Oxidative Ammonolysis of Technical Lignins. Part 3. Effect of Temperature on the Reaction Rate

Holzforschung ◽  
2002 ◽  
Vol 56 (4) ◽  
pp. 402-415 ◽  
Author(s):  
E. A. Capanema ◽  
M. Y. Balakshin ◽  
C.-L. Chen ◽  
J. S. Gratzl ◽  
A. G. Kirkman

Summary The effect of the reaction temperature on the kinetics and the reaction mechanism of oxidative ammonolysis of Repap organosolv lignin have been studied. The reaction was conducted in 0.8 M Nh4oh solution under oxygen pressure of 12 bar and at three different temperatures, 70 °C, 100 °C and 130 °C. The resulting N-modified lignins were analyzed by elemental and methoxyl group. About 20–25% of maximum nitrogen content is incorporated into the lignin very fast, in 1–2 min of the reaction. The reaction kinetics then follows a pseudo-first order reaction law and consists of two phases. The activation energies for nitrogen incorporation and lignin solubilization are rather low, in the range of 33–34 kJ/mol. Linear correlation between nitrogen incorporated into the lignin and molecular oxygen uptake, oxygen incorporation, CO2 formation, O-demethylation and total carbon loss was analyzed at the different reaction temperatures. On the basis of kinetic data obtained so far, we have postulated that the reaction temperature affects the reaction rate, but not the reaction pathways. The reaction temperature also affects the ratios between different reaction pathways, though the effect is not very strong. The results obtained are discussed in the terms of competitive reactions of lignin oxidation followed by nitrogen incorporation and lignin deactivation involving nitrogen

Holzforschung ◽  
2001 ◽  
Vol 55 (4) ◽  
pp. 405-412 ◽  
Author(s):  
Ewellyn A. Capanema ◽  
Mikhail Yu. Balakshin ◽  
Chen-Loung Chen ◽  
Josef S. Gratzl ◽  
Adrianna G. Kirkman

Summary Investigations were conducted on the effects of oxygen pressure on the oxidative ammonolysis of REPAP organosolv lignin at 130 °C under oxygen pressure of 5, 8 and 12 bar. The rates of reactions monitored, such as nitrogen incorporation, lignin solubilization, oxygen uptake and CO2 formation, increase with increasing oxygen pressure. Kinetics of nitrogen incorporation under different oxygen pressure consists of two phases and follows a first order law in each phase. Linear correlation between the rate of nitrogen incorporation and oxygen pressure implies that the reaction is first order with respect to oxygen concentration. This indicates that oxygen participates directly in the rate-determining step of nitrogen incorporation. The rate of lignin solubilization also linearly increases with increasing oxygen pressure, implying that the rate of lignin degradation directly depends on oxygen pressure. The nitrogen incorporation is linearly correlated with the oxygen uptake, CO2 formation, oxygen incorporation into lignin, loss of carbon and methoxyl group content under all values of oxygen pressure and during the entire reaction period. This suggests that the reactions in the oxidative ammonolysis of lignin proceed via the same pathways in the different kinetic phases. In addition, the changes in the oxygen pressure were found to have only minor effect upon the coefficients of these linear correlations. This is in good agreement with the structures of N-modified lignin elucidated from FTIR and indicates that oxygen pressure affects only the reaction rate, but not the reaction mechanism.


2018 ◽  
Vol 15 (2) ◽  
pp. 158-168
Author(s):  
Baghdad Science Journal

In this research, the degradation of Dazomet has been studied by using thermal Fenton process and photo-Fenton processes under UV and lights sun. The optimum values of amounts of the Fenton reagents have been determined (0.07g FeSO4 .7H2O, 3.5µl H2O2) at 25 °C and at pH 7 where the degradation percentages of Dazomet were recorded high. It has been found that solar photo Fenton process was more effective in degradation of Dazomet than photo-Fenton under UV-light and thermal Fenton processes, the percentage of degradation of Dazomet by photo-Fenton under sun light are 88% and 100% at 249 nm and 281 nm respectively, while the percentages of degradation for photo-Fenton under UV-light are 87%, 96% and for thermal Fenton are 70% and 66.8% at 249 nm and 281 nm respectively. In this research the effect of temperature on all the reactions has been studied in the range 25°C-45°C, it has been noticed that the reaction rate constant (k) has increased with increasing temperature, and the best percentage degradation of Dazomet was at 45°C in all processes, so, the thermodynamic functions ?G*, ?H*, ?S* have been calculated


Holzforschung ◽  
2001 ◽  
Vol 55 (4) ◽  
pp. 397-404 ◽  
Author(s):  
Ewellyn A. Capanema ◽  
Mikhail Yu. Balakshin ◽  
Chen-Loung Chen ◽  
Josef S. Gratzl ◽  
Adrianna G. Kirkman

Summary Investigations were conducted on the oxidative ammonolysis of REPAP organosolv lignin at 130 °C in 0.8M NH4OH solution under oxygen pressure of 12 bar. The lignin was completely solubilized at the reaction time of 165 min. The kinetics of the nitrogen incorporation consists of two phases. The first phase is up to the reaction time of approximately 35 min including 15 min heating up period. The rate of nitrogen incorporation in the first phase is 2.3 times higher than that in the second phase: κ1 = 4.58 × 10−4 s−1 versus κ2 = 1.90 × 10−4 s−1. The oxygen uptake and CO2 formation in the reaction is rather high. When the nitrogen incorporation was ceased after reaction for 255 minutes, more than 4 moles of oxygen/C9-unit of lignin were consumed and approximately 1.5 moles of carbon dioxide/C9-unit of lignin were released. In addition, extensive O-demethylation of methoxyl groups occurred. The molar ratio of the nitrogen incorporation to the methoxyl group eliminated is approximately 1.4 and 0.7 for the soluble and insoluble N-modified lignins, respectively. Structural analyses of the soluble N-modified lignins by FTIR and 1H NMR spectroscopic techniques showed only quantitative differences in the spectra obtained at different reaction times. This indicates that the reaction pathways do not change in the course of the oxidative ammonolysis. Possible reaction mechanisms of the oxidative ammonolysis are discussed on the basis of the experimental data.


2008 ◽  
Vol 368-372 ◽  
pp. 765-767 ◽  
Author(s):  
Bo Quan Zhu ◽  
Xue Dong Li ◽  
Hou Zhi Wang

ZrO2-mullite compound powders were synthesized with zircon and aluminum sulfate in molten sodium sulfate. Na2ZrSiO5 was prepared as intermediate with zircon and sodium carbonate at 900°C for 3h. Then the mixture of resultant Na2ZrSiO5 and aluminum sulfate was heated at different temperatures in molten sodium sulfate salt. The ZrO2-Al2O3-SiO2 compound powders were obtained after washing away the solvable salts. The results showed that the compound powders synthesized at 800°C were tetragonal ZrO2, SiO2 and Al2O3; the powders synthesized at 1000°C were monoclinal ZrO2 and mullite. The mullite in compound powders became to decompose when the reaction temperature increased over 1100°C.


Author(s):  
D. T. Gauld ◽  
J. E. G. Raymont

The respiratory rates of three species of planktonic copepods, Acartia clausi, Centropages hamatus and Temora longicornis, were measured at four different temperatures.The relationship between respiratory rate and temperature was found to be similar to that previously found for Calanus, although the slope of the curves differed in the different species.The observations on Centropages at 13 and 170 C. can be divided into two groups and it is suggested that the differences are due to the use of copepods from two different generations.The relationship between the respiratory rates and lengths of Acartia and Centropages agreed very well with that previously found for other species. That for Temora was rather different: the difference is probably due to the distinct difference in the shape of the body of Temora from those of the other species.The application of these measurements to estimates of the food requirements of the copepods is discussed.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Aiyan Guan ◽  
Inge Van Damme ◽  
Frank Devlieghere ◽  
Sarah Gabriël

AbstractAnisakidae, marine nematodes, are underrecognized fish-borne zoonotic parasites. Studies on factors that could trigger parasites to actively migrate out of the fish are very limited. The objective of this study was to assess the impact of different environmental conditions (temperature, CO2 and O2) on larval motility (in situ movement) and mobility (migration) in vitro. Larvae were collected by candling or enzymatic digestion from infected fish, identified morphologically and confirmed molecularly. Individual larvae were transferred to a semi-solid Phosphate Buffered Saline agar, and subjected to different temperatures (6 ℃, 12 ℃, 22 ℃, 37 ℃) at air conditions. Moreover, different combinations of CO2 and O2 with N2 as filler were tested, at both 6 °C and 12 °C. Video recordings of larvae were translated into scores for larval motility and mobility. Results showed that temperature had significant influence on larval movements, with the highest motility and mobility observed at 22 ℃ for Anisakis spp. larvae and 37 ℃ for Pseudoterranova spp. larvae. During the first 10 min, the median migration of Anisakis spp. larvae was 10 cm at 22 ℃, and the median migration of Pseudoterranova spp. larvae was 3 cm at 37 ℃. Larval mobility was not significantly different under the different CO2 or O2 conditions at 6 °C and 12 ℃. It was concluded that temperature significantly facilitated larval movement with the optimum temperature being different for Anisakis spp. and Pseudoterranova spp., while CO2 and O2 did not on the short term. This should be further validated in parasite-infected/spiked fish fillets.


Toxins ◽  
2021 ◽  
Vol 13 (2) ◽  
pp. 134
Author(s):  
Ana Isabel Galván ◽  
Alicia Rodríguez ◽  
Alberto Martín ◽  
Manuel Joaquín Serradilla ◽  
Ana Martínez-Dorado ◽  
...  

Dried fig is susceptible to infection by Aspergillus flavus, the major producer of the carcinogenic mycotoxins. This fruit may be contaminated by the fungus throughout the entire chain production, especially during natural sun-drying, post-harvest, industrial processing, storage, and fruit retailing. Correct management of such critical stages is necessary to prevent mould growth and mycotoxin accumulation, with temperature being one of the main factors associated with these problems. The effect of different temperatures (5, 16, 25, 30, and 37 °C) related to dried-fig processing on growth, one of the regulatory genes of aflatoxin pathway (aflR) and mycotoxin production by A. flavus, was assessed. Firstly, growth and aflatoxin production of 11 A. flavus strains were checked before selecting two strains (M30 and M144) for in-depth studies. Findings showed that there were enormous differences in aflatoxin amounts and related-gene expression between the two selected strains. Based on the results, mild temperatures, and changes in temperature during drying and storage of dried figs should be avoided. Drying should be conducted at temperatures >30 °C and close to 37 °C, while industry processing, storage, and retailing of dried figs are advisable to perform at refrigeration temperatures (<10 °C) to avoid mycotoxin production.


Materials ◽  
2020 ◽  
Vol 14 (1) ◽  
pp. 119
Author(s):  
Dana H. Abdeen ◽  
Muataz A. Atieh ◽  
Belabbes Merzougui

The inhibition behavior of carbon nanotubes (CNTs) and Gum Arabic (GA) on the corrosion of 316L stainless steel in CNTs–water nanofluid under the effect of different temperatures was investigated by electrochemical methods and surface analysis techniques. Thereby, 316L stainless steel samples were exposed to CNTs–water nanofluid under temperatures of 22, 40, 60 and 80 °C. Two concentrations of the CNTs (0.1 and 1.0 wt.% CNTs) were homogenously dispersed in deionized water using the surfactant GA and tested using three corrosion tests conducted in series: open circuit test, polarization resistance test, and potentiodynamic scans. These tests were also conducted on the same steel but in solutions of GA-deionized water only. Tests revealed that corrosion increases with temperature and concentration of the CNTs–water nanofluids, having the highest corrosion rate of 32.66 milli-mpy (milli-mil per year) for the 1.0 wt.% CNT nanofluid at 80 °C. In addition, SEM observations showed pits formation around areas of accumulated CNTs that added extra roughness to the steel sample. The activation energy analysis and optical surface observations have revealed that CNTs can desorb at higher temperatures, which makes the surface more vulnerable to corrosion attack.


BioResources ◽  
2020 ◽  
Vol 16 (1) ◽  
pp. 77-95
Author(s):  
Siqiao Yang ◽  
Haichao Li

Activated carbon, graphite, and GO/gelatin composite films were prepared by the blending method. The properties of composites were characterized by tensile strength (TS), elongation at break (EB), water vapour permeability (WVP), water-absorption ability, contact angle, scanning electron microscopy (SEM), and moisture at different temperatures. The properties of GO/gelatin composite films were better when each of three kinds of carbon materials were used as reinforcement phases and added into the matrix gelatin. The results showed that EB and TS of GO/gelatin composite films were both excellent. The moisture of GO/gelatin composite films was greater than the others. SEM micrographs showed that GO had better compatibility and dispersibility with gelatin than activated carbon and graphite. The water absorption of GO/gelatin composite films were low, at 15 °C and 25 °C, and the WVP was low at 35 °C. The WVP of GO/gelatin composite films was lower than the others at different temperatures. The contact angle of GO/gelatin composite films was larger than the others.


2015 ◽  
Vol 75 (7) ◽  
Author(s):  
Amir Arifin ◽  
Abu Bakar Sulong ◽  
Norhamidi Muhamad ◽  
Junaidi Syarif

Hydroxyapatite (HA) has been widely used in biomedical applications due to its excellent biocompatibility. However, Hydroxyapatite possesses poor mechanical properties and only tolerate limited loads for implants. Titanium is well-known materials applied in implant that has advantage in mechanical properties but poor in biocompatibility. The combination of the Titanium alloy and HA is expected to produce bio-implants with good in term of mechanical properties and biocompatabilty. In this work, interaction and mechanical properties of HA/Ti6Al4V was analyzed. The physical and mechanical properties of HA/Ti6Al4V composite powder obtained from compaction (powder metallurgy) of 60 wt.% Ti6Al4V and 40 wt.% HA and sintering at different temperatures in air were investigated in this study. Interactions of the mixed powders were investigated using X-ray diffraction. The hardness and density of the HA/Ti6Al4V composites were also measured. Based on the results of XRD analysis, the oxidation of Ti began at 700 °C. At 1000 °C, two phases were formed (i.e., TiO2 and CaTiO3). The results showed that the hardness HA/Ti6Al4V composites increased by 221.6% with increasing sintering temperature from 700oC to 1000oC. In contrast, the density of the composites decreased by 1.9% with increasing sintering temperature. 


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