106-89-8Relevant articles and documents
Mechanism of olefin epoxidation in the presence of a titanium-containing zeolite
Danov,Krasnov,Sulimov,Ovcharova
, p. 1809 - 1812 (2013)
The effect of the nature of a solvent on the liquid-phase epoxidation of olefins with an aqueous solution of hydrogen peroxide over a titanium-containing zeolite is studied. Butanol-1, butanol-2, propanol-1, isopropanol, methanol, ethanol, water, acetone, methyl ethyl ketone, isobutanol, and tert-butanol are examined as solvents. A mechanism of olefin epoxidation with hydrogen peroxide in an alcohol medium over a titanium-containing zeolite is proposed. Epoxidation reactions involving hydrogen peroxide and different olefins are studied experimentally.
Continuous flow upgrading of glycerol toward oxiranes and active pharmaceutical ingredients thereof
Morodo, Romain,Gérardy, Romaric,Petit, Guillaume,Monbaliu, Jean-Christophe M.
, p. 4422 - 4433 (2019)
A robust continuous flow procedure for the transformation of bio-based glycerol into high value-added oxiranes (epichlorohydrin and glycidol) is presented. The flow procedure features a central hydrochlorination/dechlorination sequence and provides economically and environmentally favorable conditions involving an organocatalyst and aqueous solutions of hydrochloric acid and sodium hydroxide. Pimelic acid (10 mol%) shows an exceptional catalytic activity (>99% conversion of glycerol, a high selectivity toward 1,3-dichloro-2-propanol and 81% cumulated yield toward intermediate chlorohydrins) for the hydrochlorination of glycerol (140 °C) with 36 wt% aqueous HCl. These conditions are validated on a sample of crude bio-based glycerol. The dechlorination step is effective (quantitative conversion based on glycerol) with concentrated aqueous sodium hydroxide (20 °C) and can be directly concatenated to the hydrochlorination step, hence providing a ca. 2:3 separable mixture of glycidol and epichlorohydrin (74% cumulated yield). An in-line membrane separation unit is included downstream, providing usable streams of epichlorohydrin (in MTBE, with an optional concentrator) and glycidol (in water). The scalability of the dechlorination step is then assessed in a commercial pilot-scale continuous flow reactor. Next, bio-based epichlorohydrin is further utilized for the continuous flow preparation of β-amino alcohol active pharmaceutical ingredients including propranolol (hypertension, WHO essential), naftopidil (prostatic hyperplasia) and alprenolol (angina pectoris) within a concatenable two-step procedure using a FDA class 3 solvent (DMSO). This work provides the first example of direct upgrading of bio-based glycerol into high value-added pharmaceuticals under continuous flow conditions.
Controlling the Morphology and Titanium Coordination States of TS-1 Zeolites by Crystal Growth Modifier
Chang, Xinyu,Chen, Ziyi,Hu, Dianwen,Jia, Mingjun,Li, Yingying,Song, Xiaojing,Yang, Xiaotong,Yu, Jihong,Zhang, Hao,Zhang, Peng,Zhang, Qiang,Zhang, Tianjun
, p. 13201 - 13210 (2020)
Developing an effective strategy to synthesize perfect titanosilicate TS-1 zeolite crystals with desirable morphologies, enriched isolated framework Ti species, and thus enhanced catalytic oxidation properties is a pervasive challenge in zeolite crystal engineering. We here used an amino acid l-carnitine as a crystal growth modifier and ethanol as a cosolvent to regulate the morphologies and the Ti coordination states of TS-1 zeolites. During the hydrothermal crystallization process, the introduced l-carnitine can not only tailor the anisotropic growth rates of zeolite crystals but also induce the formation of uniformly distributed framework Ti species through building a suitable chemical interaction with the Ti precursor species. Condition optimizations could afford the generation of perfect hexagonal plate TS-1 crystals and elongated platelet TS-1 crystals enriched in tetrahedral framework Ti sites (TiO4) or mononuclear octahedrally coordinated Ti species (TiO6). Both samples showed significant improvement in catalytic activity for the H2O2-mediated epoxidation of alkenes. In particular, the elongated platelet TS-1 enriched in "TiO6"species afforded the highest activity in 1-hexene epoxidation, with a turnover frequency (TOF) of up to 131 h-1, which is approximately twice as high as that of the conventional TS-1 zeolite (TOF: 65 h-1) and even higher than those of the literature-reported TiO6-containting TS-1 catalysts derived from the hydrothermal post-treatment of TS-1 zeolites. This work demonstrates that the morphologies and the titanium coordination states of TS-1 zeolites can be effectively tuned by directly introducing suitable crystal growth modifiers, thus providing new opportunities for developing highly efficient titanosilicate zeolite catalysts for important catalytic applications.
A New, Effective Catalytic System for Epoxidation of Olefins by Hydrogen Peroxide under Phase-Transfer Conditions
Venturello, Carlo,Alneri, Enzo,Ricci, Marco
, p. 3831 - 3833 (1983)
-
Converting wastes into added value products: From glycerol to glycerol carbonate, glycidol and epichlorohydrin using environmentally friendly synthetic routes
Dibenedetto, Angela,Angelini, Antonella,Aresta, Michele,Ethiraj, Jayashree,Fragale, Carlo,Nocito, Francesco
, p. 1308 - 1313 (2011)
Glycerol carbonate, synthesised via a non-phosgene route using glycerol and CO2 or urea in presence of a heterogeneous catalyst, was efficiently converted into a series of derivatives through the functionalization of the -OH moiety, using high yield, high selectivity synthetic routes not affecting the carbonate functionality. So, for example, glycerol carbonate was converted into epichlorohydrin, a product that has a large industrial application, under very mild conditions, using a two-step reaction with a 98% yield and 100% selectivity. The high yield and mild reaction conditions (very often close to the ambient conditions) make the environmentally friendly synthetic approach described in this work of potential applicative interest. All compounds prepared were fully characterized.
Synthesis of 1,3-dichloropropanol from glycerol using muriatic acid as chlorinating agent
Herliati,Yunus, Robiah,Rashid, Umer,Abidin, Zurina Zainal,Ahamad, Intan Salwani
, p. 2907 - 2912 (2014)
Today, one of the problems associated with biodiesel production is the availability of high amount of glycerol byproduct. Among the various possibilities, technology to convert glycerol to dichloropropanol has diverted our attention. Dichloropropanol an important raw material for epichlorohydrin production was successfully synthesized via hydrochlorination reaction of glycerol with aqueous hydrogen chloride to produce 1,3-dichloropropanol. Experimental study was carried out under temperatures ranged; 80 to 120 °C, reactant molar ratio; 1:16 to 1:32 and various carboxylic acid catalysts. The optimal reaction conditions were: temperature, 110 °C; reactant molar ratio glycerol to HCl, 1:24; catalyst, malonic acid; and time duration, 3 h.
Highly efficient and selective production of epichlorohydrin through epoxidation of allyl chloride with hydrogen peroxide over Ti-MWW catalysts
Wang, Lingling,Liu, Yueming,Xie, Wei,Zhang, Haijiao,Wu, Haihong,Jiang, Yongwen,He, Mingyuan,Wu, Peng
, p. 205 - 214 (2007)
The catalytic properties of Ti-MWW in the epoxidation of allyl chloride (ALC) with hydrogen peroxide to epichlorohydrin (ECH) were studied by comparing these properties with those of TS-1, Ti-MOR, and Ti-Beta. Issues concerning the stability and reuse of Ti-MWW were also considered. The investigation on various reaction parameters showed that Ti-MWW is an active and selective catalyst for ALC epoxidation. Ti-MWW prefers aprotic solvents, such as acetonitrile and acetone, over protic alcohols, which is favorable for suppressing the formation of solvolysis byproducts. ALC conversion and ECH selectivity were both as high as 99% on Ti-MWW. 3-Chloro-1,2-propanediol and other heavy byproducts with high boiling points had a negative effect on ALC conversion for both TS-1 and Ti-MWW. A novel secondary synthesis caused a structural rearrangement of the Ti-MWW framework and then improved its stability.
Enhanced catalytic activity of titanosilicates controlled by hydrogen-bonding interactions
Deng, Xiujuan,Zhang, Shuo,Wang, Binshen,Wang, Yuning,Wu, Haihong,Liu, Yueming,He, Mingyuan
, p. 7504 - 7506 (2013)
A typical volcano-shaped curve has been found in heterogeneous catalytic systems containing titanosilicates for the first time. A new reactive intermediate with double H-bonds is proposed. Systematic results clearly evidence another H-bond formed between the high-electronegativity atom of the H-bond acceptor and the Hend atom of Ti-Oα-O β-Hend.
Solvent effect on epoxidation of allyl chloride with hydrogen peroxide on titanium-containing silicalite
Danov,Sulimov,Sulimova
, p. 1963 - 1966 (2008)
The solvent effect on liquid-phase epoxidation of allyl chloride with an aqueous solution of hydrogen peroxide on TS-1 titanium-containing silicalite was examined. 1-Butanol, 2-butanol, 1-propanol, isopropanol, methanol, ethanol, water, acetone, methyl ethyl ketone, and 1-pentanol were tested as solvents.
Synthesis of ethyl (R)-4-cyano-3-hydroxybutyrate in high concentration using a novel halohydrin dehalogenase HHDH-PL from Parvibaculum lavamentivorans DS-1
Wan, Nan-Wei,Liu, Zhi-Qiang,Huang, Kai,Shen, Zhen-Yang,Xue, Feng,Zheng, Yu-Guo,Shen, Yin-Chu
, p. 64027 - 64031 (2014)
We identified and characterized a novel halohydrin dehalogenase HHDH-PL from Parvibaculum lavamentivorans DS-1. Study of substrate specificity indicated that HHDH-PL possessed a high activity toward ethyl (S)-4-chloro-3-hydroxybutanoate ((S)-CHBE). After optimizations of the pH and temperature, whole cell catalysis of HHDH-PL was applied to the synthesis of ethyl (R)-4-cyano-3-hydroxybutyrate (HN) at 200 g L-1 of (S)-CHBE, which gave 95% conversion and 85% yield in 14 h.
Synthesis and enzymatic resolution of racemic 2,3-epoxy propyl esters obtained from glycerol
Araujo, Yara Jaqueline Kerber,Avvari, Naga Prasad,Paiva, Derisvaldo Rosa,De Lima, Dênis Pires,Beatriz, Adilson
, p. 1696 - 1698 (2015)
A method is described for the synthesis of (±)-2,3-epoxy propyl esters from glycerol, involving reaction of epichlorohydrin with sodium or potassium salts of carboxylic acids in the presence of TBAB as catalyst, with moderate to excellent yields. Kinetic resolution of glycidyl butyrate by lipase of Thermomyces lanuginosa has been achieved with remarkable enantiomeric excess (ee >99%) using 1,4-dioxane as a co-solvent in pure buffer solution (30 and 50 °C, pH = 7.0).
EPOXIDIZATION OF ALLYL CHLORIDE BY COMBINED OXIDATION WITH ETHYLBENZENE ON LAYERED COMPOUNDS OF GRAPHITE WITH TRANSITION-METAL CHLORIDES
Kovtyukhova, N. I.,Belousov, V. M.,Novikov, Yu. N.,Vol'pin, M. E.
, p. 1566 - 1570 (1983)
-
Physicochemical relationships of the synthesis of epoxy compounds
Sulimov,Danov,Ovcharova,Ovcharov,Flid
, p. 89 - 96 (2015)
Quantitative information on the effect of process parameters on the main relationships of the liquid-phase epoxidation of propylene, allyl chloride, and allyl alcohol with hydrogen peroxide in an organic solvent in the presence of powdered titanium silicalite in a batch reactor was obtained and summarized for the first time. The influence of the solvent amount, reactant ratio, and temperature was examined, and the area of the process parameters ensuring high yields of the epoxy compounds (propylene oxide, epichlorohydrin, and glycidol) was localized.
Fully utilizing seeds solution for solvent-free synthesized nanosized TS-1 zeolites with efficient epoxidation of chloropropene
Chai, Yongming,Li, Bin,Li, Yichuan,Liu, Hanfang,Liu, Jia,Liu, Yanru,Ran, Saisai,Wang, Fupeng,Wang, Lei,Wang, Yu,Xie, Huijie,Ye, Tiantian
, (2021/12/27)
Nanosized titanium silicalite-1 (TS-1) demonstrates excellent catalytic ability in the selective catalytic oxidation reaction. However, their synthesis process is usually complicated with low yield under hydrothermal conditions, which is not in line with the concept of green chemistry. Herein, via fully utilizing untreated seeds solution, we report firstly an entirely green strategy for solvent-free synthesizing anatase-free nanosized TS-1 zeolite. The success lies in the fully utilization of seeds solution which is composed of supersaturated structure directing agent (TPAOH), unreacted silica source, water and formed MFI seeds (silicalite-1) without external purification. In the followed solvent-free synthesis of final nanosized TS-1 product, no additional TPAOH is added, which greatly reduces the synthesis cost and synthetic procedure and maintains a high product yield. The obtained nanosized TS-1 zeolite without anatase phase has high crystallinity, large specific surface area. More importantly, the nanosized TS-1 (Si/Ti ?= ?77) catalysts exhibit excellent catalytic ability for the epoxidation of chloropropene with 40.0% conversion and 97.6% selectivity. This sustainable and green synthesis method opens up a new way to regulate nanosized zeolite.
Selective synthesis of epichlorohydrin: Via liquid-phase allyl chloride epoxidation over a modified Ti-MWW zeolite in a continuous slurry bed reactor
Ding, Luoyi,Yin, Jinpeng,Tong, Wen,Peng, Rusi,Jiang, Jingang,Xu, Hao,Wu, Peng
, p. 331 - 342 (2021/01/11)
The epoxidation of allyl chloride (ALC) to epichlorohydrin (ECH) with H2O2 using a piperidine (PI)-modified Ti-MWW catalyst (Ti-MWW-PI) in a continuous slurry reactor was investigated to develop an efficient reaction system for the corresponding industrial process. The reaction parameters, including solvent, reaction temperature, t-butanol/ALC mass ratio, ALC/H2O2 molar ratio, weight hourly space velocity of H2O2, and the addition amount of ammonia, were studied in detail to pursue high H2O2 conversion and ECH selectivity. A long catalytic lifetime of 244 h was achieved at high H2O2 conversion (>97.0%) and ECH selectivity (>99.8%) under optimized reaction conditions. The crystallinity was well maintained for the deactivated Ti-MWW-PI catalyst, which was regenerated by a combination of calcination and piperidine treatment. This journal is
A method for efficient preparation of epichlorohydrin by biomass glycerol
-
Paragraph 0040-0041; 0051-0052; 0062-0063; 0073, (2022/01/10)
The present invention discloses a method for efficiently preparing epichlorohydrin by biomass glycerol, comprising the following steps: 1) the mass ratio of 1: 0.06 ~ 0.08 of biomass glycerol and a composite catalyst poured into the reactor, and then using an ultrasonic probe to extend into the reactor, 2) step 1) after the end of the reaction, the resulting material is cooled to room temperature and transferred to the reaction vessel, maintaining a temperature of 15 ~ 30 ° C, and then adding an alkaline cyclizer for the reaction; 3) after the completion of the reaction to filter the resulting solids, The filtrate is a solution of epichlorohydrin oxide; the glycerol of the present invention can be completely converted, the intermediate product dichloropropanol yield is high, and the selectivity of collecting 1,3-dichloropropanol is improved, which accelerates the reaction rate; and the process can be co-produced with biodiesel and chlor-alkali industry, and the industrialization prospect is good.