Study on reaction characteristics of phenolic hydroxyl in coal by using the model compound during direct coal liquefaction

The reaction characteristics of phenolic hydroxyl group were studied under the conditions of direct coal liquefaction. 2-naphthol was used as a coal model compound in this study. Under the conditions of with and without catalysts, a series of experiments were conducted at different temperatures, pressures and reaction time. Gas chromatography-mass spectrometry and gas chromatography were used to identify and quantify the reactants and products respectively. The conversion of 2-naphthol rises with the increase of reaction temperature, initial pressure and catalyst amount. The results indicated that tem- perature had a significant effect on 2-naphthol conversion, which promoted the dehydroxylation reaction. However, initial pressure had an important influence on the hydrogenation of 2-naphthol and naphthalene. The iron catalyst plays a significant role of cracking instead of hydrogenation. It is concluded that the harsh reaction conditions of high temperature, high pressure, and more catalyst are conducive to promoting dehydroxylation of 2-naphthol. The reaction mechanism was put forward based the experimental results, in which 2-tetralone was an intermediate.

Kinetics of the direct reaction between ozone and phenol by high-gravity intensified heterogeneous catalytic ozonation

In this study,high-gravity intensified heterogeneous catalytic ozonation is utilized for treatment of phenol-containing wastewater,and the kinetics of the direct reaction between ozone and phenol in the presence of excess tertiary butanol(TBA)is investigated.It is revealed that the direct reaction between ozone and phenol in the rotating packed bed(RPB)follows the pseudo-first-order kinetics with a reaction rate constant higher than that in the conventional bubbling reactor(BR).Under different conditions of temperature,initial pH,high-gravity factor,and gaseous ozone concentration,the apparent reaction rate constant varies in the range of 0.0160–0.115 min-1.An empirical power-exponential model is established to characterize the effects of these parameters on the direct reaction between ozone and phenol by high-gravity intensified heterogeneous catalytic ozonation.

Hollow ZIF-67-derived Co@N-doped carbon nanotubes boosting the hydrogenation of phenolic compounds to alcohols

The selective hydrogenation of highly toxic phenolic compounds to generate alcohols with thermal stability,environmental friendliness,and non-toxicity is of great importance.Herein,a series of Co-based catalysts,named Co@NCNTs,were designed and constructed by direct pyrolysis of hollow ZIF-67(HZIF-67)under H_(2)/Ar atmosphere.The evolution of the catalyst surface from the shell layer assembled by ZIF-67-derived particles to the in situ-grown hollow nitrogen-doped carbon nanotubes(NCNTs)with certain length and density is achieved by adjusting the pyrolysis atmosphere and temperature.Due to the synergistic effects of in situ-formed hollow NCNTs,well-dispersed Co nanoparticles,and intact carbon matrix,the as-prepared Co@NCNTs-0.10-450 catalyst exhibits superior catalytic performance in the hydrogenation of phenolic compounds to alcohols.The turnover frequency value of Co@NCNTs-0.10-450is 3.52 h^(-1),5.9 times higher than that of Co@NCNTs-0.40-450 and 4.5 times higher than that of Co@NCNTs-0.10-550,exceeding most previously reported non-noble metal catalysts.Our findings provide new insights into the development of non-precious metal,efficient,and cost-effective metal-organic framework-derived catalysts for the hydrogenation of phenolic compounds to alcohols.

Removal of phenol by activated alumina bed in pulsed high-voltage electric field

A new process for removing the pollutants in aqueous solution-activated alumina bed in pulsed high-voltage electric field was investigated for the removal of phenol under different conditions. The experimental results indicated the increase in removal rate with increasing applied voltage, increasing pH value of the solution, aeration, and adding Fe^2＋. The removal rate of phenol could reach 72.1% when air aeration flow rate was 1200 ml/min, and 88.2% when 0.05 mmol/L Fe^2＋ was added into the solution under the conditions of applied voltage 25 kV, initial phenol concentration of 5 mg/L, and initial pH value 5.5. The addition of sodium carbonate reduced the phenol removal rate. In the pulsed high-voltage electric field, local discharge occurred at the surface of activated alumina, which promoted phenol degradation in the thin water film. At the same time, the space-time distribution of gas-liquid phases was more uniform and the contact areas of the activated species generated from the discharge and the pollutant molecules were much wider due to the effect of the activated alumina bed. The synthetical effects of the pulsed high-voltage electric field and the activated alumina particles accelerated phenol degradation.

Addition Mechanisms of Phenol toward Formaldehyde under Acidic Condition: a Theoretical Investigation

The reaction mechanisms of phenol with formaldehyde in the first and second addition at the ortho- and para-position in acid solution were theoretically investigated at the PW91/DNP level with solvent effects included. The reaction of phenol with protonated methanediol firstly forms an adduct intermediate, via a SN2 mechanism with a water molecule as the leaving group. From the adduct intermediate, there are two reaction channels involving a proton transfer to form the addition products. One is that a proton directly transfers via a four-membered ring transition state with a notable energy barrier （Four-member mechanism）. Another mechanism involving a water molecule as catalyst to mediate the proton transfer （WCP mechanism）, is a barrierless process, indicating that the formation of the adduct intermediate, the first reaction step, is rate-limiting. The reaction products are free hydroxymethyl phenols and/or hydroxybenzy carbocation （HOC6H4CH2＋） which plays an important role in the following formation of methylene and methylene ether linkages. The second addition reactions between formaldehyde and hydroxymethyl phenol at all possible reaction sites of the phenol ring in acid solution were also investigated and discussed.

Optimization and Effects of Catalytic Ozonation of Actual Phenolic Wastewater by CuO/Al2O3

In order to improve the ability of ozone to catalyze the degradation of phenolic pollutants in wastewater,the CuO/Al2O3 catalysts was prepared by the impregnation precipitation method and an ozone catalytic oxidation system was constructed.The actual phenolic sewage was used as the treatment object.And the reaction conditions of the system were optimized,and the treatment effect was determined,while the non-catalytic system was used as a control group.At the same time,the influence of salt and ammonia nitrogen related water quality on the system was studied.The optimal reaction conditions for the treatment of phenolic wastewater covered:a catalyst dosage of 30 g/L,an ozone flow rate of 0.3 m3/h,a pH value of 8.80,and a reaction time of 15 minutes.Under these conditions,the phenol and COD removal rates of the system reached 98.7%and 49.4%,respectively,which were by 31.3 percentage points and 16.2 percentage points higher than that of the ozonation system alone.The salt and ammonia nitrogen in the sewage can reduce the oxidation effect of the system.When the salinity reached 10%and the ammonia nitrogen content reached 13 000 mg/L,the removal rate of phenol could be reduced by about 20%.The results of this paper have a reference value for phenol wastewater treatment engineering.

Preparation and Characterization of Tung Oil Toughened Modified Phenolic Foams with Enhanced Mechanical Properties and Smoke Suppression

In this study,we prepared a series of tung oil phenolic foams(TPF)by a one-pot method.The FT-IR and 1H NMR spectra confirm the successful Friedel-Crafts grafting of phenol to the long-chain alkyl group in tung oil.Modified TPFs exhibit enhanced mechanical properties,including compressive and flexural strengths of up to 0.278±0.036 MPa and 0.450±0.017 MPa,respectively,which represent increases of 68.75%and 86.72%over those of pure phenolic foam(PF).SEM spectra reveal the TPF microstructure to have uniform hexagonal cell morphology,narrower cell size distribution,and smaller mean cell size,suggesting enhanced mechanical properties.The TPF total smoke release decreased by 74.23%,indicating that the long alkyl chain significantly improves smoke suppression of the combusting foam.However,due to the flammability of the alkyl chains,the TPF limiting oxygen index decreases with increasing tung oil content.Moreover,TPF exhibits reduced thermal stability and high-temperature charring rate,elevated peak and mean heat release rates,and higher total heat release compared with pure PF.Therefore,future research will focus on the use of tung oil modified flame retardant to provide more robust phenolic foams.

Synthesis and Crystal Structure of the Derivative of Hydroquinone from Mannich Reaction

The regioselective Mannich-type aminomethylation of hydroquinone afforded a nitrogen-containing compound, 2,5-bis-(morpholinomethyl)hydroquinone A, and its crystal structure was determined by single-crystal X-ray diffraction. Crystal data for A: C16H24N2O4, Mr = 308.37, orthorhombic, space group Pbca, a = 10.479(4), b = 10.298(4), c = 14.865(5) ?, V = 1604.3(11) ?3, Z = 4, Dc = 1.277 g/cm3, F(000) = 664, μ = 0.092 mm-1, GOF = 1.078, the final R = 0.0508 and wR = 0.1075 for 1416 observed reflections with I > 2σ(I). There exist two intramolecular O–H…N hy- drogen bonds between the phenolic O atoms and the morpholine N donors and the morpholino rings assume the preferred chair conformation.

Coking and Deactivation of Catalyst Inhibited by Silanization Modification in Oxidation of Benzene to Phenol with Nitrous Oxide

The main cause to the deactivation of ZSM-5 catalyst, used for oxidation of benzene to phenol (BTOP) by nitrous oxide, is that the carbon deposition on the catalyst surface blocks the mouth of pores of the catalyst.In the experiments, ZSM-5 catalyst was modified by chemical surface deposition of silicon, and then the effect of modification condition on the catalyst activation was studied. The catalyst samples were characterized by XRF,EPS, XRD, TEM, N2 adsorption at low temperature, pyridine adsorption-infrared technique and etc. All the above results show that the uniform SiO2 membrane can be formed on ZSM-5 crystal surface. The SiO2 membrane covers the acid centers on ZSM-5 surface to inhibit surface coking, to avoid or decrease the possibility of ZSM-5 pore blockage so that the catalyst activity and stability can be improved efficiently. The optimum siliconiting conditions determined by the experiments are as follows: 4% load of silanizing agent, volume (ml)/mass (g) ratio of hexane/ZSM-5=15/1, and 16 h of modification time. Compared with the samples without siliconiting treatment,the samples treated under the above optimum condition can increase the productivity of phenol by 14% for 3 h reaction time and by 41% for 6 h reaction time respectively.

Synthesis and Characterization of New Chiral Monoanionic [ON] Ancillary Phenolate Ligands

Three new chiral monoanionic [ON] ancillary phenolate ligands with varying pendant arms have been synthesized in moderate to high yields (50% - 85%) via Mannich-type condensation reaction of chiral substituted phenol, formaldehyde and (+)-bis-[(R)-1-phenylethyl]amine. These new organic compounds were fully characterized via nuclear magnetic resonance spectroscopy (1H and 13C) and elemental analysis. The newly synthesized ligands are suitable candidates for metal-catalyzed ring-opening of lactones and asymmetric catalysis.

Approximate analytical solution of non-linear reaction diffusion equation in fluidized bed biofilm reactor

A mathematical model for the fluidized bed biofilm reactor (FBBR) is discussed. An approximate analytical solution of concentration of phenol is obtained using modified Adomian decomposition method (MADM). The main objective is to propose an analytical method of solution, which do not require small parameters and avoid linearization and physically unrealistic assumptions. Theoretical results obtained can be used to predict the biofilm density of a single bioparticle. Satisfactory agreement is obtained in the comparison of approximate analytical solution and numerical simulation.

苯酚选择性氧化还原合成对苯二酚研究

苯酚选择性氧化还原制备对苯二酚反应具有潜在的工业应用价值。本文使用复合型催化剂有机硒醚/CNTs将苯酚选择性地定向氧化为对苯醌,对苯醌在Pt/C催化剂的作用下还原为对苯二酚。为了提高对苯醌的收率,本文将硒催化组分固定在中空多孔的碳纳米管上以增大催化剂的比表面积,苯酚氧化制备对苯醌选择性高达92.5%,具有催化剂制备简单、原料转化率和产物选择性高和废水排放量少等优势。

高温改性钢渣活化过硫酸盐降解甲基橙和苯酚的反应机制

采用高温改性钢渣活化过硫酸盐(peroxymonosulfate,PMS)降解甲基橙(methyl orange,MO)和苯酚(phenol,AR)。考察了改性钢渣投加量、PMS浓度、初始pH值、反应温度对MO和AR降解效果的影响。在改性钢渣质量浓度为9.0 g/L、PMS物质的量浓度为12.0 mmol/L、初始pH值为7.0、反应温度为25℃的条件下,反应90 min,30 mg/L MO和15 mg/L AR的降解率分别达到90.5%和100%。材料表征分析结果表明,高温改性钢渣比表面积增大、孔隙率高、催化氧化PMS性能好,且重复利用仍有较好的原位恢复性能。自由基淬灭和电子顺磁共振波谱实验说明,高温改性钢渣/PMS反应体系存在非自由基(1 O 2)和自由基(SO_(4)^(-)·和·OH),发挥了碱活化PMS和铁氧化物活化PMS的共同作用,最终将MO和AR降解为小分子物质。

Kinetic Study of Curing Phenol-Formaldehyde/Tannin-Formaldehyde Composite Resins

This work presents a study on the uses of tannin-formadehyde derivative into phenolic resins. Eucalyptus tannins (T) were reacted with formaldehyde to form tannin-formaldehyde resin (TF). Then this derivative was used to prepare tannin-formaldehyde/phenol-formaldehyde resins (TFPF) at 20 and 40 %w/w. The kinetic values of thermal curing of Phenol-formaldehyde (PF), tannin-formaldehyde and tannin-formaldehyde/phenol-formaldehyde resins (TFPF) at 20 and 40 wt% from TF were studied by monitoring the weight changes which occurred in the samples weight during thermosetting process at four temperature (160°C, 180°C, 200°C and 220°C). The total evolved condensation products from curing reactions were about 32% - 36% per sample weight, and the rate of curing reaction constants was ranged between 0.163 %wt·min-1 at 160°C and 0.50 %wt·min-1 at 220°C. The path of TFPF curing and kinetic values indicated that these resins could be cured with the behavior and velocity comparable to that of PF. The activation energy of TFPF cross-linking was higher than that of PF. Increasing TF level to 20% and 40% into PF can reduce the amount of PF curing reactions density and weight loss percentage. The global kinetic properties showed that the TF participated in the thermoset network formation with acceptable activity and performance. The general results of this paper show that the TF is a suitable alternative material for partially replacement into PF resin.

钒基催化剂催化苯羟基化制苯酚反应机理

苯羟基化制苯酚是C—H键向C—O键转化及富有挑战性的课题之一。该文论述了钒基催化剂催化苯羟基化制苯酚反应机理的研究进展。以钒活性中心为主线,着重从自由基、非自由基和双催化活性机理进行了详细介绍,同时分析了双催化活性中心催化剂高效催化的本质和重要性。提出此类催化体系及催化机理能够解决苯环上C—H键难活化和苯酚的深度氧化等问题,是经济与安全并存的苯酚合成方法,依托已有的催化反应机理,开发更稳定且高性能的催化剂,以促进烃类有机化合物资源利用的原始创新。

DMSNs对酚类化合物的吸附及降解研究进展

酚类化合物广泛存在于空气、废水和土壤中,严重危害自然环境和人类健康。加强此类化合物的处理是科研工作者的研究重点。本文总结了树枝状介孔SiO_(2)纳米粒子(dendritic mesoporous silica nanoparticles,DMSNs)对酚类化合物吸附、降解的最新研究进展。重点探讨了DMSNs催化剂的设计思路以及在对硝基苯酚、苯酚、双酚A、邻氯苯酚等多种酚类化合物方面的应用和反应机制,为后续设计出绿色环保、吸附降解性能优异的功能材料提供了理论基础,并且展望了此类催化剂降解酚类污染物的发展方向。

片状ZSM-5分子筛的合成及其催化苯酚甲醇烷基化反应性能

采用晶种诱导及矿化剂辅助方法合成了一系列具有不同b轴厚度及不同硅铝原子比的片状ZSM-5分子筛,通过SEM、XRD、N_(2)吸附-脱附及NH_(3)-TPD等方法对合成的分子筛进行表征,并将其用于苯酚甲醇烷基化反应中,考察了不同b轴厚度和硅铝原子比对催化反应稳定性及甲酚选择性的影响。实验结果表明,硅铝原子比为100、b轴厚度为20 nm的片状ZSM-5分子筛在该反应中表现出较好的催化性能及良好的容碳能力,苯酚转化率可达43%以上,甲酚选择性达51%,分子筛寿命超300 h。

基于酚醛反应显色原理的莨纱绸鉴别方法研究

为了高效地鉴别莨纱绸的真伪,根据芳香醛与薯莨色素发生酚醛缩合反应的机理,将香草醛、4-甲氧基肉桂醛和4-(二甲基氨基)肉桂醛配制成的鉴别试剂分别与薯莨色素溶液混合,观察溶液颜色变化并探究鉴别试剂与薯莨色素溶液的最佳反应条件。研究结果表明,3种芳香醛的混合溶液颜色均变深,其中4-(二甲基氨基)肉桂醛组颜色最深即反应最剧烈。最佳反应条件为:质量分数0.2%的4-(二甲基氨基)肉桂醛,pH值1.4,反应温度40℃,反应时间10 min。最后,将芳香醛鉴别试剂滴加到纯正莨纱绸表面,绸面颜色变深、K/S值增加,可用于莨纱绸的高效定性鉴别。

烯丙基醚化酚醛亚胺树脂的固化动力学研究

采用差示扫描量热仪测定了不同升温速率下烯丙基醚化酚醛亚胺树脂(APMI-F树脂)的DSC曲线,用非等温热力学的研究方法研究了APMI-F树脂的固化反应动力学。用T-β外推法确定了APMI-F树脂的固化反应的起始温度Ti、峰值温度Tp和终止温度Tf,并将其作为探究APMI-F树脂固化工艺的依据。通过Kissinger法和Starink法求得APMI-F树脂的表观活化能,由Starink法得到不同固化度下的表观活化能,并将其与试验数据对比,以验证固化动力学模型的准确性。研究结果表明:(1)利用外推法确定了APMI-F树脂固化反应的Ti、Tp和Tf分别为161.09、226.81、263.42℃;(2)Starink法求得的平均活化能要高于Kissinger法所得数据;(3)在固化反应过程中,随着固化程度的升高,APMI-F树脂的表观活化能呈现先降低后升高的趋势,固化初期活化能因黏度的降低而降低,随着交联度的提高,链段运动受到限制导致活化能渐渐升高;(4)采用Málek法成功地建立了APMI-F树脂的固化动力学模型,通过与试验数据对比,发现该模型能够很好地描述APMI-F树脂的固化过程。