Nth-order Kinetic Model Research Articles

Effect of a novel metal-free green synthesis catalyst on the positive role of microwave irradiation in hydrogen production from the hydrolysis of sodium borohydride

This study demonstrates the synthesis of hydrochar, a high-value material, from watermelon seed husk, a low-value waste material, using the hydrothermal synthesis method. The microwave power effect plays an important role in the use of metal-free and environmentally friendly catalysts for the hydrolysis of sodium borohydride. The XRD, BET, SEM, and FTIR analyses characterized the catalyst. X-ray diffraction revealed the catalyst structure to be cellulosic. The surface area and total pore volume were 1.063 m2/g and 0.0195 cm3/g, respectively, in BET analysis. According to the IUPAC classification, the catalyst conformed to the type III isotherm. This study investigated how good the catalyst for the hydrolysis of sodium borohydride was when it was exposed to microwave irradiation at different microwave powers, solution temperatures, and catalyst amounts. The Langmuir-Hinshelwood and nth-order kinetic models calculated the activation energies to be 82.192 and 83.35 kJ/mol, respectively. The use of bio-waste hydrochar as a catalyst in the hydrolysis of sodium borohydride in the microwave environment shows promising results in the search for metal-free catalysts.

Green synthesis of NiO from watermelon seed shell extract for the evaluation of H2 production from NaBH4 hydrolysis and photocatalytic reduction of methylene blue

In the study, NiO nanoparticles were successfully prepared from watermelon seed shell extract as a reducing agent by the green synthesis method. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and ultraviolet–visible (UV–vis) were used for the characterization of NiO nanoparticles to evaluate the structural and morphological identifications. The NiO nanoparticles were applied for the first time as a photocatalyst in the photocatalytic reduction of methylene blue and as a catalyst in H2 production from NaBH4 hydrolysis. In the photocatalytic reduction of methylene blue with NaBH4 as a reducing agent, it was observed that there was no colour change for 24 h without catalyst, and 98 % of methylene blue was reduced in 13 min in the presence of NiO nanoparticles. The photocatalytic reduction kinetics of methylene blue was investigated using the pseudo-first-order model, and the rate constant was found to be 0.382 min−1. H2 production from NaBH4 hydrolysis using the NiO nanoparticles was investigated in terms of the effect of microwave radiation ambient and temperature. The kinetics of H2 production from NaBH4 hydrolysis was studied by applying the nth-order kinetic model. The H2 production rate (rH2), activation energy (Ea) and reaction order (n-value) were found to be 660 mLH2 min−1 gcat−1 (at 70 °C), 39.8 kJ mol−1 and 0.59, respectively. This study revealed that NiO nanoparticles prepared by an eco-friendly green synthesis method can be used as an alternative potential catalyst for the photocatalytic reduction of methylene blue and H2 production from NaBH4 hydrolysis.

Contribution of electrolyte in parametric optimization of perfluorooctanoic acid during electro-oxidation: Active chlorinated and sulfonated by-products formation and distribution

The present study investigated the roles of peroxydisulfate (PDS) radicals and sulfate radicals (SO4•−) that formed from sulfate (SO42−) during electrochemical oxidation of perfluorooctanoic acid (PFOA). The effect of operating parameters such as different types of electrolytes (NaCl, NaClO4, and Na2SO4), initial pH, current density, dose of electrolyte, and initial concentration of PFOA using electrochemical oxidation for perfluorooctanoic acid (PFOA) decomposition study was investigated. A difference in the removal efficiency with different electrolytes (i.e., Cl−, ClO4−, and SO42−) illustrated an increasing effect of electrooxidation of PFOA in the order of ClO4− < Cl− < SO42−, which suggested that •OH induced oxidation and direct e− transfer reaction continued to play a crucial role in oxidation of PFOA. At the optimum treatment condition of j = 225.2 Am−2, Na2SO4 concentration = 1.5 gL−1, [PFOA]o = 50 mgL−1 and initial pH = 3.8 maximum PFOA removal of 92% and TOC removal of 80% was investigated at 240 min. The formation of three shorter-chain perfluorocarboxylates (i.e., perfluoroheptanoic acid (PFHpA), perfluorohexanoic acid (PFHxA), and perfluoropentanoic acid (PFPeA) and formate (HCOO−) ions were detected as by-products of PFOA electro-oxidation, showing that the C–C bond first broken in C7F15 and then mineralized into CO2, and fluoride ion (F−). The fluorine recovery as F− ions and the organic fluorine as the shorter-chain by-products were also obtained. The degradation kinetic has also been studied using the nth-order kinetic model.

Tailor made CuO/ZIF-8 hybrid structure as a potential candidate for thermocatalytic degradation of nitrocellulose

CuO/ZIF-8 hybrid structure was obtained by adding the PVP-modified foliaceous CuO microstructures during the preparation of ZIF-8 polygon particles as a promising candidate for promoting the thermolysis process of NC. Thermoanalysis and pyrolysis kinetics based on the DSC and TG/DTG data revealed that the CuO/ZIF-8-NC decomposition had a weightlessness rate of 77.81%, heat release of 2882.5 J⋅g–1, the exothermic peak temperature of 471.25 K, and activation energy of 172.2 ± 16.0 kJ⋅mol–1, indicating that CuO/ZIF-8 has better catalytic activity than CuO and ZIF-8. The reconstructed nth-order kinetic models for NC/catalysis complexes were obtained using a modified fitting algorithm based on the results of isoconversional kinetic analysis, indicating that CuO/ZIF-8, CuO, and ZIF-8 had different catalytic effects on the thermolysis pathways of NC. This study suggests that CuO/ZIF-8 composite may have prospective application as a high potential and unique catalyst for accelerating NC pyrolysis.

Ruthenium-Imine catalyzed KBH4 hydrolysis as an efficient hydrogen production system

The present study focused on the increasing of hydrogen evolution through hydrolysis of potassium borohydride in the presence of Ruthenium complex catalyst. It is the first time to use the Ru-Imine complex catalyst in KBH4 hydrolysis reaction to hydrogen evolution. The new Ru complex was synthesized from the tetradentate Imine ligand namely 4,4′-methylenebis (2,6-diethyl)aniline-3,5-di-tert-butylsalisylaldimine and Ru salt under the inert atmosphere. Ru-Imine complex was fully characterized by Elemental Analysis, Infrared Spectroscopy, Scanning Electron Microscope, X-Ray Diffraction Analysis, Brunauer-Emmett-Teller Surface Area Analysis and Transmission Electron Microscopy. By the synthesized Ru-Imine complex catalyst, the potassium borohydride hydrolysis reaction resulted in a lower energy barrier with 20,826 kJ/mol activation energy (Ea) for nth order kinetic model and 18,045 kJ/mol for Langmuir-Hinshelwood (L-H) kinetic model. According to the results Ru-complex was highly active and stable catalyst in KBH4 hydrolysis reaction to hydrogen evolution with 45,466 mL H2/gcat.min and 76,815 mL H2/gcat.min hydrogen generation rates at 30 °C and 50 °C respectively. Moreover Ru-Imine complex catalyst displayed 100% stability even at fifth recycle.

A Suitable Combination of Electrodes for Simultaneous Reduction of Nitrates and Oxidation of Ammonium Ions in an Explosive Industry Wastewater

The electrochemical reduction of nitrate and ammonium ion oxidation has been performed with the cathode (Al) and anode (Ti/RuO₂) in the explosive industry wastewater polluted with a significant quantity of NO₃– and NH₄⁺. For this, the influences of various other cathode materials (Fe, Cu, and C), the current density (j = 35.71 to 142.86 A m–²), wastewater pH (pH = 3–12), and treatment time (t = 180 min) were analyzed for nitrate ion reduction, ammonium ion oxidation, nitrite ion generation, and total nitrogen (TN) degradation. The maximum nitrate removal and TN removal efficiencies were found to be ≈51 and ≈63% at j = 142.86 A m–² and wastewater natural pH after 180 min treatment time, respectively. In this condition, SEC was calculated to be 74.4 kWh (kg NO₃– reduced)⁻¹. The mechanistic analysis suggested that the atomic hydrogen molecules, H⁺, and e– help in the nitrate ion reduction and the available Cl– ion in the wastewater helps in the oxidation of the ammonium ion into gaseous nitrogen through the electrochemical process. The new and used electrodes were characterized by FE-SEM, AFM, and XRD techniques. Electrodes were also characterized within untreated and treated wastewater through CV and EIS analysis. The in situ generated oxidizing species were identified by the p-nitrosodimethylaniline (RNO) bleaching test. Pseudo-first-order and nᵗʰ-order kinetic models were applied, and the reaction rate was calculated to understand the reaction rate of the nitrate reduction. The approximate operational cost estimation has been performed for the lab-scale batch reactor treatment of the explosive industry wastewater. No scum or sludge was produced throughout the treatment process. This study helps to understand the parametric, mechanistic, and kinetic aspects of electrochemical nitrate reduction and oxidation of the previously present and produced ammonium ion in the explosive industry wastewater.

Hydrolysis of sodium borohydride solutions both in the presence of Ni–B catalyst and in the case of microwave application

In this study, the nickel boron (Ni–B) catalyst was studied in the microwave environment for hydrogen production from the hydrolysis of a sodium borohydride solution to release H2. The catalytic activity of the Ni–B catalyst was measured by hydrogen production from the hydrolysis of sodium borohydride. The catalytic properties of the Ni–B catalyst in the microwave medium were examined by considering parameters such as NaOH concentration, NaBH4 concentration, catalyst amount, temperature, and microwave power. Thus, the results obtained from the experiments carried out with Ni–B catalyst both in non-microwave and microwave media were compared. In the experiments, under microwave irradiation, the best result was the release of hydrogen gas from the Ni–B catalyst by applying 100 W of microwave energy at 40 °C. Activation energy values were calculated using the reaction rate constants obtained at different temperatures in the nth order kinetic model and the Langmuir - Hinshelwood model.

Superior reduction of nitrate with simultaneous oxidation of intermediates and enhanced nitrogen gas selectivity via novel electrochemical treatment

This study reports an electrochemical reduction of the NO3− along with oxidation of the in-situ generated NH4+ with maximum selectivity of the N2 gas as the final-product. The use of aluminum as a cathode and Ti/RuO2 as an anode showed enhanced electrochemical nitrate reduction at the cathode and oxidation of the ammonium ion at the anode. Effects of various parameters like initial NO3− concentration (Co = 100−400 mg L−1), a dose of the Cl− as NaCl (NaCl = 100−400 mg L−1), current density applied (j = 83.3-333.3 A m−2), solution pH (pH = 4–10) and electrolysis time (t = 0−120 min) were studied in terms of NO3− reduction and total nitrogen (TN) removal efficiencies. Current efficiency (CE) was elaborated with respect to end products like N2, NO2− and NH4+. Specific electrical energy consumption (SEC) was calculated in kWh kg−1 NO3− removed for the electrochemical process. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were utilized for understanding the oxidation/reduction mechanism over electrodes and the characteristics of the electrodes in a different solution. The studied mechanism suggested a circular conversion of NO3− through complex processes into the N2 gas as the final product. The ultimate nitrate and TN degradation efficiency of ≈95 % with N2 selectivity of ≈100 % were achieved at the optimum condition of Co = 100 mg L−1, NaCl = 300 mg L−1, j = 333.3 A m−2, pH = 6 and time = 120 min with SEC = 927.4 kW h kg−1 NO3− removed. The 1st, 2nd, and nth-order kinetic models were used for the reaction kinetics. FE-SEM, XRD, and AFM techniques were used for the characterization of the electrodes before and after all the electrochemical runs. The operating cost was calculated for lab-scale treatment along with a comparison with previous studies. No sludge or scum got produced for each electrochemical run. Finally, this study delivers a superior perceptive for electrochemical characteristics of Al at the cathode side and Ti/RuO2 at anode side as well as electrochemical NO3− reduction and oxidation of the generated NH4+, simultaneously.

Influence of voltage and distance on quality attributes of mixed fruit beverage during pulsed light treatment and kinetic modeling

AbstractThe study investigates the influence of pulsed light (PL) processing parameters on quality of mixed fruit beverage followed by kinetic modeling. The attributes tested were aerobic mesophiles (AM), yeast and mold (YM) counts, polyphenol oxidase (PPO) and peroxidase (POD) activity, color change (ΔE*), browning index (ΔBI), antioxidant capacity (AOC), and ascorbic acid (AA) content at varying voltage (1.8–2.4 kV), the number of pulses (2–187), and distance (2.4–9.6 cm). Weibull model described the PL inactivation rate of AM and YM and nth order kinetic model estimated the inactivate rate of PPO, POD, and AA. The maximum inactivation of PPO, POD, and AA content were 41, 51, and 36%, respectively. At the most severe PL condition, ΔE* was 6.4, ΔBI was 5.6 with 14% increment in phenolics. A secondary kinetic model adequately predicted the ratio of rate constant and fluence‐based rate (k/kF) for PPO, YM, and AA correlating voltage (V) and lamp distance (x). PL‐induced pasteurization of the beverage is possible at the fluence rate of 17.42 W/cm2 for 3 min.Practical ApplicationsExposing the food material to a high intensity pulsed light (PL) is a nonthermal way of food preservation for the shelf‐life extension. The potential of PL treatment (PLT) has been explored for a mixed fruit beverage in terms of its microbial, enzymatic, and nutritional quality. An optimized PLT condition is proposed to obtain a microbially safe fruit beverage along with a minimal loss in bioactive compounds. Subsequently, the kinetic data related to microbial and enzyme inactivation and degradation of vitamins will help in deciding the process parameters like treatment time, lamp voltage, and sample distance from the light source. The secondary kinetic model will eventually help to design a robust PL process condition for similar fruit beverages to obtain a microbiologically safe product with a minimal loss in vitamins.

Investigation of hydrothermal co-carbonization of waste textile with waste wood, waste paper and waste food from typical municipal solid wastes

In order to explore hydrothermal carbonization (HTC) behavior of municipal solid wastes (MSW), four typical components, waste textile, wood, paper and food, were employed to perform HTC and co-HTC process. The experiments were conducted at 240 ○C and 90 min with a 1:12 solid/liquid ratio, where blending ratios of 1:3, 1:1 and 3:1 with waste textile were investigated. As expected, the increase of fixed carbon and carbon content improved the fuel potential of hydrochar. The synergistic index (SI) analysis clearly indicated that significant synergistic effects occurred during co-HTC process. Specifically, all the SI values of hydrochar yield from co-HTC of waste textile with wood and paper were negative, while all SI values of hydrochar yield for waste textile with food were positive. Particularly, the SI values of fuel ratio for all hydrochars were positive which suggested co-HTC could promote to enhance the coalification degree of hydrochars. However, the undesirable increment of O content for hydrochars (derived from 75%waste textile-25% waste food and 50%waste textile-50% waste food) decreased the high heating value. The combustion behavior and nth-order kinetic model analysis showed that hydrochars derived from co-HTC rendered a more stable and lasting combustion profile.

Oxidative Desulfurization of Dibenzothiophene Using Cobalt (II) Complexes with Substituted Salen-Type Ligands as Catalysts in Model Fuel Oil

Three cobalt(II)-salen complexes (CoL1, CoL2 and CoL3) were synthesized via the reaction of the three tetradentate ligands as N,N′-ethylenebis(salicylimine) L1, N,N′-ethylenebis(3-tert-butylsalicylimine) L2 and N,N′-ethylenebis(3,5-di-tert-butylsalicylimine) L3, with a stoichiometric amount of cobalt(II) acetate tetrahydrate, respectively. All the three complexes were studied as oxidative desulfurization catalyst on dibenzothiophene taken in model fuel oil n-dodecane. The acetonitrile used as an extracting solvent and H2O2 as an oxidant. Comparatively CoL3 proved to be the best catalyst which showed the 76% DBT removal at the optimized conditions. The nth-order kinetic model is the best way to represent oxidation kinetics of complexes. This cobalt(II) Schiffs base complexes were studied as catalyst for oxidative desulfurization of dibenzothiphene (DBT) taken as model sulphur compounds in fuel model oil (n-dodecane) using H2O2 as oxidant and acetonitrile as extracting solvent for DBT sulfone in a batch experiment.

Comparison of CO2 gasification reactivity and kinetics: petcoke, biomass and high ash coal

It is desirable to exploit biomass energy along with coal and petcoke through gasification, and understanding the differences between petroleum coke (petcoke), coal and biomass gasification behaviour becomes very essential. Consequently, present investigation compares gasification components of petcoke, sawdust and high ash coal with their physico-chemical properties under isothermal conditions in CO2 atmosphere in the temperature range of 1173–1623 K. Physico-chemical characterisation includes proximate and ultimate analyses, porous structure analysis by Brunauer-Emmett-Teller (BET) surface area from nitrogen (N2) adsorption isotherm, ash composition analysis and ash fusion temperature. The effects of temperature and nature of different solid fuels on gasification reactivity have been discussed. Gasification kinetics has been investigated using two nth-order kinetic models, such as homogeneous model (HM) and shrinking core model (SCM). Influence of diffusion resistance on gasification behaviour of different solid fuels is also reported. Thus, the present study will be helpful to realise the effects of high ash in gasification behaviour as well as in designing and modelling of the suitable gasifier and to establish optimum gasification conditions for petcoke, biomass and high ash coal.

Insight into torrefaction of woody biomass: Kinetic modeling using pattern search method

Torrefaction aroused as a promising pretreatment technique that can improve the fuel properties and thermochemical conversion performance of biomass. The kinetics of biomass torrefaction is fundamental for the investigation of torrefaction reaction mechanisms, and the simulation and optimization of torrefaction processes. The commonly used empirical reaction model has some theoretical drawbacks in describing the kinetics of biomass torrefaction. In this study, the torrefaction kinetics of beech wood was studied using thermogravimetric analysis (TGA) at isothermal temperatures of 493, 523 and 553 K. The nth-order kinetic model was presented to analyze the kinetic experimental data at all torrefaction temperatures simultaneously. The pattern search method was used to optimize the kinetic parameters of the nth-order model for biomass torrefaction. Predicted results from the nth-order model with the optimal kinetic parameters were compared with the experimental data and indicated that the nth-order model satisfactorily predicted the experimental data of beech wood torrefaction at different torrefaction temperatures.

Enhancing photocatalytic degradation of quinoline by ZnO:TiO2 mixed oxide: Optimization of operating parameters and mechanistic study

This study focuses on the photocatalytic degradation of quinoline, a recalcitrant heterocyclic nitrogenous aromatic organic compound, using the mixed oxide ZnO–TiO2 photo-catalyst. Photo-catalysts were synthesized by the solid-state reaction method at different calcination temperatures of 400 °C, 600 °C, and 800 °C. Different analytical methods, including Field emission scanning electron microscope, Brunauer-Emmett-Teller surface area, X-ray diffraction, UV–vis diffuse reflectance spectroscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy analysis were used for the catalyst characterization. The highest pore surface area of 57.9 m2g−1 was obtained for the photo-catalyst calcined at 400 °C. The effects of calcination temperature, solution pH, initial concentration, catalyst dose as well as irradiation time were studied. At the optimum condition, i.e., calcination temperature of 400 °C, pH ≈8 and catalyst dose of 2.5 gL−1, maximum quinoline degradation and total organic carbon (TOC) removal efficiency of ≈92% and ≈78% were obtained after 240 min for initial quinoline amount of 50 mgL−1. The 1st, 2nd, and nth-order kinetic models were applied to analyze the quinoline degradation rate. The photocatalytic mechanism was studied by drawing energy level diagram with the help of the band-gap structures of the ZnO and TiO2, potential of the free radicals like OH and O2 and HOMO-LUMO energy gap of the quinoline molecule. The proposed pathways of quinoline mineralization were suggested on the basis of the identified intermediates by the gas chromatograph-mass spectrometer analysis and scavenger study.

Principal component analysis reveals microbial biomass carbon as an effective bioindicator of health status of petroleum-polluted agricultural soil

ABSTRACT We investigated a number of microbiological activities in the soil to serve as biomonitoring tools in assessing the ecotoxicity of diesel-contaminated soil samples during the different periods of bioremediation. Sawdust was used as the biostimulant for the biodegradation of artificial diesel-polluted soil samples. Soil microbial population, soil microbial enzymatic activities (catalase, lipase, dehydrogenase, urease, phosphatase and β-glucosidase), soil microbial biomass carbon (MBC), nitrogen (MBN) and phosphorus (MBP), soil microbial respirometric index and total petroleum hydrocarbon (TPH) concentration were monitored to evaluate the efficiency of the bioremediation process. After a period of 56 d, total petroleum hydrocarbon content reduced from 14,221 to 270 mg/kg. The parameter estimation using the nth-order kinetic model revealed that the first-order rate constants (k) for TPH removal were 4.417 d−1 and 0.2670 d−1 for sawdust-amended and unamended soil, respectively. This implied that, the sawdust amendment resulted in reaction rate 16.5 times faster than unamended soil. Thus, the biological indicators were generally more pronounced in biostimulated soil than the attenuated soil. However, to evaluate the efficiency of the sawdust-assisted bioremediation, principal component analysis, which was used in selecting the most sensitive bioindicators. It was observed that microbial biomass carbon, catalase, lipase and dehydrogenase were the most responsive bioparameters. A positive relationship between TPH removal and the four most sensitive bioparameters suggests that the use of four biological activities have proven to be effective monitoring tools for evaluating the efficiency of a bioremediation strategy.

Removal of 17β-Estradiol from water by adsorption onto montmorillonite-carbon hybrids derived from pyrolysis carbonization of carboxymethyl cellulose

In this work, we demonstrated the preparation of the carbonized montmorillonite/carboxymethyl cellulose (MMT/CMC) hybrids and their application as an adsorbent for efficient removal of 17β-Estradiol (βE2). X-ray diffractometer (XRD) results showed that CMC intercalation reached saturation at a CMC to MMT weight ratio of 1; transmission electron microscope (TEM) measurements clearly revealed that carbonization caused graphenes distribute on the MMT surfaces; pyrolysis temperature at 600 °C yielded novel MMT/CMC sample of high surface areas as reflected by Brunauer-Emmett-Teller (BET) surface area. The adsorbed amount of βE2 under various conditions decreased in the order MMT/CMC1:1(600) > MMT/CMC1:1(450) > MMT/CMC1:1(300) ∼ MMT/CMC2:1(600) ∼ MMT > MMT/CMC5:1(600). The removal of βE2 by MMT/CMC1:1(600) occurred very quickly, and the adsorption kinetics could be well fitted by the Ritchie nth-order kinetic model; the best-fit adsorption isotherm model was Freundlich model. The MMT/CMC1:1(600) also exhibited good regeneration performance after five adsorption/desorption cycles. The experimental results also showed that the adsorption of βE2 on the MMT/CMC1:1(600) composite could contribute to hydrophobic partitioning, π−π staking interaction, H-bond interaction, pore-filling effect and simple van der Waals interaction. This highly effective and novel adsorbent can be easily synthesized and regenerated, indicating its great potential in drinking and wastewater purification for endocrine disruptor compounds.

Modeling the inactivation of pectin methylesterase in pineapple puree during combined high-pressure and temperature treatments

Abstract The inactivation of pectin methylesterase (PME) in pineapple puree was studied within the domain of 0.1–600 MPa/30–70 °C/1 s–40 min. The combined effect of pressure-build up and decompression, as characterized by pulse inactivation (PI value), was modeled by the artificial neural network (ANN) through a tan-sigmoidal function of target pressure, target temperature, compression, and decompression time. Besides, nth order kinetic model was fitted during the isobaric-isothermal hold period. The extent of pulse inactivation of PME ranged from 15% (200 MPa/30 °C) to 67% (600 MPa/70 °C) and it increased at a higher temperature and/or pressure. The inactivation orders (n) during thermal (0.1 MPa/30–70 °C) and high pressure (100–600 MPa/30–70 °C) treatments were 1.15 and 1.3, respectively. The rate constant (k) ranged within 4.0 to 71.2 × 10−3 Un−1·min−1. A nonlinear model considering the pressure dependency of activation energy, and temperature dependency of activation volume was developed which adequately described the inactivation behavior of PME within the domain. Industrial relevance Pectin methylesterase (PME) in the pineapple puree results in a product with a modified texture and consistency that is usually not entertained by the consumer. Therefore, pineapple puree has to be processed to inactivate PME to avoid the cloud loss. Now-a-days, high-pressure processing is being used for fruit products to retain the heat sensitive nutrients. In this sense, a model capable of predicting the exact inactivation behavior of PME during the treatment is very much obligatory for process design. This combined model developed in the study will help the food industry to come-up with the exact pressure-temperature-holding time combination achieving a certain degree of PME inactivation.

Evaluation of isothermal kinetics of the thermal decomposition of guanidine nitrate in constant volume

ABSTRACTIn this paper, thermal decomposition characteristics of guanidine nitrate (GN) are studied by both dynamic and isothermal differential scanning calorimetry (DSC) tests in constant volume. The dynamic curve (1°C/min) shows that at least two overlapped peaks exist in the decomposition curve of GN, whereas the decomposition peaks of each isothermal experiment (305–320°C) can be clearly taken as a combination of three decomposition peaks. Besides, an isothermal kinetic model is studied. AKTS is used to decouple the isothermal decomposition peaks, to obtain three separate peaks, i.e., one decelerating model peak and two sigmoidal model peaks. An Nth order kinetic model is established for the first decomposition stage, and an autocatalytic model is established to describe the left two stages. The kinetic parameters of each stage are calculated by nonlinear fitting. The equation describing the reaction rate for the Nth order kinetic model as below, dα/dt = exp(8.92)exp(−67730/RT)(1−α)1.020, the second and the third steps can be described by the equations of dα/dt = exp(26.15)exp(−165570/RT)(1-α)0.508+ exp(23.87)exp(−159360/RT)(1-α)0.508α0.150 and dα/dt = exp(24.03) exp(−166070/RT)(1-α)0.082+exp(23.28)exp(−160000/RT)(1−α)0.082α0.210, respectively. The results calculated by these models fit well the experimental data, proving that the kinetic parameters are reliable and accurate.

Composting kinetics for mixture of poultry manure and wheat straw based on volatile solids content

The aim of this study was to determine the composting kinetics for mixture ofpoultry manure and wheat straw based on the volatile solids content.Experimental data was fitted with the first-order and the nth-order kinetic model.The nth-order kinetic model showed better prediction performance than the firstorderkinetic model. For the first-order kinetic model, maximum and meandifferences between experimental and simulation results for the content ofvolatile solids were 5.43% and 3.00%, for the first reactor, and 4.68% and2.12% for the second reactor, respectively, for the nth-order kinetic model,maximum and mean differences were 4.92% and 1.68%, for the first reactor,and 4.09% and 1.42% for the second reactor, respectively.

Local Sensitivity Analysis of Kinetic Models for Cellulose Pyrolysis

The first and nth order kinetic models are usually used to describe cellulose pyrolysis. In this work, the local sensitivities of the conversion and derivative conversion with respect to the frequency factor, the logarithm of the frequency factor, the activation energy and the reaction order for the first and nth order kinetic models are calculated by using the finite difference method. The results show that the sensitivities of the first and nth order kinetic models with respect to the activation energy and the logarithm of the frequency factor are significant, while the frequency factor and the reaction order affect the nth order kinetic model slightly. Compared with the frequency factor, the natural logarithm of the frequency factor is a better choice in the parameter estimation of the first and nth order kinetic models.