| Materials containing phosphoric/phosphonic acid groups have made great progress in the organic reactions such as catalytic pyrolysis, isomerization, cyclization and so on, but there is less application in the esterification or ester exchange reaction. In this paper, a series of materials containing phosphorus/phosphonate groups were got by simple synthesis method, and were applied to catalyzing in various esterifications. The structure and properties of the catalytic materials were systematically characterized by elemental analysis, infrared spectroscopy (FT-IR), X-ray diffractometry, porous analysis, and thermogravimetry analysis.1. By solid state synthesis method, different shapes of ammonium cadmium phosphate materials with good thermal stability are synthesized with ammonium oxalate, ammonium acetate, EDTA, triethylene diamine and imidazole as templates. The results show that the use of templates can effectively control the shapes and pevent the coacervate. This series of materials have good catalytic effect on the esterification of n-butyl alcohol with acetic aicd, especially in synthetizing phosphoric admium ammonium by taking ammonium acetate and triethylene diamine as templates.2. Solid acid catalyst (PA/NaY) is got by loading 1-hydroxyethylidenedi- phosphonic acid on NaY zeolite. Organic phosphonic acid molecules are distributed in the pores of NaY zeolite, and react and exchange with the active site of zeolite, then the acid sites are produced. Therefore, it has good effect on the catalytic synthesis of n-butyl acetate, n-butyl stearate, ethyl stearate and ethyl Oleate. The design of Box-Behnken is applied in the esterification reaction, and it can optimize the reaction conditions and predict the conversion rate. The kinetics data indicate that the catalytic synthesis of n-butyl acetate and ethyl stearate follows pseudo- homogeneous-second-order irreversible reaction model, and pseudo-homogeneous- second-order reversible reaction model provides good description for catalytic synthesis of n-butyl stearate and ethyl oleate.3. And convert Na-type amino phosphonic acid resin into the H-type, which is used in catalytic synthesis of ethyl oleate. The optimum conditions for maximum esterification percentage can be obtained by using the design of Box-Behnken with a minimum of experimental work. The oleic acid conversion reached 92.02±0.74% under 115oC and 10h of reaction time with the molar ratio of alcohol to oleic acid being 14:1 and 2.9g H-type resin as catalyst. The pseudo-homogeneous-second-order reversible reaction model for the esterification was established. By fitting the kinetic model with the experimental results, the activation energy of the positive reaction Ea+=36.89kJ/mol and the reverse reaction Ea-=11.76kJ/mol were obtained, positive and reverse pre-exponential factors are resepectively 62.18 and 3.24×10-2.4. Silica-gel supported by amino phosphonic acid material was made on the basis of our previous research work, it has good effect on catalytic synthesis of ethyl oleate. The optimal conditions were obtained at 8.5:1 of molar ratio of n-butanol to acid using 4.0g catalyst at 110oC for 10h by the design of Box-Behnken. Under these conditions, the esterification percentage was 76.55±0.80%. The kinetics of this reaction was also studied, the activation energy of the positive reaction Ea+=16.97kJ/mol and the reverse reaction Ea-=14.33kJ/mol were calculated, positive and reverse pre-exponential factors are resepectively 6.06×10-2and 8.36×10-2.
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