黄磷尾气催化氧化净化系列催化剂开发研究
摘要
本文研究了低温微氧催化氧化净化黄磷尾气的相关问题。
首先，通过载体选择实验、催化剂制备实验、基础实验和优化实验得到了脱磷、脱硫和脱磷硫三种催化剂评估了催化净化的影响因素，并通过再生实验评价了催化剂再生效果。载体选择实验表明，ZP-4活性炭对PH_3和H_2S吸附效果较好，确定ZP-4活性炭为催化剂载体。催化剂制备实验表明，碳酸钠，醋酸铜和盐酸浸渍得到的催化剂，PH_3和H_2S的净化效果可以显著提高；选择盐酸为脱磷催化剂的浸渍液，碳酸钠为脱硫催化剂的浸渍液，醋酸铜为脱磷硫催化剂的浸渍液。基础实验表明，脱磷催化剂净化PH_3时，较合适的盐酸浓度是5％；无氧时为物理吸附，较合适吸附反应温度为20℃，有氧时因化学反应吸附容量提高较大，较合适反应温度为70℃；较合适氧含量为1％。基础实验同时表明，脱硫催化剂净化H_2S时，较合适的碳酸钠浓度是7％；较合适氧含量为0.4％；随着温度的增加脱硫催化剂净化H_2S的效果逐步提高，较合适反应温度为90℃。优化实验表明，脱磷硫催化剂净化PH3时，影响因素的重要性顺序依次为反应温度，氧含量，焙烧温度，浸渍液浓度，气体流量和粒径；实验范围内影响因素的最佳值分别为反应温度95℃，浸渍液浓度0.3 mol／L，粒径3.5 mm，氧含量1％，焙烧温度300℃和气体流量0.4 L／min。优化实验同时表明，脱磷硫催化剂净化H_2S时，影响因素的重要性顺序依次为反应温度，氧含量，浸渍液浓度，焙烧温度，粒径气体和流量；实验范围内影响因素的最佳值分别为反应温度95℃，浸渍液浓度0.3 mol／L，粒径3.5 mm，氧含量1％，焙烧温度300℃和气体流量0.4 L／min。再生试验表明，再生基本可行；再生方案对含磷物质的再生效果比较好，同时再生液中磷酸含量达0.877mg／L，可回收其中的磷酸；再生方案对含硫杂质的再生不甚理想，同时再生液中硫磺回收过程比较复杂，有待于进一步研究。
接着，通过动力学实验得到了三种催化剂的动力学参数，并评估了内外扩散对催化净化的影响。动力学实验表明，用脱硫催化剂净化H_2S时，平均反应级数为—1，反应的平均活化能为23.77kJ／mol；用脱磷催化剂净化PH_3时，平均反应级数为—2，反应的平均活化能为61.3kJ／mol；用脱磷硫催化剂净化PH_3和H_2S时，平均反应级数分别为-0.8和-0.76，反应的平均活化能分别为1247.6 J／mol和134.4 J／mol。活化能数值初步证明了催化剂净化黄磷尾气是一个化学反应过程。内外扩散过程对反应过程都有重要影响，减小催化剂粒径增加空速可以显著提高脱磷硫催化剂净化PH_3和H_2S的平均反应速率。
然后，通过现场实验用江磷集团的黄磷尾气对催化剂进行了现场评价，并通过催化剂表征得到了催化剂催化氧化净化黄磷尾气的反应机理。现场实验表明，用脱硫催化剂净化黄磷尾气时，200分钟内各种杂质总含量都低于10mg／Nm~3；脱硫催化剂对H_2S的选择性较好。现场实验同时表明，脱磷硫催化剂净化黄磷尾气时，300分钟内各种杂质总含量都低于10mg／Nm~3；脱磷硫催化剂对H_2S和PH_3的选择性较好。孔径分布分析、热重差热分析和扫描电镜分析，可以初步认为脱硫催化剂和脱磷催化剂净化H_2S和PH_3时，H_2S和PH_3首先与氧在催化剂表面进行催化氧化反应生成硫或硫氧化物和磷或磷氧化物，然后沉积吸附在催化剂表面。X射线光电子能谱分析、热重差热分析和孔径分布分析，可以认为脱磷硫催化剂净化H_2S和PH_3时，H_2S和PH_3首先与氧在催化剂表面进行催化氧化反应生成S和P_2O_5，然后沉积吸附在催化剂表面。
最后，根据反应机理推导得到三种催化剂的催化净化模型，并用实验数据对模型进行了验证。拟合得到脱磷催化剂和脱硫催化剂模型的参数，其预测PH_3或H_2S的穿透曲线时，相关系数分别可以达到0.99354和0.99136；通过数值计算求解脱磷硫催化剂模型，其预测PH_3或H_2S的穿透曲线时，相关系数分别可以达到0.9976和0.9919。
This thesis is about research and discussion of purification of yellow phosphorus off-gas at low temperature and low oxygen content.
Firstly, experiments were conducted to select carrier of catalyst, to assess the efficiency of catalyst regeneration, and the influencing factors which were related with purification of yellow phosphorus off-gas. Activated carbon was an efficient adsorbent for both PH_3 and H_2S, and therefore chosen as carrier of catalyst. HCl, Na_2CO_3 and CuAc_2 were selected to be used as impregnants for phosphorus-remove catalyst, sulfur-remove catalyst and phosphorus-sulfur-remove catalyst respectively. When phosphorus-remove catalyst was used to remove PH3, it was 5% and 1% (vol%) for the appropriate concentration of HC1 and oxygen content respectively; and it was physic adsorption in anoxic atmosphere with 20℃ as appropriate temperature, and chemical reaction and adsorption in aerobic atmosphere with 70 ℃ as appropriate temperature. When sulfur-remove catalyst was used to remove H_2S, it was 7%, 0.4% (vol%) and 90℃ for the appropriate concentration of Na_2CO_3, oxygen content and reaction temperature respectively; the higher the temperature was the higher the removal efficiency was. When phosphorus-sulfur-remove catalyst was used to remove PH_3 and H_2S, for PH3 the superiority order was temperature > oxygen content > parch temperature > impregnant concentration (Cu~(2+)) > flow rate > diameter while for H_2S it was reaction temperature > oxygen content > impregnant concentration > parch temperature > diameter > flow rate. And the optimum experiment parameters for both PH_3 and H_2S were reaction temperature, 95℃; impregnant concentration (Cu~(2+)), 0.25 mol/L; diameter of catalyst, 3.5 mm; oxygen content, 1%; parch temperature, 300 ℃ and flow rate, 0.4 L/min. Regeneration of phosphorus-sulfur-remove catalyst was effective for PH_3 but not compelling for H_2S.
Secondly, experiments were carried out to acquire thermodynamic parameters and to assess the influence of internal and external diffusion on removal efficiency. When sulfur-remove catalyst was used to remove H_2S, it was -1 and 23.77kJ/mol for the average reaction order and average activation energy. When phosphorus-remove catalyst was used to remove PH_3, it was -2 and 61.3kJ/mol for the average reaction order and average
activation energy. When phosphorus-sulfur-remove catalyst was used to remove PH_3 and H_2S, reaction orders were -0.8 and -0.76 for PH_3 and H_2S respectively; and average activation energies were 1247.6 J/mol and 134.4 J/mol for PH_3 and H_2S respectively. Purification of yellow phosphorus off-gas could be primarily identified as a chemical process through these values of activation energies. Decrease of diameter of catalyst and increase of flow rate could dramatically increase the average reaction rate.
Thirdly, onsite experiments were conducted to investigate the practical purifying efficiency of catalyst on phosphorus off-gas in Jianglin Corporation; and SEM, TG/DTA, BET adsorption and XPS were used to characterize the performance of catalysts and to illustrate the reaction mechanism. When sulfur-remove catalyst was used to purify phosphorus off-gas, total impurity content was lower than 10mg/Nm~3 in 200 minutes with better selectivity on H_2S. When phosphorus-sulfur-remove catalyst was used to purify phosphorus off-gas, total impurity content was lower than 10mg/Nm~3 in 300 minutes with better selectivity on H_2S and PH_3. Analysis of pore size distribution, TG/DTA and SEM primarily indicates that, during purification, H_2S and PH_3 were firstly reacted with oxygen to produce sulfur and sulfur oxides or phosphorus and phosphorus oxides, and then adsorbed on sulfur-remove catalyst or phosphorus-remove catalyst. Analysis of XPS, TG/DTA and pore size distribution indicates that, during purification, H_2S and PH_3 were firstly reacted with oxygen to produce S and P_2O_5, and then adsorbed on phosphorus-sulfur-remove catalyst.
Finally, models were established according to reaction mechanism, and calibrated and validated through experiment data. Parameters of models of phosphorus-remove catalyst and sulfur-remove catalyst were attained through fitting of experiment data. When they were used to forecast the outlet concentration, the relativity coefficients were 0.99354 and 0.99136 for PH_3 and H_2S respectively. Model of phosphorus-sulfur-remove catalyst was solved numerically. When it was used to forecast outlet concentration, the relativity coefficients were 0.9976 and 0.9919 for PH_3 and H_2S respectively.
首先，通过载体选择实验、催化剂制备实验、基础实验和优化实验得到了脱磷、脱硫和脱磷硫三种催化剂评估了催化净化的影响因素，并通过再生实验评价了催化剂再生效果。载体选择实验表明，ZP-4活性炭对PH_3和H_2S吸附效果较好，确定ZP-4活性炭为催化剂载体。催化剂制备实验表明，碳酸钠，醋酸铜和盐酸浸渍得到的催化剂，PH_3和H_2S的净化效果可以显著提高；选择盐酸为脱磷催化剂的浸渍液，碳酸钠为脱硫催化剂的浸渍液，醋酸铜为脱磷硫催化剂的浸渍液。基础实验表明，脱磷催化剂净化PH_3时，较合适的盐酸浓度是5％；无氧时为物理吸附，较合适吸附反应温度为20℃，有氧时因化学反应吸附容量提高较大，较合适反应温度为70℃；较合适氧含量为1％。基础实验同时表明，脱硫催化剂净化H_2S时，较合适的碳酸钠浓度是7％；较合适氧含量为0.4％；随着温度的增加脱硫催化剂净化H_2S的效果逐步提高，较合适反应温度为90℃。优化实验表明，脱磷硫催化剂净化PH3时，影响因素的重要性顺序依次为反应温度，氧含量，焙烧温度，浸渍液浓度，气体流量和粒径；实验范围内影响因素的最佳值分别为反应温度95℃，浸渍液浓度0.3 mol／L，粒径3.5 mm，氧含量1％，焙烧温度300℃和气体流量0.4 L／min。优化实验同时表明，脱磷硫催化剂净化H_2S时，影响因素的重要性顺序依次为反应温度，氧含量，浸渍液浓度，焙烧温度，粒径气体和流量；实验范围内影响因素的最佳值分别为反应温度95℃，浸渍液浓度0.3 mol／L，粒径3.5 mm，氧含量1％，焙烧温度300℃和气体流量0.4 L／min。再生试验表明，再生基本可行；再生方案对含磷物质的再生效果比较好，同时再生液中磷酸含量达0.877mg／L，可回收其中的磷酸；再生方案对含硫杂质的再生不甚理想，同时再生液中硫磺回收过程比较复杂，有待于进一步研究。
接着，通过动力学实验得到了三种催化剂的动力学参数，并评估了内外扩散对催化净化的影响。动力学实验表明，用脱硫催化剂净化H_2S时，平均反应级数为—1，反应的平均活化能为23.77kJ／mol；用脱磷催化剂净化PH_3时，平均反应级数为—2，反应的平均活化能为61.3kJ／mol；用脱磷硫催化剂净化PH_3和H_2S时，平均反应级数分别为-0.8和-0.76，反应的平均活化能分别为1247.6 J／mol和134.4 J／mol。活化能数值初步证明了催化剂净化黄磷尾气是一个化学反应过程。内外扩散过程对反应过程都有重要影响，减小催化剂粒径增加空速可以显著提高脱磷硫催化剂净化PH_3和H_2S的平均反应速率。
然后，通过现场实验用江磷集团的黄磷尾气对催化剂进行了现场评价，并通过催化剂表征得到了催化剂催化氧化净化黄磷尾气的反应机理。现场实验表明，用脱硫催化剂净化黄磷尾气时，200分钟内各种杂质总含量都低于10mg／Nm~3；脱硫催化剂对H_2S的选择性较好。现场实验同时表明，脱磷硫催化剂净化黄磷尾气时，300分钟内各种杂质总含量都低于10mg／Nm~3；脱磷硫催化剂对H_2S和PH_3的选择性较好。孔径分布分析、热重差热分析和扫描电镜分析，可以初步认为脱硫催化剂和脱磷催化剂净化H_2S和PH_3时，H_2S和PH_3首先与氧在催化剂表面进行催化氧化反应生成硫或硫氧化物和磷或磷氧化物，然后沉积吸附在催化剂表面。X射线光电子能谱分析、热重差热分析和孔径分布分析，可以认为脱磷硫催化剂净化H_2S和PH_3时，H_2S和PH_3首先与氧在催化剂表面进行催化氧化反应生成S和P_2O_5，然后沉积吸附在催化剂表面。
最后，根据反应机理推导得到三种催化剂的催化净化模型，并用实验数据对模型进行了验证。拟合得到脱磷催化剂和脱硫催化剂模型的参数，其预测PH_3或H_2S的穿透曲线时，相关系数分别可以达到0.99354和0.99136；通过数值计算求解脱磷硫催化剂模型，其预测PH_3或H_2S的穿透曲线时，相关系数分别可以达到0.9976和0.9919。
This thesis is about research and discussion of purification of yellow phosphorus off-gas at low temperature and low oxygen content.
Firstly, experiments were conducted to select carrier of catalyst, to assess the efficiency of catalyst regeneration, and the influencing factors which were related with purification of yellow phosphorus off-gas. Activated carbon was an efficient adsorbent for both PH_3 and H_2S, and therefore chosen as carrier of catalyst. HCl, Na_2CO_3 and CuAc_2 were selected to be used as impregnants for phosphorus-remove catalyst, sulfur-remove catalyst and phosphorus-sulfur-remove catalyst respectively. When phosphorus-remove catalyst was used to remove PH3, it was 5% and 1% (vol%) for the appropriate concentration of HC1 and oxygen content respectively; and it was physic adsorption in anoxic atmosphere with 20℃ as appropriate temperature, and chemical reaction and adsorption in aerobic atmosphere with 70 ℃ as appropriate temperature. When sulfur-remove catalyst was used to remove H_2S, it was 7%, 0.4% (vol%) and 90℃ for the appropriate concentration of Na_2CO_3, oxygen content and reaction temperature respectively; the higher the temperature was the higher the removal efficiency was. When phosphorus-sulfur-remove catalyst was used to remove PH_3 and H_2S, for PH3 the superiority order was temperature > oxygen content > parch temperature > impregnant concentration (Cu~(2+)) > flow rate > diameter while for H_2S it was reaction temperature > oxygen content > impregnant concentration > parch temperature > diameter > flow rate. And the optimum experiment parameters for both PH_3 and H_2S were reaction temperature, 95℃; impregnant concentration (Cu~(2+)), 0.25 mol/L; diameter of catalyst, 3.5 mm; oxygen content, 1%; parch temperature, 300 ℃ and flow rate, 0.4 L/min. Regeneration of phosphorus-sulfur-remove catalyst was effective for PH_3 but not compelling for H_2S.
Secondly, experiments were carried out to acquire thermodynamic parameters and to assess the influence of internal and external diffusion on removal efficiency. When sulfur-remove catalyst was used to remove H_2S, it was -1 and 23.77kJ/mol for the average reaction order and average activation energy. When phosphorus-remove catalyst was used to remove PH_3, it was -2 and 61.3kJ/mol for the average reaction order and average
activation energy. When phosphorus-sulfur-remove catalyst was used to remove PH_3 and H_2S, reaction orders were -0.8 and -0.76 for PH_3 and H_2S respectively; and average activation energies were 1247.6 J/mol and 134.4 J/mol for PH_3 and H_2S respectively. Purification of yellow phosphorus off-gas could be primarily identified as a chemical process through these values of activation energies. Decrease of diameter of catalyst and increase of flow rate could dramatically increase the average reaction rate.
Thirdly, onsite experiments were conducted to investigate the practical purifying efficiency of catalyst on phosphorus off-gas in Jianglin Corporation; and SEM, TG/DTA, BET adsorption and XPS were used to characterize the performance of catalysts and to illustrate the reaction mechanism. When sulfur-remove catalyst was used to purify phosphorus off-gas, total impurity content was lower than 10mg/Nm~3 in 200 minutes with better selectivity on H_2S. When phosphorus-sulfur-remove catalyst was used to purify phosphorus off-gas, total impurity content was lower than 10mg/Nm~3 in 300 minutes with better selectivity on H_2S and PH_3. Analysis of pore size distribution, TG/DTA and SEM primarily indicates that, during purification, H_2S and PH_3 were firstly reacted with oxygen to produce sulfur and sulfur oxides or phosphorus and phosphorus oxides, and then adsorbed on sulfur-remove catalyst or phosphorus-remove catalyst. Analysis of XPS, TG/DTA and pore size distribution indicates that, during purification, H_2S and PH_3 were firstly reacted with oxygen to produce S and P_2O_5, and then adsorbed on phosphorus-sulfur-remove catalyst.
Finally, models were established according to reaction mechanism, and calibrated and validated through experiment data. Parameters of models of phosphorus-remove catalyst and sulfur-remove catalyst were attained through fitting of experiment data. When they were used to forecast the outlet concentration, the relativity coefficients were 0.99354 and 0.99136 for PH_3 and H_2S respectively. Model of phosphorus-sulfur-remove catalyst was solved numerically. When it was used to forecast outlet concentration, the relativity coefficients were 0.9976 and 0.9919 for PH_3 and H_2S respectively.
引文
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