Kinetic studies on Victorian brown coal hydroliquefaction

Reaction kinetics of the liquefaction of Victorian brown coal in a process development unit (PDU) having three reactors in series have been studied at temperatures of 430–470°C, and pressures of 15–25 MPa. It is shown that the rate of hydrogen consumption can be expressed as a function of the concentrations of coal and catalyst, hydrogen partial pressure, reaction temperature and residence time, and is controlled by the rates of hydrogenation of polynuclear aromatic components, and the rates of formation and stabilization of radicals. The relative contribution of these reactions, at any temperature, determine the influence of the hydrogen partial pressure on the rate of the hydrogen consumption. The kinetics of the decomposition reactions of brown coal to preasphaltene, asphaltene and to oil also have been studied. The apparent activation energies determined are 25 kJ mol^?1 for the brown coal to preasphaltene, 50 kJ mol^?1 for preasphaltene to asphaltene, 76 kJ mol^?1 for asphaltene to oil, and 184 kJ mole^?1 for oil to gases.     

Study of the reaction between resorcinol and formaldehyde

The reactions between resorcinol and formaldehyde were led in aluminium pans of a d.s.c. Perkin Elmer calorimeter. The products were separated by means of high performance liquid chromatography and identified by ¹H and ¹³C n.m.r. Depending on the catalyst concentration and molar ratio the mixtures reacted at two different temperature ranges, 317–332K and 332–366K. The heat of the reaction in the first temperature range was between 16.8 and 45.0 kJ mol^?1 for molar ratios 1:1 and 1:3 respectively. By ¹H and ¹³C n.m.r. spectroscopy five addition products were determined. The reaction heat in the second temperature range was 73.5 kJ mol^?1 and was attributed to condensation reactions. The activation energies were 95.0 and 120.0 kJ mol^?1 for addition and condensation reactions respectively. For addition, order two and for condensation, order one of reaction was established. On the basis of these foundings tentative reaction schemes were prepared.     

Hydride Transfer: A Dominating Reaction of Ozone with Tertiary Butanol and Formate Ion in Aqueous Solution

This article provides evidences that hydride transfer is an important primary step in ozone reactions of formate and tertiary butanol in aqueous media. In both systems, one argument is the fact that the free hydroxyl radical yields are relative low ((40 ± 4)% and (7 ± 0.8)% for formate and tertiary butanol, respectively). Another hint is the high exergonicity of these reactions: ΔG = –249 kJ mol^?1 for formate/ozone system and ΔG = –114 kJ mol^?1 for hydride transfer followed by a methyl shift in the reaction between tertiary butanol and ozone. In addition, the main product of tertiary butanol ozonolysis is butan-2-one [(89 ± 3)%], a compound that is formed only via hydride transfer. For the reaction of ozone with formate an activation energy of (54.6 ± 1.2) kJ mol^?1 and a pre-exponential term of (2.5 ± 1.2) × 10¹¹ were determined (in the presence of tertiary butanol as ^?OH scavenger) whereas for tertiary butanol the two activation parameters were (68.7 ± 1.9) kJ mol^?1 and (2.0 ± 1.5) × 10⁹, respectively.     

The synthetic kinetics and underwater acoustic absorption properties of novel epoxyurethanes and their blends with epoxy resin

Reaction kinetics between isocyanate-terminated prepolyurethane (PPU) and glycidol using dibutyltin dilaurate (DBTDL) as a catalyst was investigated by monitoring the change in the intensity of the absorbance peak of NCO stretching band at 2,270?cm^?1 on Fourier transform infrared spectrum at different temperatures. The results indicated that the reactions of TDI- and IPDI-type PPU with glycidol followed second-order kinetics, and their activation energies could be efficiently reduced by DBTDL. For TDI-type PPU, the reaction activation energies were 80.37?kJ?mol^?1 without catalyst, 49.86?kJ?mol^?1 with 0.1?% of DBTDLs, and 37.85?kJ?mol^?1 with 0.2?% of DBTDLs, respectively. For IPDI-type PPU, the reaction activation energies were 69.16?kJ?mol^?1 without catalyst, 63.05?kJ?mol^?1 with 0.1?% of DBTDLs, and 55.57?kJ?mol^?1 with 0.2?% of DBTDLs, respectively. This corresponding TDI- and IPDI-type epoxyurethane (EPU) were blended with epoxy resins (EPs) and cured by the Michael adduct of ethlylenediamine with butyl acrylate (molar ratio?=?1:1) curing agent, to prepare EPU/EP blend elastomers for underwater acoustic absorption materials. The TDI-type EPUs had good acoustic absorption properties and the average acoustic absorption coefficient of TDI-type EPU was 0.75, the maximum acoustic absorption coefficient was 0.94; the EPUs blended with E-51 EP had better acoustic absorption properties than those from E-44; and the EPU from PPG-2000 had better underwater acoustic absorption properties than that from PPG-1000.     

Determination of Nucleation and Crystal Growth Kinetics in Hostile Environment – Application to the Tetravalent Uranium Oxalate U(C2O4)2. 6H2O

A specific apparatus and an original batch method are developed for, respectively, nucleation and crystal growth rate measurements in a hostile environment, such as glove box. Primary nucleation and crystal growth kinetic rates for uranium oxalate are measured over a wide range of temperatures and solution concentrations. The nucleation rate obeys the Volmer‐Weber equation, with activation energies of 182 kJ.mol^?1 for the homogeneous nucleation and 102 kJ.mol^?1 for the heterogeneous one. The crystal growth rate is first order with respect to the supersaturation and controlled by a surface integration mechanism, characterized by a 29 kJ.mol^?1 activation energy.     

Adsorption of BTX compounds from aqueous solutions by water-insoluble starch

The removal of benzene, toluene and p-xylene (BTX) compounds from aqueous solutions with highly crosslinked cationic starch containing tertiary amine groups was investigated. The adsorption process has found to be initial pH- and initial concentration-dependent, endothermic, and follows the Langmuir isothermal adsorption. The heats of adsorption (ΔH) at initial pH = 4 of benzene, toluene and p-xylene compounds are 29.45 kJ mol^?1, 34.41 kJ mol^?1, and 35.58 kJ mol^?1, respectively, those at initial pH = 10 are 30.17 kJ mol^?1, 35.56 kJ mol^?1, and 39.39 kJ mol^?1, respectively. The order of the amount of adsorbed BTX compounds on the adsorbent is benzene > toluene > p-xylene.     

Thermal degradation and morphological studies on cotton cellulose modified with various arylphosphorodichloridites

Cellulose arylphosphonate compounds have been synthesized and investigated by the kinetics of thermal degradation by thermogravimetry (TG) and differential scanning calorimetry (DSC) from ambient temperature to 600°C. Various kinetic and thermodynamic parameters such as energy, entropy and free energy of activation have been obtained from TG curves using the Broido method and transition state theory. The high values of enthalpy change (1016 and 1025 J g^?1) of decomposition and oxidation reactions corresponding to the last two exotherms of the DSC curves of cellulose are decreased to a greater extent in the case of cellulose arylphosphonate compounds. The values of activation energy for the decomposition stage of cellulose arylphosphonate compounds lie in the range 25–49 kJ mol^?1 and are found to be lower than that of pure cellulose, namely 165 kJ mol^?1 in air atmosphere. Scanning electron micrographs of phosphorylated cotton cellulose and chars show furrowed and fractured surfaces although the morphology of the original fibres remains largely unchanged. Furthermore, higher char yields of cellulose derivatives leads to the conclusion that such derivitisation may give rise to flame‐retardant treatments for cellulosic materials. Copyright © 2004 Society of Chemical Industry     

Effect of particle size on thermal decomposition and devolatilization kinetics of melon seed shell

Thermogravimetric analysis (TGA) and devolatilization kinetics of melon seed shell (MSS) at different particle sizes (150?µm and 500?µm) and at different heating rates (10, 15, 20, and 25?°C/min) were investigated with the aid of TGA. The results of the TGA analysis show that the TGA curves corresponding to the first and third stages for 150?µm particle sizes exhibited some bumps that developed at the first and third stages of pyrolysis. It was also observed that at constant heating rate, the maximum peak temperature increases as the particle sizes increase from 150 to 500?µm, whereas 500?µm particle sizes exhibited higher peak temperatures compared to 150?µm particle sizes. The resulting TGA data were applied to the Kissinger (K), Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) methods and kinetic parameters (activation energy, E and frequency factor, A) were determined. The E and A obtained using K method were 74.27?kJ mol^?1 and 3.84?×?10⁵?min^?1 for 150?µm particle size, whereas for 500?µm particle size were 97.12?kJ mol^?1 and 3.74?×?10⁷?min^?1, respectively. However, the average E and A obtained using KAS and FWO methods were 82.35?kJ mol^?1, 1.29?×?10⁷?min^?1, and 88.50?kJ mol^?1, 1.32?×?10⁷?min^?1 for 150?µm particle sizes. While for 500?µm particle sizes, the E and A were 108.46?kJ mol^?1, 3.14?×?10⁹?min^?1, and 113.05?kJ mol^?1, 7.56?×?10⁹?min^?1, respectively. It was observed that E and A calculated from FWO and KAS methods were very close and higher than that obtained by K method. It was observed that the minimum heat required for the cracking of MSS particles into products is reached later at higher peak temperatures since the heat transfer is less effective as they are at lower peak temperatures.     

Laboratory-scale coal reactivity testing for entrained gasification

A relatively simple and rapid micro-gasification test has been developed for measuring gasification reactivities of carbonaceous materials under conditions which are more or less representative of an entrained gasification process, such as the Shell coal gasification process. Coal particles of < 100 μm are heated within a few seconds to a predetermined temperature level of 1000–2000 °C, which is subsequently maintained. Gasification is carried out with either CO₂ or H₂O. It is shown that gasification reactivity increases with decreasing coal rank. The CO₂ and H₂O gasification reactions of lignite, bituminous coal and fluid petroleum coke are probably controlled by diffusion at temperatures 1300–1400 °C. Below these temperatures, the CO₂ gasification reaction has an activation energy of about 100 kJ mol^?1 for lignite and 220–230 kJ mol^?1 for bituminous coals and fluid petroleum coke. The activation energies for H₂O gasification are about 100 kJ mol^?1 for lignite, 290–360 kJ mol^?1 for bituminous coals and about 200 kJ mol^?1 for fluid petroleum coke. Relative ranking of feedstocks with the micro-gasification test is in general agreement with 6 t/d plant results.     

Kinetic and thermodynamic investigation of Arthrospira (Spirulina) platensis fed‐batch cultivation in a tubular photobioreactor using urea as nitrogen source

BACKGROUND: Fed‐batch culture allows the cultivation of Arthrospira platensis using urea as nitrogen source. Tubular photobioreactors substantially increase cell growth, but the successful use of this cheap nitrogen source requires a knowledge of the kinetic and thermodynamic parameters of the process. This work aims at identifying the effect of two independent variables, temperature (T) and urea daily molar flow‐rate (U), on cell growth, biomass composition and thermodynamic parameters involved in this photosynthetic cultivation. RESULTS: The optimal values obtained were T = 32 °C and U = 1.16 mmol L^?1 d^?1, under which the maximum cell concentration was 4186 ± 39 mg L^?1, cell productivity 541 ± 5 mg L^?1 d^?1 and yield of biomass on nitrogen 14.3 ± 0.1 mg mg^?1. Applying an Arrhenius‐type approach, the thermodynamic parameters of growth (ΔH* = 98.2 kJ mol^?1; ΔS* = ? 0.020 kJ mol^?1 K^?1; ΔG* = 104.1 kJ mol^?1) and its thermal inactivation ( kJ mol^?1; kJ mol^?1 K^?1; kJ mol^?1) were estimated. CONCLUSIONS: To maximize cell growth T and U were simultaneously optimized. Biomass lipid content was not influenced by the experimental conditions, while protein content was dependent on both independent variables. Using urea as nitrogen source prevented the inhibitory effect already observed with ammonium salts. Copyright © 2012 Society of Chemical Industry     

Kinetics study on the reactive extraction of homophenylalanine enantiomers with BINAP-copper complex

This paper reports on the kinetics study of the reactive extraction of homophenylalanine (Hph) enantiomers with BINAP (2,2’-Bis(diphenylphosphino)-1,1’-binaphthalene)-copper complex (BINAP-Cu) as the chiral selector. The kinetic model was established based on the theory of interfacial chemical reactive extraction. Simultaneously, the effects of agitation speed, interface area, pH value of the aqueous phase, initial concentration of Hph enantiomers and initial concentration of BINAP-Cu on the specific rate of extraction were investigated. The forward rate constants of the reactions in reactive extraction process were found to be 6.16 × 10^?4 m^2.5mol^?0.5s^?1 for D-Hphe and 7.303 × 10^?4 m^2.5mol^?0.5s^?1 for L-Hphe.     

TRANSFER RATE AND SEPARATION OF Sr2+ and Cs+ BY SUPPORTED LIQUID MEMBRANES UTILIZING SYNERGIZED CROWN ETHER CARRIERS

ABSTRACT

The rate of the isotopic exchange of Na? and Cs? between hydrous silicon-titanium(IV) oxide in the relevant ionic form and aqueous solution was determined radiochemically. The rate was controlled by the diffusion of the ions in the exchanger particles. The diffusion coefficients at 5 °C are (3.9±0. 1)×10^?11m² s^?1 and (2.4± 0. 1)×10^?11 m² s^?1respectively, for Na? and Cs? in the exchanger equilibrated with solutions at pH 6. The activation energies are 31±5 kJ mol^?1 and 20±5 kJ mol^?1 for Na? and Cs? diffusion, respectively. The diffusion coefficients of the ions decreases with increasing pH of the solutions equilibrated with the exchanger, whereas their activation energy is independent of pH. The results were interpreted in terms of the strength of the electrostatic interaction between the counter ions and the ion-exchange sites.     

Heavy Metal Removal and Neutralization of Acid Mine Waste Water ‐ Kinetic Study

The influence of the apatite on the efficiency of neutralization and on heavy metal removal of acid mine waste water has been studied. The analysis of the treated waste water samples with apatite has shown an advanced purification, the concentration of the heavy metals after the treatment of the waste water with apatite being 25 to 1000 times less than the Maximum Concentration Limits admitted by European Norms (NTPA 001/2005). In order to establish the macro‐kinetic mechanism in the neutralization process, the activation energy, Ea, and the kinetic parameters, rate coefficient of reaction, k_r, and k_t were determined from the experimental results obtained in “ceramic ball‐mill” reactor. The obtained values of the activation energy Ea >> 42 kJ mol^?1 (e.g. Ea = 115.50 ± 7.50 kJ mol^?1 for a conversion of sulphuric acid η_H2SO4 = 0.05, Ea = 60.90 ± 9.50 kJ mol^?1 for η ^H2SO4 = 0.10 and Ea = 55.75 ± 10.45 kJ mol^‐1 for η ^H2SO4 = 0.15) suggest that up to a conversion of H2SO4 equal 0.15 the global process is controlled by the transformation process, adsorption followed by reaction, which means surface‐controlled reactions. At a conversion of sulphuric acid η ^H2SO4 > 0.15, the obtained values of activation energy Ea < 42 kJ mol^‐1 (e.g. Ea = 37.55 ± 4.05 kJ mol^‐1 for η ^H2SO4 = 0.2, Ea = 37.54 ± 2.54 kJ mol^‐1 for η ^H2SO4 = 0.3 and Ea = 37.44 ± 2.90 kJ mol^‐1 for η ^H2SO4 = 0.4) indicate diffusion‐controlled processes. This means a combined process model, which involves the transfer in the liquid phase followed by the chemical reaction at the surface of the solid. Kinetic parameters as rate coefficient of reaction, kr with values ranging from (5.02 ± 1.62) 10‐4 to (8.00 ± 1.55) 10‐4 (s^‐1) and transfer coefficient, kt, ranging from (8.40 ± 0.50) 10‐5 to (10.42 ± 0.65) 10‐5 (m s^‐1) were determined.     

Kinetics of non-catalytic hydrocracking of Athabasca bitumen

The kinetics of non-catalytic hydrocracking of Athabasca bitumen were studied in a batch reactor at 648–693 K and at an initial hydrogen pressure of 7.2 MPa. The reaction products were separated into coke, asphaltenes, resins, aromatics, saturates and gases. Reaction time versus product yield curves were obtained for the above six product groups. Two simple reaction models were proposed. In the first, bitumen is considered to be a single reactant and the hydrocracking reaction a single irreversible reaction. The activation energy for bitumen consumption was found to be 150 kJ mol⁻¹. In the second model, coke, asphaltenes, maltenes and gases are treated as components. Activation energies for the reactions were found to be in the range 142–284 kJ mol⁻¹. Hydrocracking reactions were found to be first order. Activation energies for the hydrocracking reactions are compared with those for thermal cracking reactions.     

Thermal and spectroscopic studies on flame-retardant cotton cellulose modified with THPC-urea-ADP and its transition metal complexes

Cotton cellulose has been treated with tetrakis(hydroxymethyl)phosphonium chloride (THPC), urea and small amounts of ammonium dihydrogen orthophosphate (ADP) to impart flame retardancy. Complexes of cell-THPC-urea-ADP with transition metals such as chromium, manganese, iron, cobalt, nickel, copper and zinc have been characterized by reflectance UV-visible spectra. The samples were subjected to differential thermal analysis and thermogravimetry from ambient temperature to 700°C in air to study their thermal behaviour. From the resulting data, various kinetic parameters for different stages of thermal degradation were obtained following the method of Broido. For the decomposition of cellulose and flame-retardant celluloses, the activation energy was found to increase from 242 to 322kJ mol^?1, the entropy of activation from 140 to 307 JK^?1 mol^?1 and the char yield from 2.5 to 31%. The free energy of activation for decomposition of cellulose and its derivatives was almost the same, viz. 148–162 kJ mol^?1, indicating that the basic steps in the decomposition of cellulose and its derivatives are the same. The IR spectra of the thermally degraded residues of cell-THPC-urea-ADP and its metal complexes indicate that dehydration takes place and a compound containing the carbonyl group is formed. The electron paramagnetic resonance signals indicate the formation of trapped and stable free radicals in the thermal degradation of cellulose and its derivatives.     

The external mass transfer of basic and acidic dyes on wood

The parameters affecting the initial adsorption rates of Astrazone Blue dye (Basic Blue 69) on to wood have been studied. A simple model has been proposed to determine the external mass transfer coefficients and these have been compared with values obtained using a more complex procedure. The external mass transfer coefficient, β, has been shown to vary linearly with agitation and initial dye concentration using log-log coordinates; furthermore β is independent of particle size. The effect of temperature has been studied and the activation energy for the process is 44 ± 2 kJ mol^?1. Similar correlations were obtained for the adsorption of Telon Blue dye (Acid Blue 25) on wood. Using log-log correlations, the external mass transfer coefficient was found to vary with (rev min^?1)^0.14, C₀^?0.27; and a small dependence on particle size was also observed. The activation energy for the external mass transfer process was 25 ± 2 kJ mol^?1.     

Adsorptive removal of anionic and non‐ionic surfactants from aqueous phase using Posidonia oceanica (L.) marine biomass

BACKGROUND: In this study, the capability of low‐cost, renewable and abundant marine biomass Posidonia oceanica (L.) for adsorptive removal of anionic and non‐ionic surfactants from aqueous solutions have been carried out in batch mode. Several experimental key parameters were investigated including exposure time, pH, temperature and initial surfactant concentration. RESULTS: It was found that the highest surfactant adsorption capacities reached at 30 °C were determined as 2.77 mg g^?1 for anionic NaDBS and as 1.81 mg g^?1 for non‐ionic TX‐100, both at pH 2. The biosorption process was revealed as a thermo‐dependent phenomenon. Equilibrium data were well described by the Langmuir isotherm model, suggesting therefore a homogeneous sorption surface with active sites of similar affinities. The thermodynamic constants of the adsorption process (i.e. ΔG°, ΔH° and ΔS°) were respectively evaluated as ? 8.28 kJ mol^?1, 48.07 kJ mol^?1 and ? 42.38 J mol^?1 K^?1 for NaDBS and ? 9.67 kJ mol^?1, 95.13 kJ mol^?1 and ? 174.09 J mol^?1 K^?1 for TX‐100. CONCLUSION: Based on this research, valorization of highly available Posidonia oceanica biomass, as biological adsorbent to remove anionic and non‐ionic surfactants, seems to be a promising technique, since the sorption systems studied were found to be favourable, endothermic and spontaneous. Copyright © 2007 Society of Chemical Industry     

Intensified and safe ozonolysis of fatty acid methyl esters in liquid CO2 in a continuous reactor

We demonstrate a continuous reactor for performing the ozonolysis of fatty acid methyl esters (FAMEs) using liquid CO₂ as solvent. The fast reaction kinetics allows the use of small‐volume reactors to completely convert the FAMEs, forming secondary ozonides as the primary products. The short residence times also help maximize the yields of the secondary ozonides by minimizing over‐oxidation and the formation of oligomeric products. The liquid CO₂ medium promotes safe reactor operation by providing an essential fraction of overall reactor cooling and by diluting the vapor phase organics. We also demonstrate a continuous stirred reactor for the safe thermal decomposition of the secondary ozonides to their corresponding acids and aldehydes. Using a lumped kinetic model for the thermal decomposition of the ozonolysis products, we estimate activation energy values of 108.6 ± 0.6 kJ mol^?1 for the decomposition of secondary ozonides and 122 ± 3 kJ mol^?1 for the decomposition of the undesired oligomeric species. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2819–2826, 2017     

A thermal study on the use of immobilized penicillin G acylase in the formation of 7‐amino‐3‐deacetoxy cephalosporanic acid from cephalosporin G

Penicillin G acylase (PGA) is an important enzyme for the industrial production of 7‐amino‐3‐deacetoxy cephalosporanic acid (7‐ADCA) from cephalosporin G (Ceph‐G), and 6‐aminopenicillanic acid (6‐APA) from penicillin G (Pen‐G). These products are used for the manufacture of semi‐synthetic cephalosporins and penicillins. In this study, immobilized PGA was utilized to catalyze the conversion of Ceph‐G to 7‐ADCA. The optimal conditions were found to be an operating temperature of 45 °C, 0.2 M phosphate buffer, a substrate concentration of 30 mg cm^?3 and a catalyst particle concentration of 0.01 g cm^?3 (specific activity of 623.2 U g^?1). Up to 45 °C the reaction was characterized by an activation energy of 38.66 kJ mol^?1. Beyond 57.5 °C there was a sharp decline of activity, characterized by a deactivation energy of 235.88 kJ mol^?1. Copyright © 2004 Society of Chemical Industry