环己酮肟液相Beckmann重排制己内酰胺研究进展

综述了不使用浓硫酸为催化剂的环己酮肟液相Beckmann重排生产己内酰胺的研究进展。重点介绍了分子筛等固体酸催化剂、烷基化试剂和DMF组成的催化体系、离子液体催化体系、超临界水及超临界CO_2条件下的液相重排新工艺,指出采用新型催化剂的绿色生产工艺,特别是离子液体催化体系具有良好的开发应用前景。     

Vapor phase Beckmann rearrangement of cyclohexanone oxime over metal pillared ilerite

The vapor phase Beckmann rearrangement of cyclohexanone oxime to -caprolactam has been studied using various metal pillared ilerites (M-ilerite) as catalysts. Ta- and Nb-ilerite exhibited high catalytic activities for the vapor phase Beckmann rearrangement. The oxime conversion over Ta-ilerite reached up to 98.9% with the lactam selectivity of 96.7% at 350°C. FT-IR and NH₃-TPD results revealed that the excellent catalytic performance of Ta- and Nb-ilerite should be ascribed to a large number of hydroxyl groups of the catalyst and their relatively weak acidity.     

A modified mixed-acid catalytic system for Beckmann rearrangement of cyclohexanone oxime

ε-Caprolactam (CPL) is mainly produced through Beckmann rearrangement of cyclohexanone oxime catalyzed by oleum in industry nowadays, which suffers the problems like high viscosity and bad mixing, leading to multiple by-products. To this end, a modified mixed-acid catalytic system containing oleum and trifluoroacetic acid (TFA) was proposed to intensify the reaction. The viscosity of the reaction system was studied and the effects of several experimental parameters on the reaction rate and selectivity were also investigated, including oleum/oxime ratio, TFA/oleum ratio, temperature, and SO₃ concentration. Extremely high selectivity (>99.6%) was obtained under all conditions, revealing that by-products in industrial process were mainly formed owing to the insufficient mixing and poor mass and heat transfer rather than experimental parameters. A preliminary mathematical model considering the effect of CPL was developed to predict the reaction rate. These results are helpful to improve the industrial process of CPL production.     

Beckmann rearrangement of cyclohexanone oxime over Silicalite-1: an FT-IR spectroscopic study

The study of cyclohexanone oxime (CEOX) adsorption and reaction into -caprolactam (CPL) by FT-IR spectroscopy was performed with Silicalite-1 (S-1) as a catalyst. Information of both active sites and reaction mechanism of the Beckmann rearrangement was obtained. At low temperature the physical sorption of CEOX on/in S-1 is the most relevant phenomenon. The accessibility of the internal OH’s to the reactant increases at higher temperatures due to an easier diffusion. At 200 °C CEOX molecules present inside the zeolite are in proximity of the most acidic OH groups of S-1, the OH nests. The co-operation of more than one OH site transforms CEOX into -CPL, allowing the right reactant-active site configuration and favouring the stabilisation of the intermediate.     

Synthesis of a novel super-microporous layered material and its catalytic application in the vapor-phase Beckmann rearrangement of cyclohexanone oxime

A novel well-ordered super-microporous layered material, silica-pillared niobic acid, was synthesized by a guest-exchange route and structurally characterized by powder X-ray diffraction (XRD), infrared absorption spectroscopy (IR), thermogravimetric and differential thermal analysis (TG/DTA), transmission electron micrographs (TEM), nitrogen adsorption method and ammonia-temperature-programmed desorption (NH₃-TPD). The obtained silica-pillared layered niobic acid had a supergallery of 1.78 nm, a large BET surface area of 250 m² g⁻¹, and a high thermal stability exceeding 973 K.The pillared layered material was also found to be an efficient solid acid catalyst for the vapor-phase Beckmann rearrangement of cyclohexanone oxime. When 1-hexanol was fed with cyclohexanone oxime, this solid catalyst exhibited a 100% conversion of the oxime with a selectivity of ε-caprolactam beyond 85% at a reaction temperature of 613 K and a WHSV of 0.17 h⁻¹ in terms of cyclohexanone oxime, and there was no significant change of the conversion and selectivity within 6 h.     

Theoretical study on vapour phase Beckmann rearrangement of cyclohexanone oxime over a high silica MFI zeolite

We have studied an activation mechanism of cyclohexanone oxime in a cavity of high silica MFI zeolite by using PIO analysis proposed by Fujimoto et al. DFT calculation reveals that the bond length of N–OH becomes longer when water coordinates on oxygen of oxime. The PIO clearly shows out-of-phase interaction between N and O. This out-of-phase interaction is also observed in the PIO of oxime/MFI zeolite cluster model and weakens the N---O bond. Hydrogen bond of Si–OH of nest silanols to oxime is a trigger of vapour phase Beckmann rearrangement.     

分光光度法测贝克曼重排产物中的微量环己酮肟

采用分光光度法 ,以硫酸铁铵为显色剂测定微量环己酮肟。讨论了吸收波长、显色时间、酸量、氧化剂量和显色剂量等对测量结果的影响 ,通过正交实验确定了最佳显色条件。所测表观摩尔吸光系数为5 .886× 10 3L/ (mol·cm) ,线性范围为 0 .0 5～ 1.75mg/L ,平均加标回收率为 98.3 7%～ 10 9.3 %。     

环己酮肟贝克曼重排制己内酰胺绿色催化研究进展

己内酰胺是一种重要的有机化工原料,其传统的环己酮肟贝克曼重排制己内酰胺是以发烟硫酸为催化剂的生产工艺,存在污染环境、设备腐蚀以及成本高等缺点。综述了环己酮肟贝克曼重排反应制己内酰胺的绿色催化研究进展;介绍了氧化物催化剂、钛硅分子筛催化剂,及离子液体在催化中的应用;氧化物催化剂具有较好的催化活性,但存在寿命短、再生性差的缺点;TS-1型分子筛催化剂成本高,重现性差,工业化生产有待进一步研究;S-1型分子筛催化剂催化性能好,但反应条件较苛刻,使用寿命短;离子液体作为催化剂选择性不高。指出气相重排工艺绿色催化的高硅分子筛,特别是S-1型分子筛,具有较理想的催化效果,进一步提高全硅分子筛催化剂的选择性、延长使用寿命是今后研究的重点。     

离子液体在环己酮肟Beckmann重排反应中的研究进展

己内酰胺（CPL）是一种重要的有机化工原料。传统的环己酮肟贝克曼（Beckmann）重排法制备己内酰胺是以发烟硫酸为催化剂的生产工艺,存在污染环境、腐蚀设备、能源浪费等不足。基于绿色化工理念,本文综述了离子液体用于环己酮肟贝克曼重排反应合成己内酰胺的研究进展,重点阐述了离子液体作为溶剂、催化剂和反应物3种作用方式在Beckmann重排反应中的最新应用,同时针对离子液体与产物分离困难的问题,讨论了目前文献中的解决方法。在此基础上,分析了离子液体用于Beckmann重排反应在未来的研究方向,并指出设计适宜的离子液体结构、调变酸性性能、降低CPL在离子液体中的溶解度是今后的研究重点。     

Organocatalyzed Beckmann rearrangement of cyclohexanone oxime in a microreactor: Kinetic model and product inhibition

The kinetic study of Beckmann rearrangement of cyclohexanone oxime catalyzed by trifluoroacetic acid and acetonitrile in a microreactor is presented in this article. Parametric studies are conducted varying temperature, ratio of trifluoroacetic acid to acetonitrile, and concentration of cyclohexanone oxime. The inhibition effect of ?‐caprolactam in this reaction system is firstly reported. A comprehensive mathematic kinetic model considering the product inhibition effect of caprolactam has been developed in the temperature range of 368–391 K, which agrees well with the experimental results across a broad experimental parameter space. In addition, kinetic study indicates that the esterification of cyclohexanone oxime and transposition reaction of the intermediate are both supposed to be the rate‐determining steps, and in this catalyst system, the ratio of trifluoroacetic acid and acetonitrile mainly influences the reaction rate and the activation energy of the transposition step. The developed model could provide much reliable knowledge for industrial application. © 2017 American Institute of Chemical Engineers AIChE J, 64: 571–577, 2018     

S-1催化环己酮肟气相Beckmann重排反应动力学

目前尼龙6生产中主要采用发烟硫酸催化环己酮肟液相Beckmann重排制己内酰胺,副产大量硫酸铵,而且存在设备腐蚀等问题。采用气相重排法可以克服上述缺点。本工作在以前得到的优化反应条件下,根据实验并采用催化剂失活的Wojciechowski模型获得了S-1催化环己酮肟气相Beckmann重排制己内酰胺反应动力学方程及参数。该模型将催化剂的活性与在线反应时间相关联,进而可以计算任何在线反应时间时催化剂的失活速率,或者根据要求的转化率最低允许值计算催化剂能在线反应的时间。     

P2O5液相催化环己酮肟重排制己内酰胺

研究了以环己酮肟、五氧化二磷(P_2O_5)、二甲基甲酰胺(DMF)组成的反应体系进行Beckmann重排制备己内酰胺工艺,考察了不同溶剂、催化剂用量、温度、浓度及水分含量对重排反应的影响。结果表明,由DMF、P_2O_5、少量水组成的反应体系,当P_2O_5与环己酮肟质量比为(1.0：4.5)～(1.0：5.6),温度为160～170℃,停留时间为0.75～1.00 h时,实现环己酮肟Beckmann重排制己内酰胺,转化率达99.5％以上,选择性达94.5％     

发烟硫酸条件下环己酮肟贝克曼重排工艺进展

综述了环己酮肟在发烟硫酸条件下液相重排生成己内酰胺的相关新工艺、新设备及新技术,并对其进行了概括和分析.     

Effects of acid strength and micro pore size on -caprolactam selectivity and catalyst deactivation in vapor phase Beckmann rearrangement over acid solid catalysts

The vapor phase Beckmann rearrangement of cyclohexanone oxime (CHO) over solid acid catalysts including zeolites was carried out to elucidate the effects of the acid strength and the micropore size of the catalysts on the selectivity of -caprolactam (CL) and the catalyst deactivation rate. It was found that the catalyst deactivation rate was strongly dependent on the acid strength of the acid catalysts. The improvement of catalyst life was achieved by using MFI-type metallosilicates having weak acid sites. The CL selectivity decreased over the acid catalysts with micropores larger than those of the MFI zeolites. Furthermore, using methanol and carbon dioxide as the diluent solvent and diluent gas improved CL selectivity and catalyst life, respectively.     

Beckmann rearrangement of cyclohexanone oxime to ε‐caprolactam in microreactors

Selectivities are presented of the Beckmann rearrangement of cyclohexanone oxime to ε‐caprolactam with oleum for various conditions in three microreactors, viz., Y‐junction, interdigital, and split and recombine mixers, followed by a 50‐cm long microchannel of 250 μm internal diameter. Cyclohexanone oxime is dissolved in cyclooctane, which is inert for oleum. The selectivity is measured in the temperature range of 80–132°C. The concentration range of caprolactam in the reaction mixture is 31–41 wt %, in oleum. The total volumetric flow rate is 0.4 ml/min, whereas the flow rate ratio of ε‐caprolactam/oleum over cyclohexanone oxime/cyclooctane ranges from 0.3 to 3. The selectivities measured with the three microreactors are: 70–99+%, 93–99+%, and 95–99+%, respectively. High ε‐caprolactam concentration (41 wt %), high temperature (110–132°C), and a ratio of free H₂SO₄ to SO₃ of unity have a negative effect on the selectivity. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Beckmann rearrangement of cyclohexanone oxime in a microchemical system: The role of SO3 and product inhibition

The mechanism of Beckmann rearrangement of cyclohexanone oxime in oleum is investigated with a multiphase microchemical system, which is designed to give good control of the reaction temperature and residence time. The influences of SO₃ and caprolactam concentrations in oleum on the conversion are investigated. The results indicate that SO₃ acts as the catalyst and caprolactam plays a product inhibition role. Based on these results and previous mechanism analysis, an equilibrium relation between protonated caprolactam and caprolactam hydrogen sulfate is proposed and the equilibrium constants at 70, 80, and 90^°C are gained. According to the equilibrium, the lowest acid/oxime molar‐ratio of 0.5 for sufficient conversion (>99%) at 100^°C has been provided. This quantitative mechanism analysis gives the reason for the negative influences of higher caprolactam concentration and lower temperature on the reaction conversion, which is very useful for the optimization and reliable design of Beckmann rearrangement processes. © 2011 American Institute of Chemical Engineers AIChE J, 58: 3156–3160, 2012     

Vapour phase beckmann rearrangement of cyclohexanone oxime over MEL type zeolites

The vapour phase Beckmann rearrangement of cyclohexanone oxime to -caprolactam is reported over different MEL zeolites viz., silicalite-2, titanium silicate-2 (TS-2), ZSM-11 and alumino-titanium-silicate (Al-TS-2) and fumed silica. TS-2 exhibits 100% conversions with lactam selectivities close to 90%. The titanium containing analogs are also more resistant to deactivation than the parent zeolites. The conversion of cyclohexanone oxime and selectivity for -caprolactam increase with temperature. The selectivity for -caprolactam increases with the duration of run at all the temperatures.     

Activity of modified SnO2 catalysts for acid-catalysed reactions

The effect of Lewis and Brønsted acid modification on the catalytic behaviour of SnO₂ was studied. Modified AlCl₃, FeCl₃, ZnCl₂ and H₂SO₄ were used for this purpose. Catalytic activity was tested for Friedel–Crafts alkylation, acylation and Pechmann condensation. It was observed that the alkylation activity of SnO₂ was improved upon treatment with Lewis acids and Brønsted acids. However the acylation activity was observed only when SnO₂ was treated with H₂SO₄. Moderate improvement in the activity for Pechmann condensation reaction was observed in the case of all the modified catalysts. It was inferred that this method of modification resulted in an increase in acid strength as well as acidity of the parent oxide catalyst. © 1998 SCI     

B2O3/ZrO2 for Beckmann rearrangement of cyclohexanone oxime: optimizing of the catalyst and reaction atmosphere

Optimization of zirconia-supported boria catalyst for the Beckmann rearrangement of cyclohexanone oxime was studied with the control of three preparation parameters: the temperature of support pre-calcination (PCT: 110–700°C), the calcination temperature for the catalyst activation (CAT: 250–600°C), and the load level of boria. When the CAT is limited no higher than 500°C, the lactam yield increases with the PCT and shows maximum numbers with PCT=350–500°C. This effect of PCT seems not important for the catalyst preparation when the late catalyst activation is done with CAT as high as 600°C. Catalyst preparations with CAT=600°C agrees with the model that the optimized catalyst has, on the average, about two surface overlayers of boria on the support. Another part of this work focused on effects of the reaction solvents and carrier gases. A remarkable benefit for the lactam synthesis is observed with proper combination of the solvents and carrier gases.