MnO2负载量对MnO2/HBeta分子筛催化二甲醚制六甲基苯反应性能的影响

在连续流动固定床反应器上考察了不同MnO_2负载量的MnO_2/HBeta分子筛催化二甲醚制六甲基苯的性能,结果表明:10%MnO_2改性HBeta有利于提高六甲基苯选择性。在常压、反应温度为280℃、空速为100h-1条件下,10%MnO_2/HBeta催化二甲醚反应,二甲醚转化率达76.36%,HMB选择性为25.1%。利用NH_3-TPD,Py-IR,BET及XRD等对催化剂的结构和性质进行表征,结果表明,随着MnO_2负载量的增加,MnO_2在催化剂中逐渐以晶体结构存在,且催化剂表面强酸中心逐渐增加,而催化剂B酸酸性呈现出先减弱后增强的趋势。10%MnO_2改性HBeta催化剂具有适宜的表面酸性,有利于HMB的生成。

改性HBeta分子筛催化二甲醚转化制六甲基苯的研究

以金属氧化物改性的HBeta分子筛为催化剂,对二甲醚催化转化制六甲基苯进行了初步研究。采用浸渍法制备MnO_2、ZnO、WO_3、MoO_3和K_2O改性的HBeta分子筛催化剂,并利用NH_3-TPD、Py-IR、BET及XRD等对催化剂的结构和性质进行表征,在固定床反应器中测试了其催化性能。结果表明,10%MnO2/HBeta的六甲基苯选择性最高。催化剂表征结果表明,10%MnO_2改性HBeta催化剂可提高HBeta的强酸量,适宜的强酸量有利于六甲基苯的生成;10%MnO_2改性HBeta催化剂可适量降低HBeta的B酸量,适宜的B酸量有利于六甲基苯的生成。对10%MnO_2/HBeta催化剂,六甲基苯选择性随反应温度升高或空速升高均先升高后降低,在常压、280℃、空速为100h-1反应条件下,二甲醚转化率达76.36%,六甲基苯选择性25.1%。

六甲基苯的合成研究

六甲基苯是一种有机合成原料,价格相对较贵,对它的研究主要集中在上个世纪中叶,本文主要介绍六甲基苯的研究现状和几种合成方法。最终得出的结论是以易得到的苯,一氯甲烷,二氯苯和无水氯化铁为原料进行合成,按照苯计算六甲基苯的収率可达44%,虽然収率不高,但是纯度较大,分离比较简单,是一种比较好的合成方法。

6键碳原子首获影像证实

《科技日报》电,传统教科书中,一个碳原子最多只能与4个原子通过电子对结合。但德国柏林自由大学化学家莫瑞兹·马力丝维斯基首次合成并证实,在一种椎体形碳分子内存在一个能与6个原子结合的碳原子。发表在德国《应用化学》杂志上的这一最新研究将改写教科书。据《新科学家》杂志网站11日报道,新结构是以化合物六甲基苯为基础获得的。通常情况下.

Exclusively catalytic oxidation of toluene to benzaldehyde in an O/W emulsion stabilized by hexadecylphosphate acid terminated mixed-oxide nanoparticles

A series of hexadecylphosphate acid(HDPA) terminated mixed-oxide nanoparticles have been investigated to catalyze the oxidation of toluene exclusive to benzaldehyde under mild conditions in an emulsion of toluene/water with the catalysts as stabilizers. With the HDPA-Fe2 O3/Al2 O3 as the basic catalyst, a series of transition metals, such as Mn, Co, Ni, Cu, Cr, Mo, V, and Ti, was respectively doped to the basic catalyst to modify the performance of the catalytic system, in expectation of influencing the mobility of the lattice oxygen species in the oxide catalysts. Under normally working conditions of the catalytic system, the nanoparticles of catalysts located themselves at the interface between the oil and water phases, constituting the Pickering emulsion. Both the doped iron oxide and its surface adsorbed hexadecylphosphate molecules were essential to the catalytic system for excellent performances with high toluene conversions as well as the exclusive selectivity to benzaldehyde. Under optimal conditions, ~83% of toluene conversion and >99% selectivity to benzaldehyde were obtained, using molecular oxygen as oxidant and HDPA-(Fe2 O3-Ni O)/Al2 O3 as the catalyst. This process is green and low cost to produce high quality benzaldehyde from O2 oxidation of toluene.

Synthesis, characterization, and catalytic performance of hierarchical ZSM-11 zeolite synthesized via dual-template route

Hierarchical zeolite materials were prepared via one‐pot synthesis of ZSM‐11zeolites with different molar ratios(R)of a mesoporogen,i.e.,cetyltrimethylammonium bromide template(CTAB),to a microporogen,i.e.,tetra‐n‐butylammonium bromide(TBABr).The structures,morphologies,and textural properties of the resultant materials were investigated.Initially,with increasing R,the crystal size of the synthesized product decreased,the number of intercrystalline mesopores increased,and a pure ZSM‐11zeolite phase was present.Then an MCM‐41‐like phase was produced and embedded in the ZSM‐11zeolite phase.Finally,an MCM‐41‐like phase was obtained.The alkalinity had important effects on the physicochemical and textural properties of the prepared samples.A possible mechanism of formation of the hierarchical ZSM‐11zeolite was proposed on the basis of a combination of various characterization results.The role of CTAB varied depending on the R value,and it showed a capping effect,micellar effect,and template effect.These effects of CTAB were synergetic in ZSM‐11synthesis,but they were competitive with the structure‐directing effect of TBABr.In addition,the impact of the acidic properties and porosities of the hierarchical ZSM‐11catalysts on their performances in the alkylation of benzene with dimethyl ether was investigated.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Enzyme‐like mechanism of selective toluene oxidation to benzaldehyde over organophosphoric acid‐bonded nano‐oxides

The completely selective oxidation of toluene to benzaldehyde with dioxygen,without the need touse H_(2)O_(2),halogens,or any radical initiators,is a reaction long desired but never previously successful.Here,we demonstrate the enzyme‐like mechanism of the reaction over hexadecylphosphateacid(HDPA)‐bonded nano‐oxides,which appear to interact with toluene through specific recognition.The active sites of the catalyst are related to the ability of HDPA to change its bonding to theoxides between monodentate and bidentate during the reaction cycle.This greatly enhances themobility of the crystal oxygen or the reactivity of the catalyst,specifically in toluene transformations.The catalytic cycle of the catalyst is similar to that of methane monooxygenase.In thepresence of catalyst and through O_(2)oxidation,the conversion of toluene to benzaldehyde is initiatedat 70°C.We envision that this novel mechanism reveals alternatives for an attractive route to designhigh‐performance catalysts with bioinspired structures.

Photocatalytic Reduction of 6-Chloro-3-Nitrotoluene-4-Sulfonic Acid in Presence of Surfactants

Photocatalytic reduction of 6-chloro-3-nitrotoluene-4-sulfonic acid (CNSA) was studied in UV-irradiated TiO2 suspensions in the presence of methanol and surfactants. A mixture of CNSA, TiO2, water, additives and surfactants was put into a quartz glass reactor with a jacket, which was irradiated with a high pressure Hg lamp in the purging of nitrogen gas. With methanol, the conversion of CNSA increased from 7.7% to 34.6%. Three surfactants significantly promoted the photocatalytic reduction conversion in reduced order of sodium dodecylbenzenesulfonate (DBS), cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS). In suspensions involving DBS and CTAB respectively, CNSA conversion increased in consistence with the adsorption ratio with methanol, but varied inversely with the adsorption ratio without methanol. But no obvious influence on the adsorption ratio was observed with or without methanol added when the SDS concentration was critical micelle concentration (cmc). The photocatalytic reduction of CNSA was enhanced in UV-irradiated TiO2 suspensions in the presence of methanol and surfactants. Methanol inhibited the recombination of photogenerated holes and electrons efficiently. Surfactants around 1 cmc led to the highest reduction conversion.

Dynamic Adsorption of Microwave Modified Attapulgite on Micro-polluted Phenol Wastewater

[Objective] The paper was to study the dynamic adsorption of microwave modified attapulgite on micro-polluted phenol wastewater. [Method] Cetyl trimethyl ammonium bromide （CATB） modified attapulgite was used to modify attapulgite, and conducted dynamic test on micro-polluted phenol wastewater. The dynamic charac- teristics of phenol removal were also studied. [Result] Attapulgite modified by CATB has strong adsorption ability on phenol in micro-polluted water, the phenol removal rate increased with the decrease of flow rate of wastewater. When pH value was 6- 8, phenol concentration in wastewater was 17.74 mg/L, flow rate was 2 m/s and ad- sorption time was 25 rain, the removal rate reached 93.07%. The modified atta- pulgite could be regenerated with alkali, and its adsorption ability after regeneration had no obvious decline. The dynamic adsorption process of phenol accorded with the first-order kinetic equation. [Conclusion] The study provided basis for further study on ＂organic matter removal in wastewater.