活性炭吸附催化氧化法处理低浓度H_2S研究
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摘要
本文针对炼油厂停工检修阶段恶臭污染现状,利用活性炭吸附催化氧化技术对实验室模拟含H_2S恶臭气体的治理进行了初步研究。
通过实验考察了活性炭纤维和不同来源活性炭的穿透行为,利用KOH、NaOH、Na_2CO_3等碱性物质和FeCl_3、CuCl_2、Cu(NO_3)_2等过渡金属化合物对活性炭进行浸渍改性并对比了改性效果,通过Cu(NO_3)_2和HNO_3联合改性制备了优良的脱硫剂,考察了活化温度、床层高度、预浸湿、反应温度、空速、O_2、H_2S浓度等因素对脱除H_2S的影响,通过Boehm滴定、表面pH测定、XRD、XPS、元素分析等手段对活性炭进行了表征,对生成产物和反应机理进行了探讨。
试验结果表明:不同形式和来源的活性炭脱H_2S效果不同,颗粒尺寸越小吸附H_2S性能越好,木质和果壳活性炭脱H_2S性能高于煤质活性炭;7%Na_2CO_3浸渍可显著提高粘胶基活性炭纤维穿透性能,900℃热处理后活性炭纤维穿透时间增长至220min以上;经2%KI浸渍改性后,SDA-1的穿透时间从近300min增加到1040min;浸渍负载Cu改性SDA-5效果明显,10%Cu(NO_3)_2改性SDA-5的穿透时间是未改性的8倍;H_2S平均入口浓度为2277 mg/m~3时8%Cu(NO_3)_2和HNO_3联合改性SDA-5的穿透性能是未加Cu(NO_3)_2改性活性炭的13.5倍。浸渍CuCl_2活性炭吸附H_2S后有单质硫生成,可能是铜催化活化氧使H_2S被氧化,当生成的硫阻塞了微孔后反应停止。Cu(NO_3)_2对于不同活性炭的改性效果是相同的,与活性炭的来源没有关系。浸渍后铜主要以CuO的形式固定在活性炭上,H_2S与CuO反应生成CuS使催化剂失活。经600℃活化的负载Cu(NO_3)_2活性炭穿透性能较差,原因是改性后的活性炭热稳定性差。Cu(NO_3)_2和HNO_3联合改性改变了活性炭的孔径分布和表面化学环境,H_2S全部生成了单质S和硫的氧化物。随着活性炭床层高度增加,空速减小,H_2S入口浓度降低,穿透时间增大,硫容量提高;SDA-5加水量为1.0mL水/g时穿透时间最长;改性后活性炭无O_2时的穿透时间约为有O_2时的1/10。
In order to alleviate the odour pollution of oil refining plants at downtime, the study of removal of lab simulated H_2S containing malodor gas by adsorption/ catalytic oxidation by activated carbon were progressed.
The breakthrough behaviors of ACF and other activated carbons of different origins were investigated in the laboratory experiment. The carbons modified with alkali like KOH, NaOH, Na_2CO_3 and transitional metal compounds like FeCl_3, CuCl_2, Cu(NO_3)_2 were used to adsorb H_2S. It was found that carbon samples impregnated by Cu(NO_3)_2 and HNO_3 had very excellent capacity. Influence of activation temperature, bed height, prehumidification, reaction temperature, vacancy velocity, O_2, concentration of inlet H_2S on removal of H_2S was studied. The surface properties were evaluated by means of Boehm titration, surface pH measuration, XRD( X-ray diffraction), XPS( X-ray photoelectron spectroscopy) and element analysis. The reaction product and mechanism was also discussed.
The results of lab experiments showed that the capacity of carbons of different forms and origins differ from each other, the smaller the particle size, the better the performance. The wooden-based and fruit-shell activated carbons performed better than the coal-based carbon. The breakthrough capacity of viscose-based activated carbon fiber was notable enlarged by modified with 7%Na_2CO_3. The breakthrough time of ACF rose to 220 min after heat treatment under 900℃. It was demonstrated that SDA-1 samples had a breakthrough time of 1040 min after impregnated with 2%KI when 300 min before modified. SDA-5 loaded with Cu had such a good performance that the breakthrough time of carbon impregnated with 10%Cu(NO_3)_2 was 8 times that unmodified. It was found that the breakthrough capacity of SDA-5 modified with 8%Cu(NO_3)_2 and HNO_3 was 13.5 times that hadn’t been impregnated in Cu(NO_3)_2 when the average inlet concentration of H_2S was 2277 mg/m~3 . It was found that O_2 was activated by copper and H_2S was oxidized to sulfur, but the reaction stopped when micropores were blocked by sulfur. The effect of Cu(NO_3)_2 modification was the same with activated carbons of different origins. Copper was fixed in the form of CuO on the activated carbon, and the catalyst deactivated after reacting with H_2S and CuS was created. The breakthrough performance of activated carbon impregnated by Cu(NO_3)_2 decreased after activation at 600℃because the thermal stability reduced after impregnation. The distribution of pore dimension and surface chemistry had changed after modified with Cu(NO_3)_2 and HNO_3, and sulfur and oxides of sulfur formatted. It was showed that the breakthrough time augmented as the bed height rose, but reduced when vacancy velocity and inlet H_2S concentration increased. SDA-5 sample had a longest breakthrough time as the volume of water added to carbon was 1.0mL/g. The breakthrough time of modified carbons in inlet gas of H_2S + N_2 was about 1/10 that inlet gas containing O_2.
通过实验考察了活性炭纤维和不同来源活性炭的穿透行为,利用KOH、NaOH、Na_2CO_3等碱性物质和FeCl_3、CuCl_2、Cu(NO_3)_2等过渡金属化合物对活性炭进行浸渍改性并对比了改性效果,通过Cu(NO_3)_2和HNO_3联合改性制备了优良的脱硫剂,考察了活化温度、床层高度、预浸湿、反应温度、空速、O_2、H_2S浓度等因素对脱除H_2S的影响,通过Boehm滴定、表面pH测定、XRD、XPS、元素分析等手段对活性炭进行了表征,对生成产物和反应机理进行了探讨。
试验结果表明:不同形式和来源的活性炭脱H_2S效果不同,颗粒尺寸越小吸附H_2S性能越好,木质和果壳活性炭脱H_2S性能高于煤质活性炭;7%Na_2CO_3浸渍可显著提高粘胶基活性炭纤维穿透性能,900℃热处理后活性炭纤维穿透时间增长至220min以上;经2%KI浸渍改性后,SDA-1的穿透时间从近300min增加到1040min;浸渍负载Cu改性SDA-5效果明显,10%Cu(NO_3)_2改性SDA-5的穿透时间是未改性的8倍;H_2S平均入口浓度为2277 mg/m~3时8%Cu(NO_3)_2和HNO_3联合改性SDA-5的穿透性能是未加Cu(NO_3)_2改性活性炭的13.5倍。浸渍CuCl_2活性炭吸附H_2S后有单质硫生成,可能是铜催化活化氧使H_2S被氧化,当生成的硫阻塞了微孔后反应停止。Cu(NO_3)_2对于不同活性炭的改性效果是相同的,与活性炭的来源没有关系。浸渍后铜主要以CuO的形式固定在活性炭上,H_2S与CuO反应生成CuS使催化剂失活。经600℃活化的负载Cu(NO_3)_2活性炭穿透性能较差,原因是改性后的活性炭热稳定性差。Cu(NO_3)_2和HNO_3联合改性改变了活性炭的孔径分布和表面化学环境,H_2S全部生成了单质S和硫的氧化物。随着活性炭床层高度增加,空速减小,H_2S入口浓度降低,穿透时间增大,硫容量提高;SDA-5加水量为1.0mL水/g时穿透时间最长;改性后活性炭无O_2时的穿透时间约为有O_2时的1/10。
In order to alleviate the odour pollution of oil refining plants at downtime, the study of removal of lab simulated H_2S containing malodor gas by adsorption/ catalytic oxidation by activated carbon were progressed.
The breakthrough behaviors of ACF and other activated carbons of different origins were investigated in the laboratory experiment. The carbons modified with alkali like KOH, NaOH, Na_2CO_3 and transitional metal compounds like FeCl_3, CuCl_2, Cu(NO_3)_2 were used to adsorb H_2S. It was found that carbon samples impregnated by Cu(NO_3)_2 and HNO_3 had very excellent capacity. Influence of activation temperature, bed height, prehumidification, reaction temperature, vacancy velocity, O_2, concentration of inlet H_2S on removal of H_2S was studied. The surface properties were evaluated by means of Boehm titration, surface pH measuration, XRD( X-ray diffraction), XPS( X-ray photoelectron spectroscopy) and element analysis. The reaction product and mechanism was also discussed.
The results of lab experiments showed that the capacity of carbons of different forms and origins differ from each other, the smaller the particle size, the better the performance. The wooden-based and fruit-shell activated carbons performed better than the coal-based carbon. The breakthrough capacity of viscose-based activated carbon fiber was notable enlarged by modified with 7%Na_2CO_3. The breakthrough time of ACF rose to 220 min after heat treatment under 900℃. It was demonstrated that SDA-1 samples had a breakthrough time of 1040 min after impregnated with 2%KI when 300 min before modified. SDA-5 loaded with Cu had such a good performance that the breakthrough time of carbon impregnated with 10%Cu(NO_3)_2 was 8 times that unmodified. It was found that the breakthrough capacity of SDA-5 modified with 8%Cu(NO_3)_2 and HNO_3 was 13.5 times that hadn’t been impregnated in Cu(NO_3)_2 when the average inlet concentration of H_2S was 2277 mg/m~3 . It was found that O_2 was activated by copper and H_2S was oxidized to sulfur, but the reaction stopped when micropores were blocked by sulfur. The effect of Cu(NO_3)_2 modification was the same with activated carbons of different origins. Copper was fixed in the form of CuO on the activated carbon, and the catalyst deactivated after reacting with H_2S and CuS was created. The breakthrough performance of activated carbon impregnated by Cu(NO_3)_2 decreased after activation at 600℃because the thermal stability reduced after impregnation. The distribution of pore dimension and surface chemistry had changed after modified with Cu(NO_3)_2 and HNO_3, and sulfur and oxides of sulfur formatted. It was showed that the breakthrough time augmented as the bed height rose, but reduced when vacancy velocity and inlet H_2S concentration increased. SDA-5 sample had a longest breakthrough time as the volume of water added to carbon was 1.0mL/g. The breakthrough time of modified carbons in inlet gas of H_2S + N_2 was about 1/10 that inlet gas containing O_2.
引文
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