Acrylic acid is used in the chemical industry as intermediate fort he synthesis of polyacrylates and copolymers that are being used in the formulation of colorants, lacquers, etc. It is industrially obtained from naphta via propene and is, therefore, affected by the crude oil and natural gas shortage. An alternative pathway leading to acrylic acid from renewable raw materials is the use of lactic acid and its dehydration in near- and supercritical water. Supercritical water is a clean, environment-friendly reaction medium. Lactic acid can be obtained from carbohydrates and is therefore available in large amounts, having few industrial uses. Efforts to convert lactic acid derivatives to acrylic acid derivatives are known since circa 70 years. Until now, these efforts have lead to no industrial application. Within the scope of this work is the design and carrying out of experiments to better understand this alternative reaction leading to acrylic acid. Consequently, reaction kinetics and reaction mechanisms were investigated. An experimental apparatus and the respective analytical method to quantify the substances in the reaction mixture have been brought into being. In search of optimal reaction conditions, the influence of various parameters like temperature, pressure, concentration of the reactant and residence time, on the reaction has been investigated.
Further, the influence of the addition of electrolytes (acids, bases, salts) has also been studied. An optimum for the reaction has been found at 385 °C, 350 bar and 200 seconds residence time. Under the same conditions, the selectivity of acetaldehyde (the main byproduct of the reaction) decreases with 5 to 6 percent when a quantity of 200 ppm (g g-1) potassium dihydrogen phosphate is present in the feed. The stability of aqueous acrylic acid in the vicinity of the critical point of water has been examined. It has been determined that the addition of water to acrylic acid not only yields 3-hydroxypropionic acid, the normal product of a Markovnikov-addition, but also lactic acid, especially at 390 °C, where the molar ratio of lactic to 3-hydroxypropionic acid nears a value of 1. A hitherto unclear issue regarding the reaction mechanism concerns the decarboxylation of lactic acid. Carbon dioxide has been indeed detected, but the expected decarboxylation product, ethanol, could not be found. Acetaldehyde is found instead. As a consequence, it was postulated in the literature, that the decarboxylation of lactic acid proceeds through a radical mechanism. In this work it was shown that the decarboxylation of lactic acid does not occur under the investigated conditions and the relatively large amounts of carbon dioxide are generated from carbon monoxide through the water gas shift reaction. Based on the experimental data, a kinetic model has been developed. The reaction rate constants for the reactions in which acetaldehyde, acrylic acid, lactic acid and 3-hydroxypropionic acid are involved, have been determined for three temperatures (350, 385 and 420 °C) with the help of a simulation software.
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