碱式醋酸铜前体法铜锰复合氧化物催化剂的控制合成
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摘要
本文以醋酸铜为原料,氢氧化钠为沉淀剂,采用共沉淀法和水热法合成碱式醋酸铜(Cu_2(OH)_3(OCOCH_3)·H_2O),并以碱式醋酸铜为前驱体,用高锰酸钾进行离子交换制备铜锰复合氧化物。利用XRD、TG-DTA、SEM、TEM、TPR、低温氮气吸脱附、微反色谱等表征测试手段对碱式醋酸铜及离子交换产物的织构进行了研究,着重考察了M[OH~-]/M[Cu~(2+)]对碱式醋酸铜制备过程的影响以及焙烧温度对铜锰复合氧化物织构和催化活性的影响。
碱式醋酸铜合成的研究结果表明,碱量是影响碱式醋酸铜结构生成的关键因素,当M[OH~-]/M[Cu~(2+)]=0.8～1.7,滴定终点pH值在6.29～7.33之间时,能够制得碱式醋酸铜,且M[OH~-]/M[Cu~(2+)]=1.2时,碱式醋酸铜晶型最好,衍射峰强度最高。SEM扫描电镜研究结果表明,碱式醋酸铜是一种粒径约7μm的圆形颗粒,这种颗粒是由多层碱式醋酸铜层板堆积而成,其形状呈卷心菜状。
铜锰复合氧化物制备的研究结果表明,焙烧温度对碱式高锰酸铜的织构有很大的影响,XRD和TG-DTA表明400℃焙烧温度后铜锰复合氧化物的主晶相为CuO , 600℃和800℃焙烧温度后铜锰复合氧化物的主晶相为CuO和CuMn_2O_4 ,随着焙烧温度升高, 1000℃焙烧温度后铜锰复合氧化物的主晶相为CuO和Cu_2O。TPR研究结果表明,随着焙烧温度的升高,还原温度向高温区移动。活性测试结果表明,焙烧温度对铜锰复合氧化物的活性有较大影响,1000℃焙烧后样品的活性在300℃能达到82%。
In this paper, basic copper acetate (Cu_2(OH)_3(OCOCH_3)·H_2O) was prepared by the co-precipitation method and hydrothermal method ,which based upon copper acetate was the raw material and sodium hydroxide was the precipitating agent, and then the ion-exchange method was used to the preparation of Cu-Mn Based catalyst with basic copper acetate as precursor. The synthesized samples were characterized by XRD, TG-DTA, SEM, TEM, H2-TPR , low temperature nitrogen absorption and Micro-Reactor-Chromatography. The effect of prepared of basic copper acetate was M[OH~-]/M[Cu~(2+)] molar ratios and the effect of texture and catalytic activity of copper manganese oxide was the calcinations temperature.
The study of synthesis of basic copper acetate showed that the crystallizations of basic copper acetate structure could be affecting on M[OH~-]/M[Cu~(2+)] molar ratios. At M [OH~-] / M [Cu~(2+)] = 0.8~1.7 and pH = 6.29~7.33, basic copper acetate could be obtained, and M[OH~-] / M [Cu(~2+)] = 1.2, the crystallizations of basic copper acetate was best. The results of Scanning Electron Microscopy showed that basic copper acetate was a rounded particle size about 7μm , and this particle was made up of stacked layers that was made of basic copper acetate and were cabbage-like.
The study of synthesis of Copper manganese oxide showed that the influence of baking temperature to the copper manganese oxide was considerable. The results of XRD and TG-DTA showed that the main crystal phase of Copper manganese oxide was CuO at baking temperature of 400℃and CuO and CuMn_2O_4 at baking temperatures of 600℃and 800℃, and then main crystal phase of Copper manganese oxide were CuO and Cu_2O at baking temperature of 400℃. The results of TPR showed that with the baking temperature increased, combination of Cu-Mn became stronger and reduction temperature moved in the high temperature zone. The results of activity tests showed that the influence of the high baking temperature to the activity of alkaline manganese was considerable, the activity of copper manganese oxide at baking temperature of 1000℃was the best and its activity attained to 82% at reaction temperature of 300℃
碱式醋酸铜合成的研究结果表明,碱量是影响碱式醋酸铜结构生成的关键因素,当M[OH~-]/M[Cu~(2+)]=0.8～1.7,滴定终点pH值在6.29～7.33之间时,能够制得碱式醋酸铜,且M[OH~-]/M[Cu~(2+)]=1.2时,碱式醋酸铜晶型最好,衍射峰强度最高。SEM扫描电镜研究结果表明,碱式醋酸铜是一种粒径约7μm的圆形颗粒,这种颗粒是由多层碱式醋酸铜层板堆积而成,其形状呈卷心菜状。
铜锰复合氧化物制备的研究结果表明,焙烧温度对碱式高锰酸铜的织构有很大的影响,XRD和TG-DTA表明400℃焙烧温度后铜锰复合氧化物的主晶相为CuO , 600℃和800℃焙烧温度后铜锰复合氧化物的主晶相为CuO和CuMn_2O_4 ,随着焙烧温度升高, 1000℃焙烧温度后铜锰复合氧化物的主晶相为CuO和Cu_2O。TPR研究结果表明,随着焙烧温度的升高,还原温度向高温区移动。活性测试结果表明,焙烧温度对铜锰复合氧化物的活性有较大影响,1000℃焙烧后样品的活性在300℃能达到82%。
In this paper, basic copper acetate (Cu_2(OH)_3(OCOCH_3)·H_2O) was prepared by the co-precipitation method and hydrothermal method ,which based upon copper acetate was the raw material and sodium hydroxide was the precipitating agent, and then the ion-exchange method was used to the preparation of Cu-Mn Based catalyst with basic copper acetate as precursor. The synthesized samples were characterized by XRD, TG-DTA, SEM, TEM, H2-TPR , low temperature nitrogen absorption and Micro-Reactor-Chromatography. The effect of prepared of basic copper acetate was M[OH~-]/M[Cu~(2+)] molar ratios and the effect of texture and catalytic activity of copper manganese oxide was the calcinations temperature.
The study of synthesis of basic copper acetate showed that the crystallizations of basic copper acetate structure could be affecting on M[OH~-]/M[Cu~(2+)] molar ratios. At M [OH~-] / M [Cu~(2+)] = 0.8~1.7 and pH = 6.29~7.33, basic copper acetate could be obtained, and M[OH~-] / M [Cu(~2+)] = 1.2, the crystallizations of basic copper acetate was best. The results of Scanning Electron Microscopy showed that basic copper acetate was a rounded particle size about 7μm , and this particle was made up of stacked layers that was made of basic copper acetate and were cabbage-like.
The study of synthesis of Copper manganese oxide showed that the influence of baking temperature to the copper manganese oxide was considerable. The results of XRD and TG-DTA showed that the main crystal phase of Copper manganese oxide was CuO at baking temperature of 400℃and CuO and CuMn_2O_4 at baking temperatures of 600℃and 800℃, and then main crystal phase of Copper manganese oxide were CuO and Cu_2O at baking temperature of 400℃. The results of TPR showed that with the baking temperature increased, combination of Cu-Mn became stronger and reduction temperature moved in the high temperature zone. The results of activity tests showed that the influence of the high baking temperature to the activity of alkaline manganese was considerable, the activity of copper manganese oxide at baking temperature of 1000℃was the best and its activity attained to 82% at reaction temperature of 300℃
引文
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