Evaluation of manufacturing processes for the production of atrazine

Abstract

This report describes the results of investigations carried out with the view to find an alternative for MIBK as solvent for the production of atrazine as currently practised by Dow AgroSciences in South Africa. The main motivating factors for the said investigation was: · to increase the yield of atrazine produced, · to reduce the amount of organics, consisting essentially of reaction solvent containing dissolved product, in the aqueous process effluent, and · to improve the properties of the solid (crystalline) product to enable easier product formulation. Synthetic reactions carried out in the absence of organic solvent, i.e. in essentially a 10% NaCl solution containing a surfactant, proved rather disappointing. Low yields of atrazine were obtained together with relatively large amounts of by-products such as propazine and simazine, irrespective of the nature of the surfactant. The reason for the low yield of atrazine and high yields of by-products were established in competing substitution reactions. In these reactions, IPA was reacted with an equimolar mixture of cyanuric chloride and mono-i (first reaction intermediate) in both aqueous medium and in toluene as reaction solvent. The results of these experiments indicated that in aqueous medium IPA reacts faster with mono-i than cyanuric chloride to give propazine as by-product. In toluene, however, the preferred reaction is with cyanuric chloride to give more mono-i as product. Toluene was investigated as an alternative organic solvent to MIBK in view of its desirable properties such as low solubility in water and ease of recovery and recycling. The synthesis of atrazine was optimised in terms of addition sequence and rates of amine reagents and base (HCl acceptor), both by means of benchscale reactions and reaction calorimetry. Reaction energy profiles indicated that both the reaction of secondary amine/NaOH and primary amine/NaOH were virtually instantaneous. This implies that the reaction can be performed under feed control conditions. Of particular importance in ensuring high yields of high purity product was accurate temperature control (since both reaction steps are highly exothermic) and mixing. The latter was important in view of the rapid reaction of amine/NaOH with cyanuric chloride, as well as the possible reaction of mono-i, the first reaction intermediate, with IPA in cases of local excesses of reagent. Under optimum conditions, a yield of atrazine > 97% could be achieved where the resultant product was well within stipulated product specifications. In view of the results obtained, the following recommendations regarding the synthesis of atrazine in toluene as reaction solvent can be made: · Use a reagent addition sequence that staggers the addition of amine and NaOH in such a manner that amine is added first for a short while, followed by the simultaneous addition of amine and NaOH, and ending with NaOH. Use two reaction vessels in series, one for the IPA addition reaction and one for the MEA addition reaction. In this manner the reaction can be run on a continuous basis since no lag time between amine additions is required. Also, smaller reactors may be used whilst maintaining high production rates. Smaller reactors will improve both temperature control and mixing of reagents