Kinetics of cellobiose decomposition under subcritical and supercritical water in continuous flow system

The effects of reaction temperature, pressure and residence time were investigated with a flow apparatus. Cellobiose decomposition kinetics and products in suband supercritical water were examined at temperatures from 320 to 420 °C at pressures from 25 to 40 MPa, and at residence times within 3 sec. Cellobiose was found to decompose via hydrolysis and pyrolysis. The yield of desired hydrolysis product, glucose, was the maximum value of 36.8% at 320 °C, 35 MPa, but the amount of 5-(hydroxymethyl)furfural (HMF), fermentation inhibitor increased too because residence time increased in the subcritical region owing to decrease of reaction rate. Meanwhile, though the yield of glucose is low in the supercritical region, the yield of HMF decreased compared with the subcritical region; and at the minimum yield of HMF (380 °C, 25 MPa), the yield of glucose was 21.4%. The decomposition of cellobiose followed first-order kinetics and the activation energy for the decomposition of cellobiose was 51.05 kJ/mol at 40MPa.     

Structure and thermal behaviour of nylon 6 nanocomposites

In this article, nylon 6/clay nanocomposites with 5 wt % clay (NCN5) were prepared by a twin screw extruder. The effects of annealing including solid‐state annealing (170 and 190°C) and melt‐state annealing (240°C) on the polymorphic behavior and thermal property of NCN5 and nylon 6 have been comparatively studied as a function of annealing time using modified differential scanning calorimetry (MDSC) and wide‐angle X‐ray diffraction. It was demonstrated that NCN5 and nylon 6 exhibit a similar polymorphic behavior when they were annealed at 190°C for different time durations. As the annealing temperature was elevated to 240°C, significant differences in thermal behavior and polymorphism between NCN5 and nylon 6 could be found. For example, the α crystal became the absolutely dominating crystalline phase for NCN5 sample independent on the annealing durations, whereas the formation of γ crystal is greatly enhanced in neat nylon 6 with increasing annealing time. Moreover, a small endothermic peak is observed around 180°C in both nylon 6 and NCN5 samples annealed at 170 and 190°C, which might be related to the melting of microcrystals formed in the amorphous regions during annealing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3116–3122, 2006     

Crystallization of polyamides under elevated pressure: 2. Pressure-induced crystallization of nylon-6 (polycapramide) from the melt

A study has been made on the crystallization of nylon-6 from the melt under elevated pressures. Crystallization induced by pressures of up to 8 kbar at temperatures between 270° and 310°C did not lead to a significant increase of the melting temperature for nylon-6 containing 8% caprolactam. However, the melting peak temperature, as determined by differential scanning calorimetry was found to increase from 220° to 250°C for nylon-6 without caprolactam and crystallized under pressures exceeding 5 kbar for 50 h. The heat of melting of the nylon specimen crystallized under these conditions increased from 14 to 37 cal/g. Thermal decomposition of the polymer could be diminished by heating under pressure and extruding the nylon under vacuum prior to the high pressure crystallization experiments. The specific volume diminished gradually during isothermal crystallization and the melting temperature was found to increase with crystallization time. These observations point to a one stage process for the development of extended-chain crystals of nylon-6. The highest melting peak temperature of 256°C was recorded on nylon-6 which was crystallized at 315°C and 8 kbar for a period of 320 h.     

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).     

Gas holdup in a two-phase vertical tubular reactor at high pressure

Gas holdup in a tubular reactor was measured at pressures from 5 to 14 MPa at 300°C using a differential pressure cell. The effects on gas holdup of gas density, liquid superficial velocity and gas superficial velocity were studied using vacuum tower bottoms from a Venezuelan feedstock with 95.1 wt% +524°C material. Hydrogen was used at superficial gas velocities from 0.7 to 2.0 cm/s. The feed density at 15°C (0.1 MPa), 300°C (5.57 MPa) and 400°C (13.9 MPa) was measured and showed a linear decrease with temperature. Increased gas density at a constant temperature of 300°C increased the gas holdup at all superficial gas velocities. An increase in the liquid flow rate from about 0.04 to 0.1 cm/s did not affect the gas holdup.     

Preparation of nylon 66/mesoporous molecular sieve composite under high pressure

Nylon 66/mesoporous molecular sieve (pore diameter: 2.7 nm) composites were prepared by annealing mixtures of nylon 66 and mesoporous molecular sieve (FSM) powders under high pressures and high temperature (FSM content: 0–60 wt %; pressure: 0.5–30 MPa; temperature: 300°C; time: 1 h). X‐ray diffraction and TEM measurements indicated the presence of the pores of FSM in the composite. Above 2 MPa, nylon 66 was charged in the pores of FSM. The fraction of the charged nylon 66 increased with pressure and was independent of the FSM content (pressure: 2–30 MPa; fraction of charged nylon 66: 54–66%). The infrared spectrum of the composite showed the bands based on Si O, C H, N H, CO. DSC measurement indicated that the heat of fusion of nylon 66 crystallite in the FSM pores was low compared with that of nylon 66. The composites prepared above 2 MPa were found to be superior in storage modulus to nylon 66. The modulus increased with an increase in the fraction of charged nylon 66 and the amount of FSM. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3254–3258, 1999     

Gas transport in rubbery polymers

Permeability coefficients have been measured for CO₂ and CH₄ in polyethylene membranes at 20, 30, and 40°C and at applied gas pressures up to ca. 2 MPa and for CH₄ in three kinds of rubber films at 25, 30, and 35°C and at applied gas pressures up to ca. 2.4 MPa. The pressure dependence of the logarithms of permeability coefficients became linear except for the CO₂—polyethylene system, where the pressure dependence became quadratic, with a minimum at a certain value of pressure. The linear and quadratic dependences can be interpreted by a free volume model of diffusion of a gas molecule in polymers. The temperature dependence of the permeability coefficients at zero pressure difference across the polymer film for each system obeyed an Arrhenius type equation.     

Rapid Crystallization of Silicalite Nanocrystals in a Capillary Microreactor

Silicalite nanocrystals were synthesized in a pressurized capillary microreactor at 150 °C within 11 min with synthesis solutions aged at 80 or 100 °C for 1–6 h. The effects of aging of the synthesis solution and the reaction pressure were examined. The resulting products were characterized by XRD, DLS, TEM, FT‐IR and TG‐DSC. Aging of the synthesis solution played an important role in shortening the crystallization time of the silicalites. The synthesis pressure should be higher than the saturation vapor pressure of water at 150 °C (～0.5 MPa) and silicalite nanocrystals with crystallinities of 70 % and 100 % could be produced from the synthesis solution aged at 100 °C for 2 h with residence times of 11 min at 0.7 MPa and 1 MPa, respectively. The mean particle sizes of these two samples were 102.2 nm and 166.4 nm, respectively. Thus, the crystallization time of the silicalite nanocrystals is shown to be significantly reduced in the capillary microreactor compared to a traditional batch system.     

Extraction of bioactive components from Centella asiatica using subcritical water

Bioactive components, asiatic acid and asiaticoside, were extracted from Centella asiatica using subcritical water as an extraction solvent. Extraction yields of asiatic acid and asiaticoside were measured using high-performance liquid chromatography (HPLC) at temperatures from 100 to 250 °C and pressures from 10 to 40 MPa. As temperature or pressure increased, the extraction yield of asiatic acid and asiaticoside increased. At the optimal extraction conditions of 40 MPa and 250 °C, the extraction yield of asiatic acid was 7.8 mg/g and the extraction yield of asiaticoside was 10.0 mg/g. Extracted asiatic acid and asiaticoside could be collected from water as particles with a simple filtering process. Dynamic light scattering (DLS) was used to characterize particle size. Particles containing asiatic acid were larger (1.21 μm) than particles containing asiaticoside (0.76 μm). The extraction yields of asiatic acid and asiaticoside using subcritical water at 40 MPa and 250 °C were higher than extraction yields using conventional liquid solvent extraction with methanol or ethanol at room temperature while the subcritical water extraction yields were lower than extraction yields with methanol or ethanol at its boiling point temperature.     

Synthesis and characterization of the novel nylon 12 6 based on 1,12‐diaminododecane

Successful polymerization of nylon 12 6 was accomplished in two‐steps, the preparation of nylon salts and involvement of the salts with a pressure vessel followed by high temperature melt polymerization. Chemical composition, thermal properties, crystal structure, mechanical properties, and moisture absorption were characterized in detail. Melting temperature and glass transition temperature were recorded at 234°C and 75°C, respectively, while the β‐relaxation peak was determined to be ?64°C. The results indicated that nylon 12 6 could be used at a broad range of temperatures. Characterization of the mechanical properties showed that nylon 12 6 exhibited a better flexibility and elongation compared with other industrially important nylons. The moisture absorption of nylon 12 6 decreased by 36.7% compared with that of nylon 6 12, suggesting that nylon 12 6 will exhibit a better dimensional stability in the humid environment. Overall, in this research, the novel nylon, that is, the nylon 12 6, shows a relatively low water absorption and excellent toughness contributing to its potential technological application in the future. POLYM. ENG. SCI., 59:192–197, 2019. © 2018 Society of Plastics Engineers     

Evaluation of the formability of plastic/Zn22Al/plastic sandwiched structures by gas blowing

For the manufacturing of electromagnetic interference (EMI) shielding enclosures for portable 3C (computer, communication, and consumer electronics) products, a superplastic Zn22Al thin sheet is inserted in between plastic plates and formed by in-mold blowing with gas pressure. In order to evaluate the formability of a plastic/Zn22Al/plastic sandwiched structure, free bulging tests are conducted in the temperature range between 135°C and 200°C in an infrared furnace. The results show that the ABS/Zn22Al/ABS sandwiched structure can be free bulged at 150°C with 0.21 MPa of gas pressure at a forming rate similar to that of the monolithic Zn22Al sheet. The PC/Zn22Al/PC sandwiched structure cannot be effectively bulged until the forming temperature is raised to 185°C. The optimized forming condition for PC/Zn22Al/ABS is either at 150°C with a gas pressure of 0.35 MPa or at 165°C and a gas pressure setting of 0.21 MPa. Also, the thickness distributions for Zn22Al and a variety of plastic/Zn22Al/plastic specimens after free bulging at various temperatures with various gas pressures are placed in comparison in this study.     

Recycling Nylon 6 Carpet to Caprolactam

The recycling of nylon 6 carpet via depolymerization provides the potential for an environmentally benign new process to produce world-class caprolactam. This article describes the depolymerization of nylon 6 carpet in the presence of steam under medium pressure (800-1500 kPa, 100-200 psig). A small laboratory apparatus was set up to demonstrate the feasibility of the scheme. A total of eight runs were carried out using ～180 g of pellitized carpet and 2-6 g/min steam (at 101-1500 kPa, 0-200 psig, and 300-340°C). In our best run at 340°C, 6 g/min of steam, and 1500 kPa (200 psig) for 3 h, we obtained a 95% yield of crude caprolactam. The lactam purity was 94.4%, resulting in an overall 89.7% yield of caprolactam. The laboratory data were used to construct a computer model of the process for both batch and continuous-flow stirred reactors.     

Solubility of fatty acids in subcritical water

A phase equilibrium apparatus was designed to determine the solubilities of stearic acid and palmitic acid in subcritical water at different temperatures and pressures. The dissolution equilibrium time was measured. The effect of an ultrasonic field on dissolution equilibrium was also studied. The results showed that the maximum solubilities of stearic acid and palmitic acid were 0.136 g/100 g and 0.178 g/100 g in subcritical water at temperatures of 180 °C and 160 °C, respectively, and a pressure of 15 MPa for 30 min. An ultrasonic field also clearly promoted the dissolution of fatty acids in subcritical water. The dissolution equilibrium time was shortened to 20 min using ultrasonic oscillation (250 W, 20 kHz).     

Crystallization and dissolution behaviour of polyamide 6–water systems under pressure

The solubility of polyamide 6 (PA6) in water under pressure has been reported recently and is explored further here using a pressurized differential scanning calorimeter equipped with a pressure regulator, enabling operation at constant pressure. The optimum parameters for solubility (temperature, pressure, concentration) were determined. Crystallization and melting temperature depressions of a maximum of 60 °C were found. The minimum water concentration needed to reach the maximum temperature depression was found to be approximately 30 mass%. Because in such a case the end melting/dissolution temperature for PA6 in water is approximately 165 °C, the pressure level has to be high enough to prevent water from evaporating, i.e. above 8 bar (0.8 MPa). The expected industrial uses of the water solubility of polyamides under pressure are to ease the processing of polyamides by extrusion; to make polyamide composites; to disperse temperature‐sensitive fillers in polyamides; and, in general, to realize ‘green’ routes for the formation of polyamides. Copyright © 2010 Society of Chemical Industry     

Solubility of red pepper (C<Emphasis Type="Italic">apsicum annum</Emphasis>) oil in near- and supercritical carbon dioxide and quantification of capsaicin

Red pepper oil was extracted using near- and supercritical carbon dioxide. Extraction was carried out at pressures ranging from 10 to 35 MPa and temperatures from 30 to 60 °C, with a CO₂ flow rate of 24.01 g/min using a semi-continuous high-pressure extraction apparatus. The duration for extraction was 2 h. The highest oil yield was found at high pressure and temperature. The highest solubility of oil (1.18 mg/g of CO₂) was found at 35 MPa and 60 °C. The solubility data of red pepper oil in near- and supercritical CO₂ were fitted in Chrastil model. The fatty acid composition of red pepper oil was analyzed by gas chromatography (GC). Linoleic acid was found to be the major fatty acid in the oil. Capsaicin was quantified in different extracts by high performance liquid chromatography (HPLC). The highest capsaicin yield was found at 35 MPa and 60 °C.     

Noncatalytic Hydrolysis of Iminodiacetonitrile in Near‐Critical Water – A Green Process for the Manufacture of Iminodiacetic Acid

The hydrolysis of iminodiacetonitrile (IDAN) in near‐critical water, without added catalysts, has been successfully conducted with temperature and residence time ranges of 200–260 °C and 10–60 min, respectively. The effects of temperature, pressure, and initial reactant/water ratio on the reaction rate and yield have been investigated. The final reaction products primarily included iminodiacetic acid (IDA) and ammonia associated with other by‐products; gas formation was negligible. The maximum yield of IDA was 92.3 mol.‐% at 210 °C and 10 MPa, with a conversion of almost 100 %.The apparent activation energy and ln A of IDAN hydrolysis were evaluated as 45.77 ± 5.26 kJ/mol and 8.6 ± 0.1 min^–1, respectively, based on the assumption of first‐order reaction. The reaction mechanism and scheme were similar to those of base‐catalyzed reactions of nitriles examined in less severe conditions.     

Depolymerization of poly(trimethylene terephthalate) in supercritical methanol

The depolymerization of poly(trimethylene terephthalate) (PTT) in supercritical methanol was carried out with a batch‐type autoclave reactor at temperatures ranging from 280 to 340°C, at pressures ranging from 2.0 to 14.0 MPa, and for reaction time of up to 60 min. PTT quantitatively decomposed into dimethyl terephthalate (DMT) and 1,3‐propaniol (PDO) under the designed conditions. The yields of DMT and PDO greatly increased as the temperature rose. The yields of the monomers markedly increased as the pressure increased to 10.0 MPa, and they leveled off at higher pressures. The final yield of DMT at 320°C and 10.0 MPa reached 98.2%, which was much closer to the extent of the complete reaction. A kinetic model was used to describe the depolymerization reaction, and it fit the experimental data well. The dependence of the forward rate constant on the reaction temperature was correlated with an Arrhenius plot, which gave an activation energy of 56.8 kJ/mol. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2363–2368, 2004     

The solubility of methane in aqueous solutions of monoethanolamine,diethanolamine and triethanolamine

The solubility of methane in 3 kmol/m³ solutions of monoethanolamine, diethanolamine, and triethanolamine was measured from 25° to 125°C and pressures up to about 13 MPa. Measurements were also made for the solubility of methane in water at 25° to 125°C and pressures up to 18 MPa in order to confirm the accuracy of the experimental technique. It is demonstrated that methane is more soluble (in terms of mole fraction) in the amine solution than in pure water. Furthermore, the solubility is an increasing function of the size of the alkanolamine. The solubility data were modeled using a Henry's-law approach and the results summarized in terms of salting-in coefficients.     

Monitoring epoxy and unsaturated polyester reactions under pressure—Reaction rates and mechanical properties

The effects of pressure on reaction rates and final mechanical properties were studied for an unsaturated polyester (UP) and epoxy resin. A pressure chamber where reactions can be monitored by use of Raman spectroscopy has been built for these purposes. The chamber allows for pressures up to 13.8 MPa at 200°C. An advanced temperature control system has been adapted to the vessel to precisely control and monitor sample temperature variations and overshoots. It is described how for an accelerated UP reaction increasing pressure will result in a competing effect on the reaction rate where the rate will initially lower, but with increased pressures it may accelerate due to acceleration of the reaction rate constants. The final mechanical properties exhibit a similar behavior slightly increasing with pressure but lowering as pressure is raised further. For epoxy, it was shown that the reaction kinetics were accelerated by pressure although no mechanical property differences could be noted for the pressure ranges tested. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers.     

High-pressure reaction and emissions characteristics of catalytic reactors for gas turbine combustors

The reaction and emissions characteristics of catalytic reactors comprising noble metal catalysts were investigated using homogeneous mixtures of natural gas and vitiated air at pressures up to 2.9 MPa. The mixture temperatures at inlet ranged from 500 to 700°C and the fuel-air ratio was increased till the exit gas temperature reached about 1200°C. Values of combustion efficiency greater than 99.5% and nitrogen oxides emissions for all catalytic reactors tested were less than 0.2 g NO₂/kg fuel (2 ppm (15% 0₂) ) for all reactors at reactor exit gas temperatures higher than about 1100°C. Combustion efficiency decreased with increasing pressure in the heterogeneous-reaction controlled region, though a pressure increase favored homogeneous, gas phase reactions. Appreciable reactivity deterioration by aging for 1000 h at 1000°C was observed at lower mixture temperatures. A two-stage combustor comprising a conventional flame combustion stage and a catalytic stage was fabricated and its NO,_x emissions and performance were evaluated at conditions typical of stationary gas turbine combustor operations. About 80% reduction in NO,_x emissions levels compared with flame combustion was attained at 1 MPa pressure and 1180°C exit gas temperature, together with complete hydrocarbon combustion.