吸附法净化泥磷制取次磷酸钠尾气中PH_3的研究
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摘要
磷化工行业在云南省的工业组成中占有举足轻重的地位,其中黄磷作为重要的基础原料是整个磷化工行业最主要的创汇产品。但无论采用何种方法,在黄磷的生产过程中均会产生诸如废水、废气以及废渣的污染物。以泥磷为代表的黄磷生产废渣,由于其产生量大、污染相对严重,成为环境治理的首要目标。目前处理泥磷的方法有很多种,包括电炉制磷系统自身回收、直接法和间接法提取黄磷等。结合上述处理方法的不足,从可持续发展的角度出发,将泥磷高效地转化为次磷酸钠是一种有效的综合利用途径。次磷酸钠具有很高的经济附加值,广泛应用于化学镀、电镀等多个行业。但是根据发生的反应进行物料衡算发现,约有20%的磷单质以磷化氢(PH3)的形式进入尾气后排出,引起大气污染。考虑到目前国内外磷化氢生产的空白局面、泥磷中磷元素综合回收利用率的提高以及环境保护等诸多方面的因素,需要寻求一种方法使得次磷酸钠反应尾气中的磷化氢气体得以回收利用。
本文重点研究了改性吸附剂5A分子筛吸附净化次磷酸钠反应尾气中磷化氢的吸附性能和吸附机理,将吸附效率和吸附剂的稳定性作为评判吸附剂吸附效果的依据。首先筛选了适宜的吸附剂种类和改性剂的活性组分；在活性组分确定的前提下对吸附剂吸附PH3气体做单因素实验,分别考察了浸渍液浓度、干燥温度、焙烧温度、气体流速以及反应温度等条件对吸附剂吸附磷化氢的影响规律,研究吸附剂的吸附性能；随后对改性吸附剂做正交优化实验,确定各影响因素交互作用下最适宜的实验条件；接着对吸附剂的再生进行考查,确定最适宜的再生方法和再生效果；利用吸附剂的吸附穿透曲线计算吸附速率,初步判断吸附类型；最后用扫描电镜(SEM)、光电子能谱(XPS)技术对吸附剂进行表征,为机理研究提供依据；最后通过基础实验数据、表征结果共同研究吸附剂的吸附机理,验证吸附剂的吸附性能。
研究最终选用5A分子筛作为吸附净化磷化氢气体的适宜吸附剂；洗气液选用85%的浓磷酸；吸附剂的浸渍溶液为NaCl,活性组分为Na+；吸附阶段单因素实验中最适宜的实验条件为：浸渍液浓度0.3mol.L-1、干燥温度110℃、焙烧温度300℃、载气流速20mL.min-1、吸附反应温度为常温(20℃左右)：吸附阶段设计的正交优化实验结果与单因素实验结果一致,各因素的影响程度为：吸附温度>载气流速>浸渍液浓度>焙烧温度>干燥温度：解吸方式选用氮气吹扫和加热的方法进行；解吸阶段单因素实验中最适宜的实验条件为：载气流速40mL.min-1、解吸反应温度为60℃；吸附剂再生采用高温水洗和热空气干燥的方法进行,最终能够实现吸附剂的重复利用,减少对环境的二次污染和资源的浪费。
由磷化氢的吸附穿透曲线,计算得到各个温度条件下吸附剂改性5A分子筛吸附磷化氢的速率常数,从而判断吸附反应的剧烈程度,初步推断该吸附过程为物理吸附。吸附剂样品的SEM表征结果证实了吸附剂表面、内部在吸附前后发生的变化,利用前期的实验和计算数据、表征结果初步推断吸附剂吸附磷化氢的净化机理为微孔填充；通过对吸附剂进行XPS表征,明确了吸附剂活性组分为Na+,用电子得失理论解释了吸附及解吸过程,并结合吸附机理、吸附前后气体成分和吸附剂物理化学性质的变化,初步推断PH3在吸附剂上可能是以气态分子的形式存在。整个吸附、解吸过程可逆,为微孔填充属于物理吸附。
经实验研究,获得了具有较高吸附性能的吸附剂,在常温、常压状态下即可对含磷化氢混合气进行吸附净化。用NaCl改性过后的5A分子筛具有稳定性强、活性高、易再生、价格低廉等优良性能,是一种值得进一步开发的吸附剂。
The phosphorous chemical industry held the very important status in Yunnan province's industrial composition, and yellow phosphorous was the main export products as well as the key raw material of the chemical industry. But whatever the method used, the pollutants would be generated, such as waste water, waste gas and solid waste. Phosphorus sludge was one of the harmful solid waste because of its pyrophorisity, so it was necessary to deal with it. Using phosphorus sludge to get sodium hypophosphite proved to be an effective way. Sodium hypophosphite had the considerable economical value, was widely used in chemical plating, galvanization and so on. But in this technology, almost 20% element P4 changed to be PH3, and caused new air pollution. Considered the present situation of phosphine production, the total recycling rate of phosphorus sludge and environmental protection etc., it was essential to recycle the phosphine gas from the production technology of sodium hypophosphite.
This thesis aimed to research the adsorption of phosphine. The stability of the adsorbent and adsorption effect were as the basis. This paper selected the suitable adsorbent type and impregnant of active components. When the active components was fixed, the concentration of impregnant, the temperature of roasting and drying, the flow rate of N2 and the reaction temperature were researched as the affect factors in order to get the suitable experimental conditions. Then used the orthogonal experiment to verify the optimum experimental conditions, and researched the regeneration of adsorbents, determined the most suitable regeneration method and regeneration effect. After that, calculated the adsorption rate and judged the type of adsorption. Finally, used SEM, XPS and the experimental data to research the basic mechanism of the adsorption.
5A molecular sieve was selected to be the suitable adsorbent. The impregnants was prepared by NaCl and active component was Na+. The optimum parameters of single factor experiment of adsorption were impregnant concentration 0.3mol.L-1、drying temperature 110℃、roasting temperature 300℃、the flow rate of N2 20mL.min-1 and the reaction temperature 20℃. The result of orthogonal experiment was as same as the single factor experiment, and the superiority order was reaction temperature> flow rate> impregnant concentration> roasting temperature> drying temperature. Nitrogen purging and heating were selected to be the desorption mode. The optimum experimental conditions of single factor of desorption were the flow rate of N240mL.min-1 and reaction temperature 60℃The regeneration of adsorbents were dealing by hot water and then drying by hot air, and finally realized the repeated use of 5A molecular sieve and reduced the environmental pollution.
Through the adsorption penetration curve of phosphine, obtained the adsorption rate of phosphine under the different temperatures, then judged the acuteness degree of adsorption, and deduced that the adsorption processes was physical. After used scanning electron microscopy (SEM), surface characterization and inner changes of adsorbents were got. And through XPS, the types and contents of active component was Na+. With the adsorption mechanism, gas composition and the chemical and physical properties of the changes on adsorbents, deduced that the adsorbate was phosphine on the adsorbents. The adsorption and desorption process were reversible for pore filling, belonged to the physical adsorption.
This research got the idealfor adsorbent which had high adsorption performance at room temperature and normal atmosphere. After the modification by NaCl,5A molecular sieve had strong stability, high activity, and it was also low price and easy to regenerate, so it was a very worthy of further development of the adsorbent.
本文重点研究了改性吸附剂5A分子筛吸附净化次磷酸钠反应尾气中磷化氢的吸附性能和吸附机理,将吸附效率和吸附剂的稳定性作为评判吸附剂吸附效果的依据。首先筛选了适宜的吸附剂种类和改性剂的活性组分；在活性组分确定的前提下对吸附剂吸附PH3气体做单因素实验,分别考察了浸渍液浓度、干燥温度、焙烧温度、气体流速以及反应温度等条件对吸附剂吸附磷化氢的影响规律,研究吸附剂的吸附性能；随后对改性吸附剂做正交优化实验,确定各影响因素交互作用下最适宜的实验条件；接着对吸附剂的再生进行考查,确定最适宜的再生方法和再生效果；利用吸附剂的吸附穿透曲线计算吸附速率,初步判断吸附类型；最后用扫描电镜(SEM)、光电子能谱(XPS)技术对吸附剂进行表征,为机理研究提供依据；最后通过基础实验数据、表征结果共同研究吸附剂的吸附机理,验证吸附剂的吸附性能。
研究最终选用5A分子筛作为吸附净化磷化氢气体的适宜吸附剂；洗气液选用85%的浓磷酸；吸附剂的浸渍溶液为NaCl,活性组分为Na+；吸附阶段单因素实验中最适宜的实验条件为：浸渍液浓度0.3mol.L-1、干燥温度110℃、焙烧温度300℃、载气流速20mL.min-1、吸附反应温度为常温(20℃左右)：吸附阶段设计的正交优化实验结果与单因素实验结果一致,各因素的影响程度为：吸附温度>载气流速>浸渍液浓度>焙烧温度>干燥温度：解吸方式选用氮气吹扫和加热的方法进行；解吸阶段单因素实验中最适宜的实验条件为：载气流速40mL.min-1、解吸反应温度为60℃；吸附剂再生采用高温水洗和热空气干燥的方法进行,最终能够实现吸附剂的重复利用,减少对环境的二次污染和资源的浪费。
由磷化氢的吸附穿透曲线,计算得到各个温度条件下吸附剂改性5A分子筛吸附磷化氢的速率常数,从而判断吸附反应的剧烈程度,初步推断该吸附过程为物理吸附。吸附剂样品的SEM表征结果证实了吸附剂表面、内部在吸附前后发生的变化,利用前期的实验和计算数据、表征结果初步推断吸附剂吸附磷化氢的净化机理为微孔填充；通过对吸附剂进行XPS表征,明确了吸附剂活性组分为Na+,用电子得失理论解释了吸附及解吸过程,并结合吸附机理、吸附前后气体成分和吸附剂物理化学性质的变化,初步推断PH3在吸附剂上可能是以气态分子的形式存在。整个吸附、解吸过程可逆,为微孔填充属于物理吸附。
经实验研究,获得了具有较高吸附性能的吸附剂,在常温、常压状态下即可对含磷化氢混合气进行吸附净化。用NaCl改性过后的5A分子筛具有稳定性强、活性高、易再生、价格低廉等优良性能,是一种值得进一步开发的吸附剂。
The phosphorous chemical industry held the very important status in Yunnan province's industrial composition, and yellow phosphorous was the main export products as well as the key raw material of the chemical industry. But whatever the method used, the pollutants would be generated, such as waste water, waste gas and solid waste. Phosphorus sludge was one of the harmful solid waste because of its pyrophorisity, so it was necessary to deal with it. Using phosphorus sludge to get sodium hypophosphite proved to be an effective way. Sodium hypophosphite had the considerable economical value, was widely used in chemical plating, galvanization and so on. But in this technology, almost 20% element P4 changed to be PH3, and caused new air pollution. Considered the present situation of phosphine production, the total recycling rate of phosphorus sludge and environmental protection etc., it was essential to recycle the phosphine gas from the production technology of sodium hypophosphite.
This thesis aimed to research the adsorption of phosphine. The stability of the adsorbent and adsorption effect were as the basis. This paper selected the suitable adsorbent type and impregnant of active components. When the active components was fixed, the concentration of impregnant, the temperature of roasting and drying, the flow rate of N2 and the reaction temperature were researched as the affect factors in order to get the suitable experimental conditions. Then used the orthogonal experiment to verify the optimum experimental conditions, and researched the regeneration of adsorbents, determined the most suitable regeneration method and regeneration effect. After that, calculated the adsorption rate and judged the type of adsorption. Finally, used SEM, XPS and the experimental data to research the basic mechanism of the adsorption.
5A molecular sieve was selected to be the suitable adsorbent. The impregnants was prepared by NaCl and active component was Na+. The optimum parameters of single factor experiment of adsorption were impregnant concentration 0.3mol.L-1、drying temperature 110℃、roasting temperature 300℃、the flow rate of N2 20mL.min-1 and the reaction temperature 20℃. The result of orthogonal experiment was as same as the single factor experiment, and the superiority order was reaction temperature> flow rate> impregnant concentration> roasting temperature> drying temperature. Nitrogen purging and heating were selected to be the desorption mode. The optimum experimental conditions of single factor of desorption were the flow rate of N240mL.min-1 and reaction temperature 60℃The regeneration of adsorbents were dealing by hot water and then drying by hot air, and finally realized the repeated use of 5A molecular sieve and reduced the environmental pollution.
Through the adsorption penetration curve of phosphine, obtained the adsorption rate of phosphine under the different temperatures, then judged the acuteness degree of adsorption, and deduced that the adsorption processes was physical. After used scanning electron microscopy (SEM), surface characterization and inner changes of adsorbents were got. And through XPS, the types and contents of active component was Na+. With the adsorption mechanism, gas composition and the chemical and physical properties of the changes on adsorbents, deduced that the adsorbate was phosphine on the adsorbents. The adsorption and desorption process were reversible for pore filling, belonged to the physical adsorption.
This research got the idealfor adsorbent which had high adsorption performance at room temperature and normal atmosphere. After the modification by NaCl,5A molecular sieve had strong stability, high activity, and it was also low price and easy to regenerate, so it was a very worthy of further development of the adsorbent.
引文
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