液相加氢制琥珀酸酐和3，4—二羟基苯乙醇
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摘要
本文将改性骨架镍和Pd／C两种催化剂分别应用于马来酸酐和2-羟基-1-(3’,4’-二羟基苯基)-乙酮的加氢反应上。
将骤冷法制备的改性骨架镍用于马来酸酐的催化加氢,发现其可在温和条件下高选择性的制备琥珀酸酐。考察了不同反应条件对底物的转化率和目标产物选择性的影响,并进行了催化剂稳定性考察。研究表明,当采用1,4-二氧六环为溶剂,在0.2MPa和30℃的温和条件下反应60min,马来酸酐的转化率和琥珀酸酐的选择性均可达到100%。在上述条件下,该反应表现为零级反应,其表观活化能为27.1kJ／mol。在该条件下催化剂循环11釜,通过少量补加,反应时间稳定在85min左右,选择性保持在99.4%以上,催化剂表现出良好的活性和稳定性。
原料2-羟基-1-(3’,4’-二羟基苯基)-乙酮是从邻苯二酚出发,经过酰基化得到2-氯-1-(3’,4’-二羟基苯基)-乙酮,最后水解制得。经过重结晶提纯,原料纯度在98%以上。通过不同催化剂的比较,发现Pd／C对2-羟基-1-(3’,4’-二羟基苯基)-乙酮液相催化加氢制3,4-二羟基苯乙醇有较好的选择性。考察了不同反应条件对底物的转化率和目标产物选择性的影响,结果表明以5wt.%的Pd／C为催化剂、水做溶剂、4MPa、140℃下反应110min,2-羟基-1-(3’,4'-二羟基苯基)-乙酮转化率达到100%,3,4-二羟基苯乙醇选择性为87.4%。
In this article, Modified skeletal Ni and Pd/C were used in preparation of succinic anhydride and hydroxytyrosol separately in liquid phase hydrogenation.
Modified skeletal Ni was made by rapid quenching method. Maleic anhydride was selectively hydrogenated into succinic anhydride over modified skeletal Ni under mild conditions. Effects of different solvents, initial concentration of maleic anhydride, reaction temperature and pressure have been investigated. Under the optimized reaction conditions of 0.2 MPa,30℃and using dioxane as solvent, the conversion of maleic anhydride and the selectivity of succinic anhydride are both up to 100% in 60 minutes. The reaction is a pseudo-zero order reaction, and the apparent activation energy of the catalytic hydrogenation of maleic is 27.1kJ/mol. The catalyst was repeatedly used for 11 times in 1,4-dioxane, the selectivity of succinic anhydride was always higher than 99.4%, which showed high activity and stability of the catalyst.
2-hydroxy-3',4'-dihydroxyacetophenone was obtained by acylation and hydrolysis from catechol. By compared with different catalysts, Pd/C showed higher selectivity than the rests on the liquid phase hydrogenation of 2-hydroxy-3',4'-dihydroxyacetophenone to hydroxytyrosol. Effects of different solvents, reaction temperature and pressure have been investigated. Under the optimized conditions of 5wt.% Pd/C as catalyst in aqueous water,4 MPa and 140℃, the conversion of 2-hydroxy-3',4'-dihydroxyacetophenone in 110 minutes is 100%, and the selectivity of hyroxytyrosol is 87.4%.
将骤冷法制备的改性骨架镍用于马来酸酐的催化加氢,发现其可在温和条件下高选择性的制备琥珀酸酐。考察了不同反应条件对底物的转化率和目标产物选择性的影响,并进行了催化剂稳定性考察。研究表明,当采用1,4-二氧六环为溶剂,在0.2MPa和30℃的温和条件下反应60min,马来酸酐的转化率和琥珀酸酐的选择性均可达到100%。在上述条件下,该反应表现为零级反应,其表观活化能为27.1kJ／mol。在该条件下催化剂循环11釜,通过少量补加,反应时间稳定在85min左右,选择性保持在99.4%以上,催化剂表现出良好的活性和稳定性。
原料2-羟基-1-(3’,4’-二羟基苯基)-乙酮是从邻苯二酚出发,经过酰基化得到2-氯-1-(3’,4’-二羟基苯基)-乙酮,最后水解制得。经过重结晶提纯,原料纯度在98%以上。通过不同催化剂的比较,发现Pd／C对2-羟基-1-(3’,4’-二羟基苯基)-乙酮液相催化加氢制3,4-二羟基苯乙醇有较好的选择性。考察了不同反应条件对底物的转化率和目标产物选择性的影响,结果表明以5wt.%的Pd／C为催化剂、水做溶剂、4MPa、140℃下反应110min,2-羟基-1-(3’,4'-二羟基苯基)-乙酮转化率达到100%,3,4-二羟基苯乙醇选择性为87.4%。
In this article, Modified skeletal Ni and Pd/C were used in preparation of succinic anhydride and hydroxytyrosol separately in liquid phase hydrogenation.
Modified skeletal Ni was made by rapid quenching method. Maleic anhydride was selectively hydrogenated into succinic anhydride over modified skeletal Ni under mild conditions. Effects of different solvents, initial concentration of maleic anhydride, reaction temperature and pressure have been investigated. Under the optimized reaction conditions of 0.2 MPa,30℃and using dioxane as solvent, the conversion of maleic anhydride and the selectivity of succinic anhydride are both up to 100% in 60 minutes. The reaction is a pseudo-zero order reaction, and the apparent activation energy of the catalytic hydrogenation of maleic is 27.1kJ/mol. The catalyst was repeatedly used for 11 times in 1,4-dioxane, the selectivity of succinic anhydride was always higher than 99.4%, which showed high activity and stability of the catalyst.
2-hydroxy-3',4'-dihydroxyacetophenone was obtained by acylation and hydrolysis from catechol. By compared with different catalysts, Pd/C showed higher selectivity than the rests on the liquid phase hydrogenation of 2-hydroxy-3',4'-dihydroxyacetophenone to hydroxytyrosol. Effects of different solvents, reaction temperature and pressure have been investigated. Under the optimized conditions of 5wt.% Pd/C as catalyst in aqueous water,4 MPa and 140℃, the conversion of 2-hydroxy-3',4'-dihydroxyacetophenone in 110 minutes is 100%, and the selectivity of hyroxytyrosol is 87.4%.
引文
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