Production of Highly Pure Methyl tert-Butyl Ether

Russian Journal of Applied Chemistry - The batch processing of an organic solvent methyl tert-butyl ether with obtaining a product of high purity was investigated. The separation coefficients of...     

Synthesis of Methyl tert-Butyl Ether from tert-Butyl Alcohol and Methanol Using Beta Zeolite Catalysts

MTBE synthesis from tert-butyl alcohol (t-BA) and methanol has been studied using beta zeolites. Increasing the reaction temperature results in an increase of t-BA conversion with concomittant decrease of MTBE selectivity. The t-BA conversion decreases with increasing calcination temperature and alkali metal ion exchange of H zeolite. The catalytic results are correlated with the surface area and the acidity of catalysts.     

合成甲基叔丁基醚的分子筛催化剂研究

通过对ＨＺＳＭ－５,ＨＺＲＰ－１和Ｈβ三种类型分子筛催化剂上合成甲基叔丁基醚的活性测定和结构表征,初步考察了分子筛孔结构对催化活性的影响。在此基础上,对适宜孔结构的分子筛进行了水热改性,考察了改性条件对分子筛催化剂的性质及其合成甲基叔丁基醚反应催化活性的影响,得到了催化活性较好的分子筛催化剂。     

无铅汽油样品中甲基-叔丁基醚的定量测定

1　引　　言由于含铅汽油给环境带来的不利影响 ,近几年来 ,无铅汽油已开始在我国大范围使用。甲基叔丁基醚 (ｍｅｔｈｙｌｔｅｒｔ ｂｕｔｙｌｅｔｈｅｒ,ＭＴＢＥ)是无铅汽油中的一种常用添加剂 ,可提高辛烷值使汽油燃烧更完全 ,从而减少环境污染。但是 ,ＭＴＢＥ的使用在许多发达国家特别是美国引起了很大争议。这是因为ＭＴＢＥ在自然条件下很难降解 ,在水中的溶解度较高(42 0 0 0ｍｇ/Ｌ) ,由于地下储油罐泄露和汽车尾气的排放 ,环境中尤其是地下水中ＭＴＢＥ的含量正在迅速增加。同时 ,研究发现ＭＴＢＥ存在潜在的致瘤性 ,可破坏小鼠…     

PAHs Formation in the Depositions in a Methyl tert-Butyl Ether/Ar,a Methyl tert-Butyl Ether/O2/Ar and a Methyl tert-Butyl Ether/H2/Ar RF Plasma Environment

Contents and distributions of polycyclic aromatic hydrocarbons (PAHs) in the depositions were investigated and discussed in a MTBE/Ar, a MTBE/O₂/Ar and a MTBE/H₂/Ar plasma systems. A radio-frequency (RF) plasma system was used to produce the depositions under the designed operational condition. The identification and quantification of PAHs was accomplished by using a GC with a mass selectivity detector (GC/MS). Results indicated that when the input power controlled at high wattage (70 W) in the three systems, the contents of total-PAH in the MTBE/Ar system are higher than those of total-PAH in other system with adding O₂ or H₂. The comparison of three systems indicated the formation and accumulation of PAHs in the MTBE/Ar system is easier than other systems. At high input power wattage, when the MTBE/Ar mixture added O₂ or H₂, the domain pattern was shifted from both 3- and 4-ring PAH to 2-ring PAH. As far as the total-PAH content is concerned, the MTBE/Ar system at 70 W was found to have the highest mean total-PAH content (1540 g/g), while the MTBE/O₂/Ar system at 20 W had the lowest mean total-PAH content (44.4 g/g).     

Electrotreatment of Wastewaters from High-Octane Fuel Production To Remove Methyl tert-Butyl Ether and Methanol

The possibility is examined of removing methyl tert-butyl ether from wastewaters by electrotreatment.     

Pervaporation Membranes for Separating Mixtures of Methanol and Methyl tert-Butyl Ether

Transport characteristics of new types of bi- and multilayer composite polymer pervaporation membranes and asymmetrical membranes in separating mixtures of methanol and methyl tert-butyl ether were studied. The principles of design of the membranes and their mass-exchange characteristics are treated in terms of the Henis-Tripodi resistance model.     

毛细管气相色谱法分析清洁汽油中甲基叔丁基醚含量

1 引 言为了提高汽油的辛烷值及抗爆性能,甲基叔丁基醚(MTBE)可作为一种重要的调和组分。但由于其对健康的不良影响，其含量应严格地进行控制。以往气相色谱法中较准确的内标法，由于对相对校正因子的计算不准确而使定量的准确度较差，低含量时结果偏高。因而开发一种更准确的分析方法势在必行。2 实验部分2.1 仪器与试剂 HP6890plus型气相色谱仪及具程序升温功能的其它型号的气相色谱仪均可,具一个十通切换阀、FID检测器、HP6890化学工作站。极性预分离柱:0.56 m×0.35 mm i.d 内填充为20%(m/m)TCEP/Chromosorb 0.1　mm;非极性分离…     

Excess Enthalpies of (2,2,4-Trimethylpentane or Cyclohexane) + Methyl tert-Butyl Ether + tert-Amyl Methyl Ether at 25°C

Microcalormetric measurements of excess molar enthalpies at 25°C are reported for two ternary mixtures 2,2,4-trimethylpentane + methyltert-butyl ether +tert-amyl methyl ether and cyclohexane + methyltert-butyl ether +tert-amyl methyl ether. Smooth representations of the results are presented and used to construct constant-enthalpy contours on Roozeboom diagrams. Comparisons of the experimental results with estimates based on the Flory theory of mixtures are also described.     

Synthesis of Ethyl Methyl Ether Over Solid Acid Catalysts

The alkylation of methanol by triethylamine to form ethyl methyl ether was studied in the temperature range 310-330°C using γ-alumina and silica-aluminas differing in their silica content. The effect of treating γ-alumina with hydrochloric and boric acid on the reaction rate was also investigated. The results obtained for ether formation over γ-alumina show that the reaction is first order for methanol and zero orde for triethylamine. Alumina-H₃BO₃ was found to be the most active catalyst whereas alumina-HCl is the least active towards ether formation. The activity of silica-alumina is proportional to its silica contents.     

Determination of Trace of Methyl tert-Butyl Ether in Water Using Liquid Drop Headspace Sampling and GC

The possibility of applying headspace microextraction into a single drop of solvent for the determination of methyl tert -butyl ether in aqueous solutions has been demonstrated. A drop of benzyl alcohol is used for extraction. The analyte is extracted by suspending a 1.8 μL extracting drop directly from the tip of a microsyringe fixed above an extraction vial with a septum such that the needle passes through the septum and the needle tip is positioned above the surface of the solution. After the extraction is finished, the drop is retracted back into the needle and injected directly into a GC column. Optimization of experimental variables (time, temperature, stirring rate and ionic strength of the solution) with respect to the extraction efficiency was investigated. The calibration range for methyl tert-butyl ether was 0.01–10 ppm and the detection limit 7 ppb. The relative standard deviation for 0.1 ppm methyl tert -butyl ether in water was 5.5%.     

轻质烃类中微量甲醇、甲基叔丁基醚等含氧化合物的测定

在乙烯厂生产中微量含氧化合物的测定非常重要,含氧化合物的存在可引起催化剂中毒,致使生产不能长周期运行。对乙烯、丁烯-1中含氧化合物的测定已有报道。但随着仪器和数据处理设备的更新有些缺陷就显现出来。近年来,毛细管色谱柱在含氧化合物的测定上也得到应用,但所使用的极性柱对甲醇、甲基叔丁基醚（MTBE）等含氧化合物分析时常有C3,C4和C5等烃类的干扰,在分析实际样品时会有合峰出现,无法得到准确结果。本文采用超强极性的LOWOX色谱柱,可以排除轻质烃类的干扰,降低检出限。     

Study of the Surface Tensions of Binary Mixtures of Isomeric Chlorobutanes with Methyl tert-Butyl Ether

In the present work we report experimental surface tensions for binary mixtures of isomeric chlorobutanes with methyl tert-butyl ether from 283.15 to 303.15 K, measured with a drop volume tensiometer. From these experimental data the corresponding surface tension deviations were calculated and correlated using a Redlich-Kister type polynomial. Finally, we include the calculation of excess surface compositions for all of the mixtures from 288.15 K to 308.15 K.     

A Sensitive Method for Methyl tert-Butyl Ether Analysis in Water Samples by a New HS-SPME Vial and GC

In this study, a new sample vial has been designed for the extraction and determination of methyl tert-butyl ether (MTBE) in water samples by headspace solid-phase microextraction method. The special feature of this new vial is cooling the HS above the aqueous sample by cold water stream for maximum analyte absorption on SPME fiber coating. The analysis was by a gas chromatograph equipped with flame ionization detector and a capillary column (CP-sil 13 CB). Some significant variables affecting the extraction procedure were optimized. By use of divinylbenzene/carboxen/polydimethylsiloxane fiber, a sample volume of 10 mL, stirring rate of 1,000 rpm, salt concentration of 24%, extraction time of 15 min and extraction temperature of 83 °C, detection limit of 0.022 μg L⁻¹ and a good linearity (R ² = 0.998) in a calibration range of 0.1–400 μg L⁻¹ were achieved. The relative standard deviation for triplicate runs ranged between 6 and 8%. The method could be applied to the analysis of trace levels of MTBE in various water samples.

     

A Sensitive Method for Methyl tert-Butyl Ether Analysis in Water Samples by a New HS-SPME Vial and GC

In this study, a new sample vial has been designed for the extraction and determination of methyl tert-butyl ether (MTBE) in water samples by headspace solid-phase microextraction method. The special feature of this new vial is cooling the HS above the aqueous sample by cold water stream for maximum analyte absorption on SPME fiber coating. The analysis was by a gas chromatograph equipped with flame ionization detector and a capillary column (CP-sil 13 CB). Some significant variables affecting the extraction procedure were optimized. By use of divinylbenzene/carboxen/polydimethylsiloxane fiber, a sample volume of 10 mL, stirring rate of 1,000 rpm, salt concentration of 24%, extraction time of 15 min and extraction temperature of 83 °C, detection limit of 0.022 μg L^?1 and a good linearity (R ² = 0.998) in a calibration range of 0.1–400 μg L^?1 were achieved. The relative standard deviation for triplicate runs ranged between 6 and 8%. The method could be applied to the analysis of trace levels of MTBE in various water samples.     

Dimethyl Ether—Reforming Catalysts for Hydrogen Production

This article reviews our recent works on dimethyl ether steam reforming (DME SR) over nanocomposite catalysts of copper-based spinel oxide and solid-acid catalyst. A series of Cu-based spinels was prepared by citric acid complexation method and their catalytic performance was studied in terms of activity, selectivity, and stability. The influence of preparation conditions, such as calcination temperature, reduction temperature, and chemical composition, and reforming conditions, such as steam-to-carbon ratio and reaction temperature, was systematically studied. Effect of type of solid-acid catalyst was also reported. Zeolite-based composites and alumina-based ones are highly active in temperature ranges of <300 °C and >300 °C, respectively. The composite of CuFe₂O₄ and alumina treated thermally in air at 700–800 °C exhibited excellent activity and stability in DME SR. Upon H₂ reduction, phase separation of copper spinel to metallic copper nanoparticles and host oxides proceeds. The high dispersion of the Cu particles (Cu¹⁺-rich surface of ca. 70%) on the hosts, and the strong chemical interaction between them could be observed. The H₂-rich reformate (>70% H₂) could be attained for longer than 800 h at 375 °C, showing the good potential for practical use in H₂ and fuel cell applications. Doping Ni to CuFe₂O₄ significantly enhanced the stability of the catalyst, in accordance with the alloying effect. Regeneration of the degraded catalysts could be obtained by simple heat-treatment since carbon deposits were removed, and spinel structures were reconstructed.     

Development of Efficient Zeolite-Containing Catalysts for Petroleum Refining and Petrochemistry

The role of various technologies in oil refining and petrochemistry changes due to amendments to the requirements for fuel quality. The development of these technologies requires the improvement of catalysts. This paper outlines main procedures for the production of dealuminated zeolites, as well as the advantages and drawbacks of these procedures. Catalysts with a high desulfurizing ability for the hydrocracking of vacuum gas-oil to gasoline and diesel fractions and catalysts for the isomerization of fuel hydrocarbons can be prepared using ultrastable Y-type zeolites. The results of testing of zeolite-containing binary catalytic systems in Fischer-Tropsch synthesis are presented.     

Structure and Reactivity of the Radical Cations of Methyl tert-Butyl Ether in Condensed Phase: An ESR and Quantum Chemical Study

The structure of the methyl tert-butyl ether (MTBE) radical cation and mechanism of its thermal and photochemical reactions in irradiated freons (CFCl₃, CF₂ClCFCl₂, and CF₃CCl₃) were studied. Radical products of MTBE radiolysis in the liquid phase were investigated by the spin trapping technique. The quantum-chemical calculations of the structure of MTBE radical cations and products of their transformations were carried out by density functional theory (DFT) and ab initioMP2 methods. The primary MTBE radical cations are stabilized in dilute solutions in CFCl₃and CF₃CCl₃. The ion–molecule reaction (proton transfer from the radical cation) was found to occur in concentrated solutions in CFCl₃immediately during irradiation. The action of light ( = 436 to 546 nm) at 77 K on the MTBE radical cation in CFCl₃and CF₃CCl₃matrices results in intramolecular migration of the methyl group to yield the distonic radical cation (CH₃)₂ ^.CO⁺(CH₃)₂. The primary MTBE radical cations undergo an irreversible transformation with methane elimination resulting in formation of the 2-methoxypropene radical cation ^.CH₂=⁺(₃)₃in CFCl₃and CF₃CCl₃matrices in the temperature range 110–130 K. In the case of CF₂ClCFCl₂matrix, such a reaction occurs during irradiation at 77 K. Using the spin trapping technique, it was shown that the liquid-phase radiolysis of the neat ether resulted in the formation of fragmentation products (^.CH₃,CH₃^., and t-BuO^. radicals) from the primary radical cations, as well as the products of their rearrangements and ion–molecule reactions.     

Conjugate Conversion of Methanol and Lower Alkanes C3-C4 on Zeolite-Containing Catalysts

Simultaneous conversion of methanol and lower alkanes C₃-C₄ on high-silica zeolites of ZSM-5 type of various compositions (SiO₂/Al₂O₃ 30, 50, 90) was studied. The catalytic activity of zeolite catalysts and their physicochemical properties (acidity, sorption capacity, and pore structure) were evaluated.