。最终鉴定出６种烯烃参与了醚化过程,生成了４种醚。经查证,这些醚对提高汽油辛烷值均有贡献。     

固相萃取-气相色谱法测定甲醇制烯烃副产汽油及甲醇制汽油产物中的含氧化合物

采用纯硅胶柱固相萃取技术对甲醇制烯烃副产汽油或甲醇制汽油产物进行预处理,将产物中的含氧化合物与烃类进行色谱分离,采用质谱鉴定产物中的含氧化合物。使用标准溶液优化纯硅胶小柱的洗脱条件,比较预处理方法的回收率,考察预处理方法的重复性。结果表明,标准溶液的各含氧化合物组分回收率为87.7%~95.3%。采用气相色谱-火焰离子化检测器(GC-FID)通过内标法对实际样品中除甲醇和乙醇外的含氧化合物进行定量分析,使用丁酮、叔戊醇、戊酮和己酮的响应因子作为同碳数醛、酮、醇的FID响应因子,定量甲醇制烯烃副产汽油和甲醇制汽油产物中的含氧化合物。对于甲醇和乙醇,采用GC-MS分析提取特征离子用外标法定量。结果表明,甲醇制烯烃副产汽油和甲醇制汽油产物中的含氧化合物以酮类、醛类为主,并有少量的醇类。     

全二维气相色谱-飞行时间质谱对催化裂化汽油的定性与定量分析

采用全二维气相色谱-飞行时间质谱(GC×GC-TOF MS)对催化裂化汽油全馏分进行了定性与定量分析,建立了相应的分析方法.结果表明,汽油族组成中的烷烃、烯烃、环烷烃、芳烃在全二维点阵谱图中呈分区域、带状的分布特点.GC×GC-TOF MS根据催化裂化汽油组分内分子的沸点及极性差异对其进行两个维度分离,极大地避免了普通色谱法分析过程中沸点相似化合物共流的弊端,实现催化裂化汽油组分的精确分离和准确定性分析.通过引入响应因子,修正了不同性质的烃类在电离源上电离效率的差异,使得TOF对催化裂化汽油族组成的定量结果与普通气相色谱法的定量结果的相关性较好,且应用GC×GC-TOF MS方法获得了催化裂化汽油更为精确的族组成信息.GC×GC-TOF MS为催化裂化汽油精确表征提供了一种有效方法.     

通过Hβ分子筛上的烯烃水合反应提高FCC汽油品质

 以Hβ分子筛为催化剂,通过烯烃水合反应可以降低FCC轻汽油(≤80 ℃)中烯烃含量并提高含氧化合物含量,从而提高汽油的品质. 在V(H2O)/V(oil)=0.6,WHSV=1 h-1,p=5.0 MPa,θ=140 ℃和t=10 h的条件下,FCC轻汽油中烯烃的转化率为16.7%,产物中含氧化合物的含量为9.5%.     

催化裂化轻汽油及醚化产品的气相色谱分析

1引言催化裂化轻汽油醚化工艺将催化裂化汽油中的叔碳烯烃转化为甲基叔烷基醚,不但可以提高辛烷值,增加含氧量,还可以降低蒸汽压和烯烃含量,因而是生产环境友好汽油的理想工艺。在催化裂化轻汽油醚化工艺的研究过程中,原料与产品需要快速准确的分析手段。本文采用气相色谱／质谱法（GC／MS）结合标准样对照法进行定性,根据采用自制的标准样测定的甲醇和醚类的相对重量校正因子进行定量分析,取得了满意的结果,为试验研究和工业生产提供了一种快速准确的分析方法。2实验部分2．1仪器与试剂MAT90型GC/MS联用仪（德国菲尼根公司）…     

气相色谱法测定汽油含氧化合物与苯

本着降低生产成本,开发仪器功能,提高工作效率,建立了双柱切换-反吹技术-气相色谱法(内标法)同时测定汽油中含氧化合物与苯。考察色谱阀的切换时间,柱温等因素对结果的影响,确定了最佳操作条件,同时对方法的精密度和重复性进行验证。结果表明,含氧化合物和苯的相对标准偏差为0.05%～0.2%,加标回收率分别为98.8%和96.7%,同时测定汽油中含氧化合物和苯方法的建立,其分析结果与石化标准方法分析结果一致。     

FCC汽油低温改质过程的烯烃转化及催化剂积炭

利用微反-色谱联合实验装置和连续式小型提升管催化裂化实验装置研究了催化裂化汽油低温改质过程中烯烃转化和催化剂积炭的过程和规律。通过对模型化合物和催化裂化汽油改质过程中催化剂活性、催化裂化汽油窄馏分、反应温度、剂油比和反应时间对烯烃转化和催化剂积炭的研究表明,大部分烯烃转化和催化剂积炭的反应发生在油剂接触极短的反应时间内,并随着催化剂活性、反应物活性、剂油比和反应温度的提高而增加。在油剂接触后很长的反应时间内,生焦量、积炭速率和烯烃的转化程度都很小,烯烃转化损失率降低,因此,催化裂化汽油在低温改质的条件下可以通过延长反应时间来提高烯烃的转化率。因此,催化裂化汽油改质的最佳工艺条件为,390℃～440℃,剂油比6,催化剂活性61～65,长反应时间,轻馏分进料。     

我国催化裂化工艺技术进展

自我国第一套流化催化裂化装置于1965年实现工业化以来,先后开发出沸石催化剂-提升管催化裂化、渣油催化裂化、催化裂解、变径串联提升管催化裂化和正在开发的高选择性催化裂化;经历了催化裂化装置从无到有,技术水平由低到高,装置规模和加工能力从小到大,研究思路从跟踪模仿到自主创新,取得了巨大的成就,已跻身国际先进水平.到目前为止,全国催化裂化装置总加工能力已达到近150 Mt/a,其中渣油占催化裂化总进料约40%,所生产的汽油和柴油组分分别占全国汽油和柴油成品总量的70%和30%左右,所生产的丙烯量约占全国丙烯总产量的40%.同时,此催化裂化装置还可为烷基化装置和醚化装置提供原料.这些成果对我国炼油行业加工重质原料、提高轻质油收率和改善产品质量,进而提高经济效益起着举足轻重的作用.     

气相色谱法测定催化裂化轻汽油及其醚化产物中6种组分的含量北大核心CSCD

选用150m长的DB-1色谱柱,在程序升温的条件下,用气相色谱法分离并测定了催化裂化(FCC)轻汽油及其醚化产物中甲醇、异戊烷、3-甲基-1-丁烯、2-甲基-1-丁烯、2-甲基-2-丁烯及叔戊基甲醚等6种组分。根据相应组分的峰面积Ai及其相对响应因子Ri,用校正归一法计算上述6种组分的含量;在计算相对响应因子时,取碳及氢的相对原子质量(分别为12.011,1.008 0)为基础。甲醇的检出限为0.002%,其余5种组分的检出限均为0.001%。应用该方法分析了醚化FCC轻汽油样品,测得上述6种组分测定值的相对标准偏差(n=6)依次为0.82%,0.64%,1.1%,0.54%,0.33%,1.3%。用标准加入法测定了6种组分的回收率,所得回收率在88.9%～99.0%之间。为对催化裂化装置的催化剂反应性能作出评价,可从预反应器出口物料、醚化蒸馏塔顶物料和后反应器出口物料中分别取得样品,应用该方法对其中相应组分进行测定。异戊烷在此反应工艺中不参与反应,根据每个反应器入口和出口的异戊烯与异戊烷的比值可以计算出异戊烯在整个工艺过程中的转化率。经计算得异戊烯在预反应器中的转化率为66.5%,在醚化蒸馏塔中的转化率为76.1%,在后反应器中的转化率为37.5%,醚化反应的总转化率为95.0%。     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。