A new method for the preparation of peroxyacetic acid using solid superacid catalysts

A new method for the preparation of peroxyacetic acid from acetic acid and hydrogen peroxide in the presence of solid superacids as a catalyst under mild conditions has been proposed. The preparation of peroxyacetic acid could be carried out in a batchwise operation as well as in a flow-system operation. Nafion-H was found to be active and very stable catalyst for the preparation of peroxyacetic acid and to be regenerated without the loss of catalytic activity.     

乙炔法合成醋酸乙烯催化剂载体表面羧基与羰基作用机理的研究

比较了硝酸、硫酸、过氧乙酸改性对载体比表面积、孔结构、pH值以及载体表面基团的影响. 研究了过氧乙酸(PAA)改性条件对催化剂活性的影响. 改性提高了活性炭表面羧基和羰基的含量, 由在最佳PAA改性条件下制备的乙炔法合成醋酸乙烯催化剂生产能力比未经过氧乙酸改性活性炭制备的催化剂提高了14.58%. 得到了过氧乙酸改性后活性炭表面羧基和羰基总量(m)和合成醋酸乙烯催化剂生产能力(P)之间的关系为P＝1.83＋2.26×10－3×e3.17m, 并讨论了催化剂表面羧基与羰基提高催化剂活性的机理.     

Highly active catalyst for vinyl acetate synthesis by modified activated carbon

A new zinc acetate catalyst which was prepared from modified activated carbon exhibited extreme activity towards the synthesis of vinyl acetate.The activated carbon was modified by nitric acid,vitriol and peroxyacetic acid(PAA).The effect on specific area, structure,pH and surface acidity groups of carriers by modification was discussed.Amount of carbonyl and carboxyl groups in activated carbon was increased by peroxyacetic acid treatment.The productivity of the new catalyst was 14.58%higher than that of...     

Supported Polyoxometalate Catalysts for Oxidation Processes

Procedure for synthesis of heterogeneous polyoxometalate catalysts based on sodium vanadomolybdophosphate or sodium peroxo vanadomolybdophosphate and supported by AV-17-8ChS anion exchanger was developed, their synthesis was performed, and the catalysts were studied in the course of oxidation of ferulic acid with peroxyacetic acid. A chromato-mass-spectrometric analysis was used to determine the main oxidation products, the composition of which agrees with the suggested conversion mechanism of ferulic acid in the process under study. It was shown that the regeneration of a spent catalyst via treatment with peroxyacetic acid can restore its original activity.     

The role of Acid catalysis in the baeyer-villiger reaction. A theoretical study

Quantum mechanical calculations at the B3LYP/6-311+G(d,p) level have examined the overall mechanism of the Baeyer-Villiger (BV) reaction with peroxyacetic acid. A series of reactions that include both the addition step and the subsequent alkyl group migration step included ketones, acetone, t-butyl methyl ketone, acetophenone, cyclohexyl methyl ketone, and cyclohexyl phenyl ketone. The combined data suggested that the first step for addition of the peroxyacetic acid oxidation catalyst to the ketone carbonyl to produce the Criegee or tetrahedral intermediate is rate-limiting and has activation barriers that range from 38 to 41 kcal/mol without the aid of a catalyst. The rate of addition is markedly reduced by the catalytic action of a COOH functionality acting as a donor-acceptor group affecting both its proton transfer to the ketone C═O oxygen in concert with transfer of the OOH proton to the carboxylic acid carbonyl. The second or alkyl group migration step has a much reduced activation barrier, and its rate is not markedly influenced by acid catalysis. The rate of both steps in the BV reaction is greatly influenced by the catalytic action of very strong acids.     

四正丁基溴化铵催化氧化柴油中硫化物的研究

研究了相转移催化剂四正丁基溴化铵催化氧化柴油中硫化物的效果。结果表明,较适宜的脱硫条件是:反应时间60 min,柴油/氧化体系质量比1∶1,过氧乙酸/乙酸酐质量比1∶2,四正丁基溴化铵用量为柴油质量的0.1%,反应温度45℃。反复使用氧化体系可使柴油脱硫率达到95.3%。初步探讨了相转移氧化反应机理,认为氧化产物砜的极性是产生脱硫效果的直接原因。     

Cr2O3-Co3O4／SiO2对十八醇氧化生成十八酸反应的催化性能

 制备了一系列不同Cr／Co比例的Cr2O3－Co3O4／SiO2催化剂，并用XRD，FT－IR和BET等手段对催化剂进行了表征；考察了催化剂对十八醇氧化生成十八酸反应的催化性能，及反应条件（反应温度和反应时间）对催化性能的影响，确定了最佳反应条件．结果表明，金属硝酸盐在773K焙烧后转变成相应的氧化物并负载于二氧化硅上．Cr2O3－Co3O4／SiO2催化剂对十八醇氧化反应有很高的催化活性，十八酸选择性最高可达99．93％，收率可达52．44％．Cr2O3－Co3O4／SiO2催化剂的活性明显高于单一的Cr2O3／SiO2或Co3O4／SiO2催化剂     

一种无机-有机高分子杂化催化剂Pd(0)-CS/MCM-41的制备及其性能研究

将天然高分子聚合物壳聚糖负载到MCM-41介孔分子筛上,再在室温与氯化钯乙醇溶液作用,制得了一种无机-有机天然高分子杂化催化剂Pd(0)-CS/MCM-41,并利用XPS、FTIR、XRD、热重等手段对其进行了表征。以碘代苯与丙烯酸的Heck芳基化反应考察了所得催化剂的催化性能。结果表明,催化剂具有较高的催化活性和良好的重复使用性能,催化剂在氮气保护下能有效地催化碘代苯与丙烯酸的Heck反应,高产率地得到反式肉桂酸。经8次重复使用后,肉桂酸的产率仍达80%以上。     

Kinetics of Formation of Peroxyacetic Acid

The kinetics of the reaction of acetic acid with hydrogen peroxide, leading to peroxyacetic acid, were studied at various molar reactant ratios (AcOH-H₂O₂ from 6 : 1 to 1 : 6) at 20, 40, and 60°C and sulfuric acid (catalyst) concentrations of 0 to 9 wt %. The reaction is reversible, and the equilibrium constant decreases as the temperature rises: K = 2.10 (20°C), 1.46 (40°C), 1.07 (60°C); Δ_r H ⁰ = − 13.7±0.1 kJ mol⁻¹, Δ_r S = −40.5±0.4 J mol⁻¹ K⁻¹. The maximal equilibrium concentration of peroxyacetic acid (2.3 M) is attained at 20°C and a molar AcOH-to-H₂O₂ ratio of 2.5 : 1. The rate constants of both forward and reverse reactions increase with increase in sulfuric acid concentration from 0 to 5 wt %. Further raising the catalyst concentration does not affect the reaction rate. The reaction mechanism is discussed.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 7, 2005, pp. 1187–1193.Original Russian Text Copyright © 2005 by Dul’neva, Moskvin.     

The electronic structure of peracids. Functional models for cytochrome p-450

An extensive set of ground state ab initio and semiempirical molecular orbital calculations has been performed on both peroxytrifluoroacetic and peroxyacetic acids. The equilibrium geometry of peroxyacetic acid was calculated with the STO-3G and MINDO/3 methods, and peroxide rotational barriers for both peracids were obtained with STO-3G and PCILO. Extended basis set calculations with the 6-31G^** basis were performed for both peracids to compare the electronic structures of these two compounds. Electrostatic potential maps in the region of the peroxide bonds of both peracids were also calculated using INDO wavefunetions. These results are discussed with respect to the enhanced reactivity of peroxytrifluoracetic acid relative to peroxyacetic acid and the nature of the oxygen electrophilicity in these compounds and by analogy in cytochrome P-450, for which peroxytrifluoroacetic acid is considered to be an effective chemical model.     

己内酰胺三氟甲磺酸离子液体中甲苯的区域选择性硝化

以三氟甲磺酸和己内酰胺为原料制备了一种新型离子液体己内酰胺三氟甲磺酸([CP]OTf),用1HNMR、FTIR对其结构进行了表征。并把[CP]OTf作为催化剂和溶剂,用于催化甲苯的硝化反应。借助气相色谱研究了[CP]OTf的用量、硝化温度、反应时间、硝酸浓度和离子液体的重复使用等因素对甲苯硝化反应区域选择性和产率的影响。结果表明：在反应温度55℃,反应时间6h,甲苯与95%浓硝酸的摩尔比为1：1,离子液体用量占甲苯摩尔数的15%时,产物中邻对位硝基甲苯摩尔比为1.12,较浓硫酸催化硝化的相应值(1.67)显著降低,硝基甲苯的产率达到78.41%,[CP]OTf表现出了优良的催化活性和对位选择性。[CP]OTf) 重复使用5次,其催化活性及对位选择性变化很小。     

溴化苄的合成工艺研究

以二苄醚和氢溴酸为原料,SO42-/TiO2为催化剂,环已烷为带水剂,合成了溴化苄。实验分别考察了反应物摩尔比、反应时间、反应温度、带水剂的用量,催化剂的使用量等因素对溴化苄收率的影响,得出了用此方法合成溴化苄的最佳反应条件:氢溴酸与二苄醚的摩尔比为3:1,反应时间为8 h,环已烷为8 mL,SO42-/TiO2催化剂的用量为0.5 g,溴化苄的收率达80.2%。     

Cationic polymerization of formaldehyde in liquid carbon dioxide. Part II: A kinetic study of the polymerization

The kinetic behavior on the polymerization of formaldehyde with and without acidic catalyst, in liquid carbon dioxide, in the temperature range of 30 to 50°C. was investigated. In the polymerization without catalyst both the polymer yield and the degree of polymerization increased with reaction time and also with rising temperature. With acidic catalyst, such as acetic acid and dichloroacetic acid, both the polymer yield and the degree of polymerization increased more than that in the polymerization without catalyst. The overall rate of polymerization with and without acidic catalyst was expressed by the first-order rate equation with respect to monomer concentration. From the results it was concluded that the polymerizations belonged to a type of successive polymerization with rapid initiation and no termination. The rate constant and the activation energy of each elementary process of polymerization were estimated on the basis of the results.     

氨基磺酸催化合成-萘乙酸甲酯

氨基磺酸能够代替硫酸作为酯化催化剂。在氨基磺酸存在下,由1-萘乙酸和甲醇酯化合成了高收率的1-萘乙酸甲酯。研究了反应的影响因素和催化剂的重复使用性能。当1-萘乙酸、甲醇和氨基磺酸的质量比为1:10:1,回流反应5h时,酯收率达97.5%。     

己内酰胺对甲基苯磺酸离子液体中甲苯的选择性硝化反应

制备了一种低毒性的新型Brφnsted酸性离子液体己内酰胺对甲基苯磺酸([CP]PTSA)作为催化剂和溶剂,用于催化甲苯与等摩尔的体积分数为67%HNO3的硝化反应,用核磁共振、红外光谱对[CP]PTSA的结构进行了表征。考察了不同的反应温度、反应时间及催化剂用量等因素对甲苯硝化反应的产率和对位选择性的影响。得出最佳反应条件为:温度55℃,时间24h,离子液体用量占甲苯摩尔分数的20%,产物硝基甲苯中邻与对位异构体质量比为1.2,较硝-硫混酸硝化的相应比值(1.6)显著降低,硝基甲苯的产率达37.1%。离子液体重复使用4次仍表现出较好的催化活性及对位选择性。用质谱分析对回收的离子液体的结构进行了表征。结果表明,该离子液体的结构稳定。     

Nicotinic acid functionalized organomodified silica as an efficient heterogeneous catalyst for the synthesis of benzoyl fumarate

A new hybrid catalyst has been developed by incorporating nicotinic acid onto an organomodified silica. The catalyst was applied as a heterogeneous catalyst for the synthesis of benzoyl fumarate. The reactions work well in the presence of 20 wt % of the catalyst at room temperature to produce the desired products in high yield. The catalyst could be recovered and reused without appreciable change in activity.     

稻壳碳基固体酸催化剂的制备及在木糖脱水制备糠醛反应中的催化性能

以工业生产中碱法溶硅剩余的稻壳残渣为碳源,采用硫酸磺化法制备稻壳碳基固体酸催化剂,考察了其催化木糖脱水制备糠醛的性能.采用红外光谱、元素分析及表面酸浓度测定等手段对催化剂进行了表征.对固体酸催化剂的制备条件进行了优化,所得催化剂的表面酸浓度可达1.03 mmol/g.以木糖脱水制备糠醛为模型反应,考察了溶剂类别、反应温度和反应时间对固体酸催化剂催化性能的影响.实验结果表明,以二甲基亚砜(DMSO)为反应溶剂效果优于水,并且随着反应温度的升高和反应时间的延长,反应产率逐渐增加,最高可达75.8%.此外,还对催化剂的循环性能进行了研究,探讨了其失活原因和再生方法.     

硫酸氢钠催化合成富马酸二乙酯的研究

以富马酸和乙醇为原料,硫酸氢钠作催化剂合成富马酸二乙酯。用正交实验讨论了最佳合成条件:反应温度130℃,n(乙醇)∶n(富马酸)=4∶1,时间6h,催化剂用量为富马酸质量的5.0%,酯化率达93.5%。该法操作简单,酯化率较高,催化剂可回收利用。     

Ab initio study of the internal rotation in peroxyformic acid

The internal rotation in peroxyformic acid was investigated using the ab initio SCF MO LCAO method with the STO-3G and 4-31G basis-sets and with experimental and optimum values of the geometrical parameters. Both basis sets yield a rather flat double-minimum potential for the COOH torsion, the trans planar form being lightly preferred in comparison with the cis one. The effects on the internal rotation of the geometry relaxation, of the intramolecular hydrogen bond and of the methyl group of peroxyacetic acid are also discussed.     

铌酸催化液相合成乙酸乙酯

报道了铌酸催化乙醇与乙酸的液相酯化反应考察了反应温度、催化剂用量、酸醇比、反应时间对产品乙酸乙酯经的影响。在优化条件下,产品收率棕达８８．０％,选择性为１００％,同时我们采用自制间式反应,对催化剂的稳定性进行了考察,发现铌酸在该实验条件下,能保持较高的稳定性和较高的催化活性。