Poly(oxymethylene) dimethyl ethers (OME) reduce the soot formation during the combustion process, when added to diesel fuels. OME are a Gas-to-Liquid (GtL) option as they can be produced via methanol from natural gas or renewable feedstocks. This work deals with the synthesis of OME from the educts formaldehyde and methanol in aqueous solutions. The studied mixtures are complex reacting systems in which besides OME, also poly(oxymethylene) glycols and poly(oxymethylene) hemiformals are present. The chemical equilibrium of the OME formation is studied in a stirred batch reactor varying in the educts' overall ratio of formaldehyde to methanol and the amount of water and varying the temperature between 333.15 K and 378.15 K. A mole fraction-based, as well as an activity-based model of the chemical equilibrium of the OME formation are developed, which explicitly account for the formation of poly(oxymethylene) glycols and poly(oxymethylene) hemiformals. Information on the latter reactions from literature are confirmed by NMR experiments in the present work.
General remarks on the oxidation reactions of hydrocarbons involved in in-situ combustion are followed by estimates of heat releases. A formula is derived for computing the heat of combustion in the high-temperature zone. Reaction kinetics in porous media applied to the in-situ combustion porous media applied to the in-situ combustion process is discussed. It is observed that there is process is discussed. It is observed that there is some similarity between the kinetics of reverse and partially quenched combustion processes. The influence of additives on crude oil oxidation in porous media is illustrated by effluent gas analysis experiments. Some information concerning the values of the kinetic parameters of the reaction controlling the velocity of a reverse combustion front is derived from the interpretation of laboratory experiments, using a numerical model.
Introduction
A great deal of laboratory and field work has been done on thermal recovery methods. The importance and limitations of these techniques have been extensively studied. However, some of the chemical and physical problems involved that needed to be elucidated were studied as part of a research program carried out by the Institut Francais du Petrole. Specific problems are created by in-situ combustion since both the possibility of combustion-front propagation and the air requirement are controlled by the extent of the exothermic oxidation reactions. Actually, the propagation velocity of a forward combustion front depends on the fuel formation and combustion, which are controlled by the kinetics of these processes; furthermore, the peak temperature is related to the heat released by oxidation and combustion reactions. Therefore, a quantitative estimation of the parameters related to the chemical aspects of the parameters related to the chemical aspects of the process is a necessary step in studying combustion process is a necessary step in studying combustion through a porous medium. General and theoretical considerations on heats of reaction and kinetics are presented and illustrated by experimental data and numerical interpretation of the results.
HEAT RELEASED IN THE OXIDATION OF HYDROCARBONS
DESCRIPTION OF OXIDATION REACTIONS
A great number of reaction products are produced by the oxidation of hydrocarbons. By taking into account the formation of bonds between one carbon atom and oxygen, it is possible to derive the most important processes.
Complete combustion,
(1) 2 2 2 2H H3R C R + ---- O → RR + CO + H O
Incomplete combustion,
(2) 2 2H H R C R + O → RR + CO + H O
Oxidation to carboxylic acid,
(3) 2 2 2H OH H3 OR C H + --- O → R - C + H O
Oxidation to aldehyde,
(4) H H R C
Oxidation to ketone,
(5) 2 2H O H R C R ' + O → R - C - R; + H O
Oxidation to alcohol,
(6) R' R; R C H
SPEJ
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