The Study Of Copper Metal-Organic Frameworks Catalysts Based On Wet Catalytic Oxidation Technology

With the development of chemical industry, the discharge of phenolic organic effluents is increasing, which resultes in serious pollution of the environment and leads to much attention being paid to the disposal of phenolic organic wastewater. Catalytic wet hydrogen peroxide oxidation technology has been the focus in the study of phenolic organic wastewater treatment due to its mild operating conditions and satisfactory degradation effect. MOFs materials have shown good application prospect in the field of catalysis because of large specific surface area, uniform and controllable pore structure. Comparing to others catalysts, MOFs have many advantages when they are selected as heterogeneous catalysts for wet catalytic oxidation of phenol.Two different MOFs:HKUST-1 and Cu(BDC) were synthesized by solvothermal method in this paper. HKUST-1 and Cu(BDC) were octahedral and hexahedral structure, respectively. The content of Cu in the two MOFs was 24.18% and 15.21%, respectively. The two MOFs have been applied as heterogeneous catalysts for catalytic degradation of phenol wastewater with H2O2 as oxidant. The conditions including reaction temperature, catalyst dose, H2O2 dose and the pH of phenol wastewater which could affect the catalytic degradation performance of phenol have been investigated. In addition, the reusability and stability of Cu-MOFs have been investigated and the catalystic degradation mechanism has been preliminary investigated, too. The result shows that:Cu(BDC) framework showed better catalytic performance than HKUST-1 framework. When the reaction temperature, H2O2 dose, Cu(BDC) dose and the pH of phenol solution were separately 60℃,1.0 mL,20 mg and 6.65, the optimal catalytic degradation efficiency of phenol were reached with phenol conversion and COD removal efficiency of 99% and 93% obtained. After reused twice, Cu(BDC) could still keep good catalytic performance with phenol conversion and COD removal efficiency of 99% and over 85% obtained. Simular to other catalysts, the catalytic oxidation of phenol by Cu(BDC) also followed hydroxyl radical mechanism. And Cu(BDC) framework showed satisfactory stability with Cu2+ leaching of 7 ppm.In this paper, GrO/HKUST-1 composites with lwt%,3wt% and 5wt% content of GrO have been synthesized by solvothermal method. And they have been applied as catalysts for catalytic degradation of phenol. The result shows that:The added GrO didn’t prevent the formation of HKUST-1 framework and most HKUST-1 crystals could still keep well octahedral structure. The added GrO adhered to the surface of HKUST-1 crystals. As the added GrO increased, the catalytic performance of GrO/HKUST-1 composites for phenol degradation improved and then decreased. When the content of GrO was 3wt%, GrO-3/HKUST-1 composite catalyst showed best catalytic performance. Higher temperature were beneficial to the catalytic oxidation of phenol by GrO-3/HKUST-l composite. The GrO-3/HKUST-1 composite catalyst showed satisfactory catalytic performance in the pH range of 4 to 9 indicating the GrO-3/HKUST-1 composite catalyst owned strong acid and alkali resistance ability. After doping GrO, the developed GrO-3/HKUST-1 showed preferable reusability and the catalytic oxidation of phenol also relied on hydroxide radicals.