Phase behavior and kinetics of polystyrene degradation in supercritical toluene

The phase behavior of polystyrene (PS) degradation in toluene was investigated in a visual high‐pressure reactor. The system of PS and toluene was heated from room temperature and atmospheric pressure to 350°C and 5.0 MPa. It was observed that during this process, PS dissolved quickly, and then, the system appeared to be a homogeneous phase, and PS degradation occurred in this system. With another high‐pressure batch reactor, PS degradation was studied in the temperature range 275–360°C and the pressure ranges 4.5–10.5 MPa. The drop‐in molecular weights in the temperature ranges and the amount of PS converted into volatile products were observed. Moreover, the effects of the temperature, pressure, and ratio of toluene to PS on the rate of PS degradation are discussed. The kinetic studies showed that the rate of PS degradation in supercritical toluene increased substantially because the degradation occurred in a homogeneous phase. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Degradation of polystyrene in supercritical n-Hexane

Degradation of polystyrene was carried out in supercritical n-hexane under reaction temperature ranging from 330 °C to 390 °C, pressure ranging from 30 bar to 70 bar and reaction duration of 90 min. The conversion of polystyrene increased with rising temperature and pressure. The degradation performance was influenced by the temperature rather than applied pressure. Polystyrene rapidly degraded in 30 min after reaching a prescribed temperature ranging from 350 °C to 390 °C. At a prescribed temperature of 390 °C, the degree of degradation was higher than 90%. The degradation reaction was examined experimentally at a relatively low temperature of 330 °C. The degradation of polystyrene by using supercritical n-hexane has been found to be more effective compared to general pyrolysis (thermal degradation). Among the selectivity of liquid products, that of a single aromatic ring group like styrene at 390 °C increased up to 65% in 90 min. It was found from the analysis by a gel permeation Chromatograph (GPC), that high molecular-weight compounds decreased but oligomers increased with rising temperature.     

Nonisothermal kinetics of wood degradation in supercritical methanol

The kinetic analysis of wood degradation in supercritical methanol has been studied by a nonisothermal weight loss technique. The weight loss data according to degradation temperature have been analyzed using two integral methods based on Arrhenius form to obtain the kinetic parameters, such as apparent activation energy and overall reaction order. The experiments were carried out for three heating rates of 5.2, 11.6 and 16.3 °C/min. It was found that there are the distinct mass changes over the temperature range of 260–370 °C for all three heating rates, and the weight loss curves were displaced to higher temperatures as increasing of heating rate. The activation energies of wood degradation in supercritical methanol were 73.5–74.5 kJ/mol and 45.2–48.8 kJ/mol, and the reaction orders were 0.59–0.64 and 0.25, depending on the mathematical approach taken in the analysis and the heating rate.     

超临界甲醇法制备生物柴油的动力学研究进展

超临界甲醇法制备生物柴油技术由于其独特的优势,从首次被提出以来,就受到国内外众多研究者的关注和研究。综述了超临界甲醇无催化制备生物柴油的相关动力学研究成果,讨论了反应机理、反应速率常数和活化能等,旨在阐明反应规律。另外也介绍了超临界流体二步法制备生物柴油技术及其动力学研究成果,并提出了这种技术的优势、存在问题及发展方向。     

Synthesis of higher alcohols from syngas over Zn–Cr–K catalyst in supercritical fluids

An investigation was carried out on the selective synthesis of higher alcohols from syngas in a supercritical fluid (a mixture of C₁₀–C₁₃ alkanes) by using a fixed bed reactor. Experiments were conducted over Zn–Cr–K catalyst in the temperature range of 360–400°C, a partial pressure of syngas of 7.5 MPa and a partial pressure of supercritical medium of 1.78 MPa. Comparison of results in the gas phase with those in the supercritical phase indicated that CO conversion was higher in the supercritical phase reaction. Alcohol selectivity decreased slowly with increasing temperature in the supercritical phase reaction but decreased rapidly in the gas phase reaction, due to the special properties of supercritical fluids (SCF). Product distributions were different in both reaction phases. The introduction of the supercritical medium promoted carbon chain growth and the content of C₂⁺OH was increased. The product distribution features with high methanol content of the gas phase synthesis were changed.     

A comparative study of polystyrene decomposition in supercritical water and air environments using diamond anvil cell

Polystyrene (PS) decomposition in supercritical water (SCW) and in air was studied with the diamond anvil cell (DAC) technique coupled with microscopy and FTIR. Apparent concentrations were calculated by using digital imaging analysis. When PS + water systems (11.8–22.6 wt % PS) were rapidly heated at a rate of 2.3°C/s, the PS particle melted at 279.8–320.2°C. After formation of a globule at 409.3–452.5°C, the globule started to dissolve in color to yellow at 496.1°C. At 570.3°C and 742.5 MPa, solubility reached the maximum of 91.5 wt % (11.8 wt % PS). The soluble material was a styrenelike liquid, which was identified by IR after cooling. In isothermal runs at 400 and 450°C, two heterogeneous liquid phases consisting of water and decomposed PS were found. Styrenelike liquid products were identified after the reactions. PS decomposition stages in air consisted of melting, gas generation, liquid ring configuration, and finally yellow volatile products formation at 583.2°C. The results show conclusively that PS can be dissolved in SCW above 496.1°C and homogenous reaction is likely to occur above 570.3°C. Reactions in SCW at 400 and 450°C take place in heterogeneous liquid phases, while in the PS + air system, a formed liquid ring undergoes depolymerization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3565–3577, 2001     

流化床中甲烷芳构化过程

在石英流化床反应器中研究了无氧条件下甲烷直接催化转化制备芳烃的过程.发现催化剂的诱导期长短、甲烷的总转化率与温度、甲烷分压及甲烷空速相关.在973 K下,液体产品中苯的选择性与萘的选择性随着催化剂的失活呈现不同的变化趋势.所得主要技术指标（甲烷转化率、苯的收率与选择性等）与固定床微型反应器中的结果相近.还研究了催化剂上的积炭对甲烷转化率、催化剂失活的影响,为将来的进一步研究提供了基础.     

Pyrolysis of 1,3-butanediol as a model reaction for wood liquefaction in supercritical water

1, 3-Butanediol was pyrolyzed at 425°C in a batch reactor as a model system for liquefaction of lignocellulosic materials such as wood. The observed gas and liquid products were consistent with fragmentation, dehydration, and condensation/polymerization reaction pathways. Reaction in supercritical water altered the selectivity of the reactions to give mainly propene and formaldehyde. Dehydration and the formation of two-carbon products were suppressed by water. The conversion of 1, 3-butanediol in dilute aqueous solutions increased three to four fold when the reaction density was increased by 33%. Trace oxygen was an important inhibitor, particularly in the dilute solution, but had only a minor effect on the reaction selectivity.     

Hydrothermal Treatment of Carboxy‐methyl Cellulose Salt: Formation and Decomposition of Furans,Pentenes and Benzenes

Carboxymethyl cellulose salt as a model compound was treated hydrothermally to understand the degradation and formation of several chemicals (furfural, 5‐(hydroxymethyl)‐furancarboxaldehyde, and benzene derivatives) that might be interesting as platform chemicals or fuels. To realize a manageable control, closed quartz capillaries were chosen as reactor. Experiments were conducted at temperatures from 250 (subcritical water) to 450 °C (supercritical water) and reaction times from 1 to 60 min. By studying the gas chromatography‐mass spectrometry analysis results of the liquid products, their formation and degradation were detected. It was observed that certain substances only appear for several minutes and are then degraded, while for others the concentration increases at lower rate and keeps stable even for long reaction times. The formation of several benzoic structures from a non‐ring‐structured precursor showed that different reaction mechanisms are involved. Different reaction temperatures showed good correlation to the formation rate of several substances.     

Membranes based on polyimide–polyaniline nanocomposites for pervaporation of organic mixtures

Polyimide–polyaniline nanocomposites were obtained by mixing poly{[4,4′‐bis(4″‐N‐phenoxy)diphenylsulfone]imide‐1,3‐bis(3,4‐dicarboxyphenoxy)benzene} (PI) and polyaniline (PANI) solutions in N‐methylpyrrolidone. These solutions were used for the preparation of homogeneous and composite membranes. Uniform distribution of PANI particles in the membranes, resulted from interactions between macromolecules, was confirmed by transmission electron microscopy. Membranes based on PI and PI–PANI were tested in pervaporation of binary organic mixtures: methanol/toluene and methanol/cyclohexane and showed a remarkable selectivity with respect to methanol. In both pervaporation processes, selectivity was improved in PANI‐containing membranes. Interactions between membrane polymers and liquid penetrants (methanol, toluene, and cyclohexane) were studied by measurements of surface tension, sorption, and pervaporation parameters. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Degradation of poly(butylene terephthalate) in different supercritical alcohol solvents

Reactions were carried out in a batch autoclave reactor. Poly(butylene terephthalate) (PBT) and different alcohol solvents were used in the vessel. The reaction products were analyzed by infrared spectroscopy and gas chromatography/mass spectrometry. Alcoholysis of PBT occurred in supercritical methanol, ethanol, and propanol, and we obtained dimethyl terephthalate (DMT), diethyl terephthalate (DET), and dipropyl terephthalate (DPT), respectively. The conversion of PBT at different temperatures showed similar trends but different degradation degrees. The reactivity for the alcoholysis of PBT in supercritical methanol was much higher than those in supercritical ethanol and propanol. DMT and 1,4‐butanediol obtained from the depolymerization of PBT in supercritical methanol reached 98.5 and 72.3%, respectively, at 583 K for 75 min. The yield of DET reached 76% for 75 min. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Catalytic effects of ferric chloride and sodium hydroxide on supercritical liquefaction of thistle (Cirsium yildizianum)

Cirsium yildizianum stalks were liquefied in organic solvents under supercritical conditions with and without catalyst in a cylindrical reactor at temperatures of 260, 280 and 300 °C. The effects of liquefaction temperature, catalyst type and solvent on product yields were investigated. The liquid products (bio-oils) were extracted with diethyl ether and benzene using an extraction procedure. The liquid yields in supercritical methanol, ethanol and acetone were found to as 45.66%, 49.34% and 60.05% in the non-catalytical runs at 300 °C, respectively. The highest conversion (liquid + gaseous products) was obtained in acetone with 10% ferric chloride at 300 °C in the catalytic runs. The produced liquids at 300 °C were analyzed and characterized by elemental, GC–MS and FT-IR. 85, 79 and 60 different types of compounds were identified by GC–MS obtained in methanol, ethanol and acetone, respectively. The liquid products were composed of various organics including aromatics, nitrogenated and oxygenated compounds.     

Methanolysis of Poly（ethylene terephthalate）in Supercritical Phase

1 INTRODUCTIONPoly(ethylene terephthalate), commonly known as PET polyester, is extensively used for making synthetic fibers and package containers. The volume of PET consumed is rising by year, and thus the chemical recycling and reuse of waste PET are drawing much attention for the preservation of resources and the protection of environment. Through chemical recycling, waste PET is depolymerized into its valuable monomers such as dimethyl terephthalate (DMT), bis (hydroxyethyl) ter…     

聚对苯二甲酸丁二醇酯在超临界甲醇中降解机理的研究

在高压间歇无搅拌反应器中研究了聚对苯二甲酸丁二醇酯(PBT)在高温甲醇溶液中的降解行为,通过对降解产物的各种定性和定量的分析,提出了超临界甲醇降解PBT的机理为在甲醇的作用下聚合物分子链的随机断裂和酯交换反应双重作用下发生的降解反应,建立了降解-反应模型.PBT在甲醇溶液中的降解可分为超临界区、非超临界区和中间过渡区三个区域.通过分子量测定考察了PBT在不同的区域中降解规律.在非临界区PBT在溶剂中处于溶胀状态,其数均分子量Mn下降缓慢,解聚程度低;在过渡区PBT的溶解性能提高,聚合物大分子发生断裂,降解速率加快;在超临界区,Mn随反应的进行而迅速下降,聚合物很快完全降解.在超临界区中PBT可实现完全降解,其主要产物为单体对苯二甲酸二甲酯(DMT)和丁二醇(BG),它们的收率可分别可达98.1%和72.3%.     

微藻超临界甲醇直接酯交换法制备生物柴油

以规模化养殖的小球藻为原料,采用超临界甲醇酯交换法开展了制备生物柴油的实验研究。通过对原料藻粉的主要组成和实验产物的元素、化合物组成及基本理化特性进行分析,考察了不同工艺条件对产率的影响。结果表明,在甲醇与湿藻(50% 含水量)配比为8∶1(mL∶g)、反应温度 260℃、反应压力 8 MPa 和停留时间 10 min 的条件下,微藻生物柴油产率高达 9% 以上,具有与石化柴油接近的理化性质和成分组成。     

微藻超临界甲醇直接酯交换法制备生物柴油

以规模化养殖的小球藻为原料,采用超临界甲醇酯交换法开展了制备生物柴油的实验研究。通过对原料藻粉的主要组成和实验产物的元素、化合物组成及基本理化特性进行分析,考察了不同工艺条件对产率的影响。结果表明,在甲醇与湿藻（50%含水量）配比为8∶1（mL∶g）、反应温度260℃、反应压力8 MPa和停留时间10 min的条件下,微藻生物柴油产率高达9%以上,具有与石化柴油接近的理化性质和成分组成。     

Transesterification Kinetics of Soybean Oil for Production of Biodiesel in Supercritical Methanol

A kinetic study on soybean oil transesterification without a catalyst in subcritical and supercritical methanol was made at pressures between 8.7 and 36 MPa. It was found that the conversion of soybean oil into the corresponding methyl esters was enhanced considerably in the supercritical methanol. The apparent activation energies of the transesterification are different with the subcritical and the supercritical states of methanol, which are 11.2 and 56.0 kJ/mol (molar ratio of methanol to oil: 42, pressure: 28 MPa), respectively. The reaction pressure considerably influenced the yield of fatty acid methyl esters (FAME) in the pressure range from ambient pressure up to 25 MPa (280 °C, 42:1). The reaction activation volume of transesterification in supercritical methanol is approximately −206 cm³/mol. The PΔV ^≠ term accounts for nearly 10% of the apparent activation energy, and can not be ignored (280 °C, 42:1).     

Poly(styrene–divinyl benzene)‐immobilized Fe(III) complex of 1,3‐bis(benzimidazolyl)benzene: Efficient catalyst for the photocatalytic degradation of xylenol orange

A polymer‐supported Fe(III) complex of 1,3‐bis(benzimidazolyl)benzene [PS–Fe(III)BBZNH] was used in the photodegradation of xylenol orange (XO) dye with H₂O₂ under UV irradiation. The catalyst was synthesized and characterized by elemental analysis, and Fourier transform infrared, far‐infrared, and UV–visible–diffuse reflectance spectroscopy, Scanning electron microscopy, Brunauer–Emmett–Teller surface area measurements, thermogravimetric analysis, and magnetic measurements. An octahedral coordination around Fe(III) was confirmed by electronic spectral data, and a decrease in the intensity of the ν_CH2Cl peak in PS–Fe(III)BBZNH was observed compared to the polymer support; this indicated the binding of the ligand to the support. An array of experiments were carried out to assess the influence of various reaction parameters on its photocatalytic performance to ensure maximum dye degradation. The maximum photocatalytic activity was observed at pH 8 with 125 mg of catalyst, 300 ppm of XO, and 200 ppm of H₂O₂ with complete mineralization after 90 min, as confirmed by chemical oxygen demand measurements. Furthermore, the reactions were repeated under sunlight and under dark conditions to check the photocatalytic efficiency of PS–Fe(III)BBZNH. It displayed better catalytic performance compared than the unsupported complex, PS–Cu(II)BBZNH [Cu(II) complex of 1,3‐bis(benzimidazolyl)benzene], and PS–VO(IV)BBZNH [VO(IV) complex of 1,3‐bis(benzimidazolyl)benzene]. PS–Fe(III)BBZNH could be recycled for up to seven runs. A tentative mechanism involving ·OH radical was proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46480.     

Heterogeneous Catalysis in Supercritical Media: 1. Carbon Dioxide

Over the past few years, supercritical fluids have received considerable interest as reaction media. Supercritical fluids combine properties of gases and liquids. Densities are lower than in the liquid phase, but significantly higher than in the gas phase. This makes supercritical fluids excellent solvents for a variety of substances. The good dissolution capacity exists only in or near the supercritical range. Reaction products can be separated, for instance, simply by decreasing temperature and pressure. This may be used to intensify the process as complex separation processes, like distillation, are avoided.