水在甲缩醛与三聚甲醛合成聚甲氧基二甲醚中的作用研究

聚甲醛二甲醚（PODE）添加到柴油中,可以减少不完全燃烧造成的空气污染。在不同温度下,以HZSM-5为催化剂,三聚甲醛（TOX）和甲缩醛（DMM）为原料,加入不同含量的水以模拟甲醛原料水含量（0~10 wt%）对PODE合成的影响。结果表明：在相同的甲醛/甲缩醛摩尔比的条件下,随着TOX中水含量的增加,TOX和DMM的转化率变化不明显,而产物中PODE_3-8的含量则明显降低,从无水时的39.55%减少到3 wt%水时的32.09%,10 wt%水时的23.66%。同时,发现MeOH等的含量随着含水量的增加明显增加,由无水时的0.53%增加至3wt%水时的2.82%和10 wt%时的4.42%。进一步研究表明:反应体系中的水与MeOH的生成密切相关。通过物料衡算证实PODE合成过程中的水主要与DMM反应生成MeOH。      

HZSM-5分子筛用于合成聚甲醛二甲基醚

以磷酸二氢铵为前驱体,使用浸渍法制备了一系列不同磷含量改性的HZSM-5分子筛,并结合X射线衍射、N2吸附和氨程序升温脱附等表征结果探讨了催化剂硅/铝比、粒径尺寸、晶体结构、孔结构及表面酸性对其催化甲醇和三聚甲缩反应生成聚甲醛二甲基醚(PODEn)反应性能的影响,同时与商业催化剂进行了比较.结果表明,硅铝比为50,粒径尺寸为5μm,P2O5含量较低(0～6%)的HZSM-5分子筛表现出较高的催化活性和PODEn选择性.在130℃,原料甲醇和三聚甲醛的质量比为2:1的优化条件下反应时,三聚甲醛转化率可达到95.2%,PODEn(n=2～5)的选择性为62.9%,略好于商业催化剂.     

合成聚甲醛二甲基醚反应热力学的理论计算

采用密度泛函理论(DFT)方法在B3LYP/6-31＋G(d,p)水平上对聚甲醛二甲基醚(PODE)系列化合物进行了全优化和振动分析计算, 获得了该系列化合物的最优构型及热力学函数值. 通过设计等键反应计算了PODE的生成热, 并进一步计算了生成PODE的反应平衡常数及转化率, 进而判断这些反应的热力学可行性.     

二氧化碳和甲醇合成碳酸二甲酯研究进展

本文综述了以二氧化碳和甲醇为起始原料合成碳酸二甲酯（DMC）的研究状况。提出以CO₂和甲醇直接合成DMC,不仅对合成化学,碳资源利用和环境保护具有重大意义,而且可使生产成本显著降低,它是发展DMC生产的一个具有很大潜力的方面。     

Intrinsic Kinetics of Dimethyl Ether Synthesis from Syngas

The intrinsic kinetics of dimethyl ether (DME) synthesis from syngas over a methanol synthesis catalyst mixed with methanol dehydration catalyst has been investigated in a tubular integral reactor at 3-7MPa and 220-260℃. The three reactions including methanol synthesis from CO and H2, CO2 and H2, and methanol dehydration were chosen as the independent reactions. The L-H kinetic model was presented for dimethyl ether synthesis and the parameters of the model were obtained by using simplex method combined with genetic algorithm. The model is reliable according to statistical analysis and residual error analysis. The synergy effect of the reactions over the bifunctional catalyst was compared with the effect for methanol synthesis catalyst under the same conditions based on the model. The effects of syngas containing N2 on the reactions were also simulated.     

Kinetics of Dimethyl Carbonate Synthesis From Ethylene Carbonate and Methanol Using Alkali-Metal Compounds as Catalysts

Dimethyl carbonate (DMC) was synthesized by the ester exchange reaction of ethylene carbonate and methanol. K₂ CO₃ , KOH, LiOH and NaOH were used as catalysts for DMC synthesis and their catalytic abilities were compared in terms of kinetics. LiOH showed the best reaction rate among the catalysts. The rate constant was estimated to be 0.02538 (dm 3 /mol) 0.21 /min at 298 K.     

Kinetics of Reaction between Magnesium Hydroxide and Dimethyl Phosphite

The kinetic of the reaction between magnesium hydroxide and dimethyl phosphite in nitrobenzene was studied.     

聚甲醛结晶动力学研究

用解偏振光强法和差示扫描量热法（ＤＳＣ）分别研究了聚甲醛和聚甲醛助剂Ｐ的等温结晶动力学和非等温结晶动力学。探讨了助剂Ｐ对聚甲醛的结晶成核作用。     

铁锆复合氧化物催化甲醇与CO2直接合成 DMC反应性能

采用溶胶-凝胶法制备的铁锆复合氧化物催化甲醇与CO2直接合成碳酸二甲酯（DMC）反应,其催化活性远高于氧化铁和氧化锆,当铁锆摩尔比为5：1时,其催化活性是氧化锆的2倍。利用XRD、XPS、IR、TPD和N2物理吸附-脱附等技术对催化剂进行了表征。结果表明,氧化铁主要以六方晶相的α-Fe2O3形式存在,氧化锆主要以四方晶相存在,铁锆之间发生了相互作用,使铁锆复合氧化物表面L酸增强和少量B酸产生。L酸的增强和B酸的产生是催化剂催化活性增加的主要原因,并对催化剂的催化作用机理进行了探讨。     

Promotion of Ionic Liquid to Dimethyl Carbonate Synthesis from Methanol and Carbon Dioxide

Introduction Dimethyl carbonate (DMC) is an important carbon-ylating and methylating agent substituting dimethyl sul-fate and toxic phosgene, and an intermediate for higher carbonates and carbamates.1 In addition, it is also a promising octane enhancer.2 The widely used method of its preparation is the oxidative carbonylation of metha-nol by carbon monoxide with copper(II) or palladium(II) catalysts.3 Recently, the utilization of carbon dioxide as the raw material for DMC synthesis has bee…     

利用Wittig反应合成苯乙烯醚

醛(1)与ROCH=PPh3在混合碱(DBU/K2CO3)的存在下发生Wittig反应,合成了4个苯乙烯醚(3a~3d);3经水解合成了比1延长一个碳的醛,其结构经1HNMR,IR,MS和元素分析表征。     

New Synthesis of (±)-Cherylline and Mono- and Dimethyl Ethers

The synthesis of 4-aryl-1,2,3,4-tetrahydroisoquinolines is achieved via the ether rearrangement methodology. Subsequent reactions yielded cherylline and ether derivatives of amaryllidaceac alkaloids.     

Research Progress in the Direct Synthesis of Dimethyl Carbonate from CO2 and Methanol

The direct synthesis of dimethyl carbonate (DMC) from CO₂ and methanol is one attractive way for the reduction of greenhouse gas emission and the utilization of carbon resources. Recent progress in the direct synthesis of DMC from CO₂ and methanol is reviewed with the focus on the catalyst systems, including organic metal compounds catalyst, base catalyst, acetate catalyst, metal oxide and supported metal oxide catalysts, heteropolyacid catalyst and photocatalyst. Moreover, the application of supercritical system, ionic liquid system, electrochemical system, membrane reactor and nitriles hydration in the direct synthesis of DMC are also introduced. Finally, future research direction in this area is proposed.     

二氧化碳和甲醇直接合成碳酸二甲酯的研究进展

碳酸二甲酯是一种重要的绿色化工原料,二氧化碳和甲醇直接合成碳酸二甲酯是一种绿色合成方法.本文介绍了近年来此方法的催化剂及其催化机理研究的进展,讨论了不同催化体系设计的理论基础和催化剂的作用机理,并对助催化剂和吸水剂以及反应条件对催化剂活性和选择性的影响进行了评述.     

在改性高岭土催化剂上甲醇脱水生成二甲醚的动力学考察

采用积分反应器,考察了常压下在改性高岭土（ＭＫ）催化剂上甲醇脱水生成二甲醚的反应动力学,根据Ｌａｎｇｍｕｉｒ均匀吸附理论,采用Ｒ－Ｅ机理,推断吸附的甲醇分子与气相主体中的甲醇分子发生的表面反应为速率控制步骤（ＲＤＳ）,得到双曲线型动力学方程为：ｒ＝ｋｓｂＭｐＭ＾２／（１＋ｂＭｐＭ＋ｂｐＥ）ｒ为反应速率,ｋｓ为反应速率常数,ｂＭ为甲醇的吸附平衡常数,ｂ为二甲醚和水的吸附平衡常数之和,ｐＭ、ｐＥ分别为     

Efficient Synthesis of Dimethyl Ether from Methanol in a Bifunctional Zeolite Membrane Reactor

A sandwich FAU–LTA zeolite dual‐layer membrane has been developed and used as a catalytic membrane reactor for the synthesis of dimethyl ether (DME). In the top H‐FAU layer with mild acidity, methanol is dehydrated to DME. The other reaction product, water, is removed in situ through a hydrophilic Na‐LTA layer, which is located between the porous alumina support and the H‐FAU top layer. The combination of mild acidity with the continuous removal of water results in high methanol conversion (90.9 % at 310 °C) and essentially 100 % DME selectivity. Furthermore, owing to the selective and continuous removal of water through the Na‐LTA membrane, catalyst deactivation can be effectively suppressed.     

甲醇直接气相氧化羰基化合成碳酸二甲酯

碳酸二甲酯(DMC)是一种重要的绿色有机合成中间体.合成DMC有多种方法,甲醇直接气相氧化羰基化法对设备腐蚀小,产物易分离,原料易得,有着诱人的工业化前景.本文综述了甲醇直接气相氧化羰基化合成DMC的研究进展,包括反应条件的影响,催化剂的选择,反应机理及动力学的研究.针对反应副产物水会造成催化剂快速失活、设备腐蚀等问题,提出将二甲醚引入反应体系,通过耦合二甲醚水解反应消除水引起的负面效应,改善催化剂的稳定性.     

Synthesis of Aryl Ethers via a Sulfonyl Transfer Reaction

A general synthesis of aryl ethers from primary and secondary alcohols and aryl mesylates is presented. The reaction proceeds via a sulfonyl-transfer mechanism. In this paper, we compare the sulfonyl transfer reaction to Mitsunobu ether formation. The reaction can be employed in a multistep synthesis where the aryl mesylate is used as a phenol protecting group and then as an activating group for ether formation. This protecting/activating group strategy is demonstrated using raloxifene as the target.     

New Strategies on Green Synthesis of Dimethyl Carbonate from Carbon Dioxide and Methanol over Oxide Composites

Dimethyl carbonate is a generally used chemical substance which is environmentally sustainable in nature and used in a range of industrial applications as intermediate. Although various methods, including methanol phosgenation, transesterification and oxidative carbonylation of methanol, have been developed for large-scale industrial production of DMC, they are expensive, unsafe and use noxious raw materials. Green production of DMC from CO₂ and methanol is the most appropriate and eco-friendly method. Numerous catalysts were studied and tested in this regard. The issues of low yield and difficulty in tests have not been resolved fundamentally, which is caused by the inherent problems of the synthetic pathway and limitations imposed by thermodynamics. Electron-assisted activation of CO₂ and membrane reactors which can separate products in real-time giving a maximum yield of DMC are also being used in the quest to find more effective production method. In this review paper, we deeply addressed green production methods of DMC using Zr/Ce/Cu-based nanocomposites as catalysts. Moreover, the relationship between the structure and activity of catalysts, catalytic mechanisms, molecular activation and active sites identification of catalysts are also discussed.