Kinetics and modelling of heptane steam-cracking

2014 ◽  
Vol 68 (12) ◽  
Author(s):  
Natália Olahová ◽  
Martin Bajus ◽  
Elena Hájeková ◽  
Lukáš Šugár ◽  
Jozef Markoš
Keyword(s):  
Flow Reactor ◽  
Frequency Factor ◽  
Product Distribution ◽  
Reaction Scheme ◽  
Reaction Products ◽  
Primary Products ◽  
Molecular Reaction ◽  
Secondary Reactions ◽  
Steam Cracking ◽  
Good Agreement

AbstractThe kinetics and product distribution during the cracking of heptane in the presence of steam were investigated. The experiments were performed in a flow reactor under atmospheric pressure in a temperature range of 680–760°C with a mass ratio of steam to heptane of 3: 1. The overall decomposition of heptane is represented by a first-order reaction with activation energy of 249.1 kJ mol−1 and a frequency factor of 3.13 × 1013 s−1. The reaction products were analysed using gas chromatography, the main product being ethylene. The molecular reaction scheme, which consists of a primary reaction and 24 secondary reactions between primary products, was used for modelling the experimental product yields. The yields of ethylene and hydrogen were in good agreement; however the experimental yields of propylene were higher than the predicted yields.

Thiirene formation in the reactions of sulfur atoms with alkynes

1983 ◽  
Vol 61 (10) ◽  
pp. 2268-2281 ◽  
Author(s):  
Bela Verkoczy ◽  
Alden G. Sherwood ◽  
Imre Safarik ◽  
Otto P. Strausz
Keyword(s):  
Gas Phase ◽  
New Products ◽  
Reaction Products ◽  
Gas Phase Reactions ◽  
Bimolecular Reactions ◽  
Primary Products ◽  
End Products ◽  
Secondary Reactions

The gas phase reactions of S(1D2) and S(3PJ) atoms with alkynes have been studied by photolyzing COS in the presence of CH≡CH, CF3C≡CH, and CF3C≡CCF3. In the reactions with CH≡CH, CS2, benzene, and thiophene were formed; with CF3C≡CH, eight products were found with disubstituted thiophenes and trisubstituted benzenes as the major products. In the case of CF3C≡CCF3, only perfluorotetramethylthiophene was detected at low conversion but at long photolysis several new products were observed. Many of the reaction products characterized here have not been reported before.The formation and distribution of the reaction products could be rationalized by an overall mechanism in which the formation of the highly reactive primary adducts, thiirene and thioformylmethylene, is followed by bimolecular reactions yielding the principal end products. The formation of minor products could be explained by secondary photoisomerizations, secondary photolysis, and by secondary decompositions and the secondary reactions of sulfur atoms with primary products.

scholarly journals Representative model compounds for understanding the pyrolytic behavior of pre-oxidized β-ether-type lignin

BioResources ◽  
2020 ◽  
Vol 15 (3) ◽  
pp. 6989-7008
Author(s):  
Shuyun Liu ◽  
Weikun Jiang ◽  
Bo Jin ◽  
Yu Liu ◽  
Lucian A. Lucia
Keyword(s):  
Simultaneous Thermal Analysis ◽  
Product Distribution ◽  
Gas Chromatography Mass Spectrometry ◽  
Pyrolysis Gas ◽  
Och3 Group ◽  
Primary Products ◽  
Bridge Structures ◽  
Secondary Reactions ◽  
Representative Model

To achieve a better understanding of the pyrolysis behavior of pre-oxidized β-ether-type lignin, three Cα=O type dimers with different substituent groups on the aromatic ring were synthesized and analyzed by a simultaneous thermal analysis instrument (STA), in-situ Fourier transform infrared spectroscopy (in-situ FTIR), and pyrolysis-gas chromatography/ mass spectrometry (Py-GC/MS). The results showed that major primary pyrolysis reactions of Cα=O type models normally occurred at 200 to 400 °C, and connecting bridge structures of models were completely destroyed, causing the emission of abundant volatiles. Substituent groups of aromatic rings played direct roles in thermal stability of models, volatiles emission, product characteristics, and secondary reaction pathways of major primary products. Particularly, the aryl–OCH3 group clearly enhanced the reactivity of intramolecular linkages and was an important active functional group for secondary reactions. As major primary products and intermediates, guaiacol and 2-methoxy-benzaldehyde were formed via the cleavage of Cα–O and Cα–Cβ bonds and could also be converted into phenol, benzaldehyde, and 2-methylphenol via rearrangement of aryl–OCH3 into an aryl–CH3 group or –OCH3 group removal. Oxidization of benzylic alcohol to benzylic ketone not only simplified depolymerization pathways, but also resulted in better selectivity of phenolic monomers and a predictable product distribution.

scholarly journals Effect of Temperature on Gas and Liquid Products Distribution in Thermal Cracking of Nigerian Bitumen

2021 ◽  
Vol 22 (2) ◽  
pp. 7-16
Author(s):  
ABIMBOLA GEORGE OLAREMU ◽  
Ezekiel Oluyemi ODEBUNMI ◽  
Jim A ANDERSON
Keyword(s):  
Thermal Cracking ◽  
Product Distribution ◽  
Reaction Scheme ◽  
Effect Of Temperature ◽  
Gas Chromatography Mass Spectrometry ◽  
Reaction Products ◽  
Sulphur Compounds ◽  
Oil Reserves ◽  
Liquid Products ◽  
Cracking Reaction

The increasing population growth resulting in the tremendous increase in consumption of fuels, energy, and petrochemical products and coupled with the depletion in conventional crude oil reserves and production make it imperative for Nigeria to explore her bitumen reserves so as to meet her energy and petrochemicals needs. Samples of Agbabu bitumen were subjected to thermal cracking in a tubular steel reactor operated at 10 bar pressure to investigate the effect of temperature on the cracking reaction. The gas produced was analyzed in a Gas Chromatograph while the liquid products were subjected to Gas Chromatography-Mass Spectrometry (GC-MS) analysis. Heptane was the dominant gas produced in bitumen cracking at all temperatures and the reaction products show a distribution of lighter hydrocarbons most of which are in the gasoline range. The product distribution of bitumen conversion depends strongly on the cracking temperature and the oil produced contains the valuable liquid fractions. The products of thermal cracking of bitumen can be classified into the following groups; alkanes, alkenes, amines, aromatics, alkanoic acids, alkanols, esters, ethers, ketones, sulphur compounds, and nitrogen compounds. The activation energies of the products formed were determined. The LNG produced all have unusually low values activation energy (hence easily converted) pointing to the high quality of Agbabu crude      The conversion process was affected by the reaction time and suggests that the transformation of bitumen into smaller fractions follows a definite reaction scheme in which the heavy oil transformed to lower fractions and was subsequently converted to smaller liquid fractions and gases.

COMPUTER MODELING OF CHEMICAL EQUILIBRIUMS IN WO3–H2O SYSTEM

2017 ◽  
pp. 35-48 ◽  
Author(s):  
V.P. Bondarenko ◽  
O.O. Matviichuk
Keyword(s):  
Transition Temperature ◽  
Gas Phase ◽  
Single Phase ◽  
Reference Data ◽  
Maximum Amount ◽  
Reaction Products ◽  
Influence Of Temperature ◽  
Equilibrium Chemical ◽  
Program Data ◽  
Good Agreement

Detail investigation of equilibrium chemical reactions in WO3–H2O system using computer program FacktSage with the aim to establish influence of temperature and quantity of water on formation of compounds of H2WO4 and WO2(OH)2 as well as concomitant them compounds, evaporation products, decomposition and dissociation, that are contained in the program data base were carried out. Calculations in the temperature range from 100 to 3000 °С were carried out. The amount moles of water added to 1 mole of WO3 was varied from 0 to 27. It is found that the obtained data by the melting and evaporation temperatures of single-phase WO3 are in good agreement with the reference data and provide additionally detailed information on the composition of the gas phase. It was shown that under heating of 1 mole single-phase WO3 up to 3000 °С the predominant oxide that exist in gaseous phase is (WO3)2. Reactions of it formation from other oxides ((WO3)3 and (WO3)4) were proposed. It was established that compound H2WO4 is stable and it is decomposed on WO3 and H2O under 121 °C. Tungsten Oxide Hydrate WO2(OH)2 first appears under 400 °С and exists up to 3000 °С. Increasing quantity of Н2О in system leads to decreasing transition temperature of WO3 into both liquid and gaseous phases. It was established that adding to 1 mole WO3 26 mole H2O maximum amount (0,9044–0,9171 mole) WO2(OH)2 under temperatures 1400–1600 °С can be obtained, wherein the melting stage of WO3 is omitted. Obtained data also allowed to state that that from 121 till 400 °С WO3–Н2O the section in the О–W–H ternary system is partially quasi-binary because under these temperatures in the system only WO3 and Н2O are present. Under higher temperatures WO3–Н2O section becomes not quasi-binary since in the reaction products WO3 with Н2O except WO3 and Н2O, there are significant amounts of WO2(OH)2, (WO3)2, (WO3)3, (WO3)4 and a small amount of atoms and other compounds. Bibl. 12, Fig. 6, Tab. 5.

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.

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.

scholarly journals Study of the Synchrotron Photoionization Oxidation of Alpha-Angelica Lactone (AAL) Initiated by O(3P) at 298, 550, and 700 K

Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 4070
Author(s):  
Golbon Rezaei ◽  
Giovanni Meloni
Keyword(s):  
Atomic Oxygen ◽  
Fossil Fuels ◽  
Reaction Products ◽  
Photoionization Mass Spectrometry ◽  
Natural Substances ◽  
Primary Products ◽  
Major Reaction ◽  
Angelica Lactone ◽  
Significant Attention

In recent years, biofuels have been receiving significant attention because of their potential for decreasing carbon emissions and providing a long-term renewable solution to unsustainable fossil fuels. Currently, lactones are some of the alternatives being produced. Many lactones occur in a range of natural substances and have many advantages over bioethanol. In this study, the oxidation of alpha-angelica lactone initiated by ground-state atomic oxygen, O(3P), was studied at 298, 550, and 700 K using synchrotron radiation coupled with multiplexed photoionization mass spectrometry at the Lawrence Berkeley National Lab (LBNL). Photoionization spectra and kinetic time traces were measured to identify the primary products. Ketene, acetaldehyde, methyl vinyl ketone, methylglyoxal, dimethyl glyoxal, and 5-methyl-2,4-furandione were characterized as major reaction products, with ketene being the most abundant at all three temperatures. Possible reaction pathways for the formation of the observed primary products were computed using the CBS–QB3 composite method.

Nitroxides as reaction intermediates

1982 ◽  
Vol 60 (12) ◽  
pp. 1414-1420 ◽  
Author(s):  
Hans Gunter Aurich
Keyword(s):  
Electron Spin Resonance ◽  
Electron Spin ◽  
Isopropyl Alcohol ◽  
High Reactivity ◽  
Reaction Intermediates ◽  
Reaction Products ◽  
Nitronyl Nitroxide ◽  
Reaction Conditions ◽  
Spin Resonance ◽  
Secondary Reactions

Vinyl nitroxides 4 are obtained by oxidation of the nitrones 3, as was shown by esr studies and by identification of the reaction products. The formation of 4d–f is even observed in oxidation of the hydroxylamines 1d–f, nitroxides 2d–f and nitrones 3d–f being the intermediates. The high reactivity of the vinyl nitroxides 4 at their β-position is illustrated by the reactions of 4a with various compounds affording the nitroxides 7–10, respectively. Compound 4c reacts with its precursor 3c to give 11, 12, or 13, depending on the reaction conditions. From oxidation of 3a, c, and e the dimerization products 5a, c, and e, respectively, could be isolated. Whereas further oxidation of 5d yields 6d, the acyl nitroxides 14a and c are formed in the oxidation of 5a and c, respectively.The formation of quinone 23 in the reaction of 2-methyl-2-nitrosopropane with potassium tert-butoxide in isopropyl alcohol in the presence of oxygen is discussed. The nitroxide 20 has been detected in the reaction mixture. Imines 24 react with nitrosobenzene giving nitroxides 26. These are further oxidized by nitrosobenzene to afford nitrones 27. Whereas 27a and b could be isolated, 27c and d undergo further reaction yielding the diimines 30c and d along with dinitrone 29.The formation and reactions of imino nitroxides 31 and of the nitronyl nitroxide 41 are discussed. Electron spin resonance studies revealed the high reactivity of the imidazolyl-1,3-dioxides 46 and the imidazolyl-1-oxides 50, which easily form radicals 47–49 and 51, respectively, which are derived from secondary reactions.

scholarly journals Continuous-flow Heck synthesis of 4-methoxybiphenyl and methyl 4-methoxycinnamate in supercritical carbon dioxide expanded solvent solutions

2013 ◽  
Vol 9 ◽  
pp. 2886-2897 ◽  
Author(s):  
Phei Li Lau ◽  
Ray W K Allen ◽  
Peter Styring
Keyword(s):  
Carbon Dioxide ◽  
Supercritical Carbon Dioxide ◽  
Methyl Acrylate ◽  
Heck Reaction ◽  
Continuous Flow ◽  
Flow Reactor ◽  
Product Distribution ◽  
Internal Diameter ◽  
Palladium Metal ◽  
Supercritical Carbon

The palladium metal catalysed Heck reaction of 4-iodoanisole with styrene or methyl acrylate has been studied in a continuous plug flow reactor (PFR) using supercritical carbon dioxide (scCO2) as the solvent, with THF and methanol as modifiers. The catalyst was 2% palladium on silica and the base was diisopropylethylamine due to its solubility in the reaction solvent. No phosphine co-catalysts were used so the work-up procedure was simplified and the green credentials of the reaction were enhanced. The reactions were studied as a function of temperature, pressure and flow rate and in the case of the reaction with styrene compared against a standard, stirred autoclave reaction. Conversion was determined and, in the case of the reaction with styrene, the isomeric product distribution was monitored by GC. In the case of the reaction with methyl acrylate the reactor was scaled from a 1.0 mm to 3.9 mm internal diameter and the conversion and turnover frequency determined. The results show that the Heck reaction can be effectively performed in scCO2 under continuous flow conditions with a palladium metal, phosphine-free catalyst, but care must be taken when selecting the reaction temperature in order to ensure the appropriate isomer distribution is achieved. Higher reaction temperatures were found to enhance formation of the branched terminal alkene isomer as opposed to the linear trans-isomer.

scholarly journals Preparation of isocyanates by carbamates thermolysis on the example of butyl isocyanate

2019 ◽  
Vol 58 (4) ◽  
pp. 40-47
Author(s):  
Ratmir R. Dashkin ◽  
◽  
Dmitry A. Gordeev ◽  
Khusrav Kh. Gafurov ◽  
Sergey N. Mantrov ◽  
...  
Keyword(s):  
Gas Phase ◽  
High Performance ◽  
Gas Flow ◽  
Flow Reactor ◽  
Packed Column ◽  
Biologically Active ◽  
Dibutyltin Dilaurate ◽  
Reaction Products ◽  
Uv Detector ◽  
Laboratory Setup

Butyl isocyanate is widely distributed as a precursor for the production of a number of biologically active substances: fungicides, preservatives, insecticides, personal care products, etc. Nowadays, there are a number of methods for the preparation of isocyanates, which can be divided into liquid phase and gas phase. One of the perspective methods for the production of isocyanates is the thermolysis of carbamate and/or the actions of various reaction activating agents, accompanied by the elimination of alcohol, but this process is reversible, which greatly complicates its use in industry. The paper presents the results of studies of non-catalytic thermal decomposition of N-alkylcarbamates with the formation of alkylisocyanates on the example of butylisocyanate in the gas phase, flow reactor in a wide temperature range (200 to 450 °C). In addition, a series of experiments was carried out using a catalyst, dibutyltin dilaurate, in order to reduce the thermolysis temperature and increase the yield of the final product. To implement the isocyanate production process, an experimental laboratory setup, consisting of a gas flow meter (argon) regulator, a packed column (for heating) and a sorption solution tank, was developed and tested. The thermolysis of N-n-butylcarbamate was carried out in two variations: the preparation of an individual n-butylisocyanate and the passage of reaction products through a sorption solution linking the n-butyl isocyanate to N-n-butyl-N '-(1-phenylethyl)urea, which allows to estimate the yield of the target n-butylisocyanate without additional losses. The analysis of the obtained substances was carried out by high performance liquid chromatography with a UV detector (target product) and a mass detector (analysis of by-products). According to the results of research, a modification of the laboratory facility was proposed, as well as n-butylisocyanate was obtained with a yield of 49% on the basis of a new technique.

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