scholarly journals Thermal Decomposition of Nitrated Tri-n-Butyl Phosphate in a Flow Reactor

2012 ◽  
Vol 2012 ◽  
pp. 1-9 ◽  
Author(s):  
Lalit K. Patil ◽  
Vilas G. Gaikar ◽  
Shekhar Kumar ◽  
U. Kamachi Mudali ◽  
R. Natarajan
Keyword(s):  
Thermal Decomposition ◽  
Atmospheric Pressure ◽  
Flow Reactor ◽  
Degradation Products ◽  
Reaction Pathway ◽  
Operating Conditions ◽  
Purex Process ◽  
Power Law Model ◽  
Reaction Products ◽  
Instrumental Methods

Tri-n-butyl phosphate (TBP) is a universal nuclear extractant, commercially used in the PUREX process for the last 60 years. However, it is prone to nitration and thermal degradation, and as a consequence a red-oil event may be initiated under several operating conditions resulting in severe pressurization of vessel/cell if venting is inadequate. In this work, an attempt was made to understand the reaction pathway of thermal decomposition of nitrated TBP in a flow reactor at atmospheric pressure. Many reaction products were identified and quantified by instrumental methods like HPLC-RI and GC-TCD. The experimental data was analysed with a power law model and the apparent rate constants were estimated. The activation energy for thermal decomposition of nitrated TBP, assuming an Arrhenius type of temperature dependency, was estimated to be 47.39 ± 0.25 kJ·mol−1. The effect of both varying temperature and concentration of nitric acid on conversion of TBP into degradation products and products distribution was experimentally studied. Based on the experimental observations, a reaction mechanism framework for thermal decomposition of nitrated TBP is proposed.

Analogues of the active and inactive sodium carbonate

1982 ◽  
Vol 47 (12) ◽  
pp. 3348-3361 ◽  
Author(s):  
Erich Lippert ◽  
Karel Mocek ◽  
Emerich Erdös
Keyword(s):  
Thermal Decomposition ◽  
Time Dependence ◽  
Water Vapour ◽  
Sulphur Dioxide ◽  
Atmospheric Pressure ◽  
Flow Reactor ◽  
Kinetic Measurements ◽  
Sodium Potassium ◽  
Alkaline Metals ◽  
Hydrogen Carbonates

The reactivity of the anhydrous carbonates of alkaline metals with sulphur dioxide has been studied experimentally in dependence both on the nature of the cation and on the way of preparation of the anhydrous carbonate. The carbonates were prepared either by thermal decomposition of hydrogen carbonates or by thermal dehydration of carbonate hydrates. The carbonates of lithium, sodium, potassium, rubidium and caesium have been investigated. Kinetic measurements were carried out in a flow reactor in the integral regime at 423 K under atmospheric pressure, with a gas containing 0.2 vol.% of sulphur dioxide and 2.0 vol.% of water vapour in the nitrogen as a carrier gas. The reactivities have been compared on the basis of time dependence of the conversion of carbonate to sulphite.

Kinetics of the catalytic hydrodesulphurization reaction system; hydrogenolysis of thiophene

1980 ◽  
Vol 45 (10) ◽  
pp. 2728-2741 ◽  
Author(s):  
Pavel Fott ◽  
Petr Schneider
Keyword(s):  
Atmospheric Pressure ◽  
Active Sites ◽  
Flow Reactor ◽  
Kinetic Equations ◽  
Reaction System ◽  
Reaction Products ◽  
Molybdenum Catalyst ◽  
Cobalt Molybdenum Catalyst ◽  
Kinetics Of ◽  
Reaction Schemes

Kinetics have been studied of the reaction system taking place during the reaction of thiophene on the cobalt-molybdenum catalyst in a gradientless circulation flow reactor at 360 °C and atmospheric pressure. Butane has been found present in a small amount in the reaction products even at very low conversion. In view of this, consecutive and parallel-consecutive (triangular) reaction schemes have been proposed. In the former scheme the appearance of butane is accounted for by rate of desorption of butene being comparable with the rate of its hydrogenation. According to the latter scheme part of the butane originates from thiophene via a different route than through hydrogenation of butene. Analysis of the kinetic data has revealed that the reaction of thiophene should be considered to take place on other active sites than that of butene. Kinetic equations derived on this assumption for the consecutive and the triangular reaction schemes correlate experimental data with acceptable accuracy.

Characterization of dissolved material during the initial phase of softwood kraft pulping

TAPPI Journal ◽  
2013 ◽  
Vol 12 (1) ◽  
pp. 37-43 ◽  
Author(s):  
HANNU PAKKANEN ◽  
TEEMU PALOHEIMO ◽  
RAIMO ALÉN
Keyword(s):  
Mass Transfer ◽  
Molecular Mass ◽  
Initial Phase ◽  
Degradation Products ◽  
Kraft Pulping ◽  
Reaction Products ◽  
Cooking Temperature ◽  
Molecular Masses ◽  
Aliphatic Carboxylic Acids

The influence of various cooking parameters, such as effective alkali, cooking temperature, and cooking time on the formation of high molecular mass lignin-derived and low molecular mass carbohydrates-derived (aliphatic carboxylic acids) degradation products, mainly during the initial phase of softwood kraft pulping was studied. In addition, the mass transfer of all of these degradation products was clarified based on their concentrations in the cooking liquor inside and outside of the chips. The results indicated that the degradation of the major hemicellulose component, galactoglucomannan, typically was dependent on temperature, and the maximum degradation amount was about 60%. In addition, about 60 min at 284°F (140°C) was needed for leveling off the concentrations of the characteristic reaction products (3,4-dideoxy-pentonic and glucoisosaccharinic acids) between these cooking liquors. Compared with low molecular mass aliphatic acids, the mass transfer of soluble lignin fragments with much higher molecular masses was clearly slower.

Hydrogenolysis of glucose and fructose in glycol solutions over CuO-MgO-ZrO2 catalyst

2020 ◽  
pp. 48-55
Author(s):  
M.E. Sharanda ◽  
◽  
E.A. Bondarenko ◽  
Keyword(s):  
Ethylene Glycol ◽  
Propylene Glycol ◽  
Flow Reactor ◽  
General Trend ◽  
Raw Materials ◽  
Reaction Products ◽  
Renewable Raw Materials ◽  
High Partial Pressure ◽  
Zro2 Catalyst ◽  
Phase Process

Ethylene glycol and propylene glycol are important representatives of polyols. On an industrial scale, they are obtained from petrochemical raw materials. Within a decade, significant efforts were made for the producing of polyols from biologically renewable raw materials - carbohydrates. The general trend for carbohydrate hydrogenolysis includes application of liquid-phase process with the use of modified metal-oxide catalysts, at 120-120 ° C and pressure of 3MPa or above. So high pressure is used for the reason to increase hydrogen solubility, and also due to the high partial pressure of low boiling solvents. We supposed that usage of high boiling solvents could allow hydrogenolysis to be performed at the lower pressure. Ethylene glycol and propylene glycol are of particular interest as such kind of solvent since they are both the main products of glucose hydrogenolysis. In this work, the process of hydrogenolysis of glucose and fructose over Cu / MgO-ZrO2 catalyst have been studied at temperature range of 160-200 °C and a pressure of 0.1-0.3 MPa in a flow reactor. The solvents were simultaneously the target products of the reaction - ethylene glycol and / or propylene glycol. Gas chromatography and 13C NMR were used for the reaction products identification. It was found that the solubility of glucose in propylene glycol is 21 % by weight, and in ethylene glycol 62% by weight. It was pointed out that the process of hydrogenolysis can take place at a pressure close to atmospheric. Under these conditions, the conversion of hexoses reaches 96-100 %. The reaction products are preferably propylene glycol and ethylene glycol. The total selectivity for C3-2 polyols is 90-94 %, that is higher than in the hydrogenolysis of glucose in aqueous solution.

Thermocatalytic Hydrodeoxygenation and Depolymerization of Waste Lignin to Oxygenates and Biofuels in a Continuous Flow Reactor at Atmospheric Pressure

2020 ◽  
Vol 8 (35) ◽  
pp. 13195-13205 ◽  
Author(s):  
Swathi Mukundan ◽  
Daria Boffito ◽  
Abhijit Shrotri ◽  
Luqman Atanda ◽  
Jorge Beltramini ◽  
...  
Keyword(s):  
Atmospheric Pressure ◽  
Continuous Flow ◽  
Flow Reactor ◽  
Continuous Flow Reactor

Thermal decomposition of 1,2-dichlorobenzene part I: Effect of operating conditions

Chemosphere ◽  
1992 ◽  
Vol 24 (5) ◽  
pp. 525-536 ◽  
Author(s):  
Craig M. Young ◽  
Kent J. Voorhees
Keyword(s):  
Thermal Decomposition ◽  
Operating Conditions

Ambient Condition Effects on NOx and CO Emissions From Process Heaters

2008 ◽  
Author(s):  
Wesley R. Bussman ◽  
Charles E. Baukal
Keyword(s):  
Atmospheric Pressure ◽  
Ambient Air ◽  
Operating Conditions ◽  
Nox Emissions ◽  
Ambient Conditions ◽  
Fuel Gas ◽  
Natural Draft ◽  
Actual Operating ◽  
Wide Range ◽  
Pollution Emissions

Because process heaters are typically located outside, their operation is subject to the weather. Heaters are typically tuned at a given set of conditions; however, the actual operating conditions may vary dramatically from season to season and sometimes even within a given day. Wind, ambient air temperature, ambient air humidity, and atmospheric pressure can all significantly impact the O2 level, which impacts both the thermal efficiency and the pollution emissions from a process heater. Unfortunately, most natural draft process burners are manually controlled on an infrequent basis. This paper shows how changing ambient conditions can considerably impact both CO and NOx emissions if proper adjustments are not made as the ambient conditions change. Data will be presented for a wide range of operating conditions to show how much the CO and NOx emissions can be affected by changes in the ambient conditions for fuel gas fired natural draft process heaters, which are the most common type used in the hydrocarbon and petrochemical industries. Some type of automated burner control, which is virtually non-existent today in this application, is recommended to adjust for the variations in ambient conditions.

One-Step Simultaneous Differential Scanning Calorimetry-FTIR Microspectroscopy to Quickly Detect Continuous Pathways in the Solid-State Glucose/Asparagine Maillard Reaction

2013 ◽  
Vol 96 (6) ◽  
pp. 1362-1364 ◽  
Author(s):  
Deng-Fwu Hwang ◽  
Tzu-Feng Hsieh ◽  
Shan-Yang Lin
Keyword(s):  
Differential Scanning Calorimetry ◽  
Solid State ◽  
Maillard Reaction ◽  
Reaction Pathway ◽  
Molar Ratio ◽  
Maillard Reaction Products ◽  
Reaction Products ◽  
Scanning Calorimetry ◽  
Ftir Microspectroscopy ◽  
Amadori Product

Abstract The stepwise reaction pathway of the solid-state Maillard reaction between glucose (Glc) and asparagine (Asn) was investigated using simultaneous differential scanning calorimetry (DSC)-FTIR microspectroscopy. The color change and FTIR spectra of Glc-Asn physical mixtures (molar ratio = 1:1) preheated to different temperatures followed by cooling were also examined. The successive reaction products such as Schiff base intermediate, Amadori product, and decarboxylated Amadori product in the solid-state Glc-Asn Maillard reaction were first simultaneously evidenced by this unique DSC-FTIR microspectroscopy. The color changed from white to yellow-brown to dark brown, and appearance of new IR peaks confirmed the formation of Maillard reaction products. The present study clearly indicates that this unique DSC-FTIR technique not only accelerates but also detects precursors and products of the Maillard reaction in real time.

scholarly journals Reactions of Titanocene- and Zirconocene-Bis(trimethylsilyl)acetylene Complexes with Selected Heterocyclic and Aromatic NH and OH Acid Compounds

2007 ◽  
Vol 72 (4) ◽  
pp. 475-491 ◽  
Author(s):  
Perdita Arndt ◽  
Vladimir V. Burlakov ◽  
Ulrike Jäger-Fiedler ◽  
Marcus Klahn ◽  
Anke Spannenberg ◽  
...  
Keyword(s):  
Bond Activation ◽  
Reaction Pathway ◽  
Reaction Products ◽  
X Ray ◽  
X Ray Crystallography

The titanocene complexes Cp'2Ti(η2-Me3SiC2SiMe3) (Cp' = Cp (1), Cp* (2)) react with pyrrole under the formation of the titanium(III) mono-N-pyrrolides Cp'2Ti(NC4H4) (Cp' = Cp (6), Cp* (7)); whereas the corresponding zirconocene system Cp2Zr(η2-Me3SiC2SiMe3)(thf) (3) forms in a different reaction pathway first the Cp2Zr(NC4H4)[C(SiMe3)=CH(SiMe3)] (8) and then the zirconium(IV) bis-N-pyrrolide Cp2Zr(NC4H4)2 (11). With Cp*2Zr(η2-Me3SiC2SiMe3) (4) and pyrrole, the zirconium(IV) mono-N-pyrrolide with an agostic alkenyl group Cp*2Zr(NC4H4)[C(SiMe3)=CH(SiMe3)] (9) was obtained. In the reaction of the ethylenebistetrahydroindenyl (ebthi) complex rac-(ebthi)Zr(η2-Me3SiC2SiMe3) (5) with 2,3,5,6-tetrafluoroaniline under N-H bond activation, a complex with an agostic alkenyl group rac-(ebthi)Zr(NH-C6HF4)[C(SiMe3)=CH(SiMe3)] (10) was formed. Compound 10 reacts with additional 2,3,5,6-tetrafluoroaniline to give the bisanilide rac-(ebthi)Zr(NH-C6HF4)2 (12) which was obtained directly from 5 with two equivalents of 2,3,5,6-tetrafluoroaniline. In reactions of complex 5 with unsubstituted aniline to rac-(ebthi)Zr(NH-C6H5)2 (13) and with pentafluorophenol to bisphenolate rac-(ebthi)Zr(O-C6F5)2 (14), no intermediates could be isolated. The new reaction products 6, 9, 10, 12, 13 and 14 were investigated by X-ray crystallography.

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