摘要
使用吸油材料治理海洋石油污染是一种经济有效的方法。随着人们环保意识的提高,吸油材料的环保性也越来越重要。天然有机吸油材料具有可降解、廉价和可再生等优点,粘土类吸油材料具有环保、储量大等优点。近年来这两种材料得到广泛的关注,因此,研究其在海洋石油污染治理中的应用具有重要的现实意义。
本文以天然有机吸油材料(灯心草和吸油草)和粘土类吸油材料(钙基膨润土)为吸附剂,研究其吸油能力和对海水中石油的吸附特点。首先,研究了吸油材料对不同粘度油品(97#汽油、0#柴油、摩托车机油)的吸附性能及对水和油的优先吸附性能;接下来,研究了吸油材料对海水中柴油的吸附、解吸特点及其影响因素,并初步探讨了吸附机理;最后,通过对比吸油材料的吸油特点,确定了各吸油材料的使用方案。通过研究得到以下结论:
(1)随着油品粘度的增大,灯心草、吸油草和钙基膨润土的吸油量都随之增大。灯心草对于各油品(97#汽油、0#柴油、摩托车机油)的吸附量最大,其次是吸油草和钙基膨润土。
(2)极性物质(海水)和非极性物质(油类污染物)同时存在时,吸油草对二者的吸附为选择性吸附(优先吸附油),灯心草和钙基膨润土对二者的吸附为非选择性吸附。
(3)三种吸油材料对海水中柴油的吸附与解吸动力学曲线均符合Lagergren准二级动力学模型。并且随初始含油量的增多(0.2ml-0.7ml)、温度的降低(25℃、15℃、5℃)、盐度的增大(20‰、25‰、31‰)、pH的降低(9.48、8.09、6.49)三种吸附剂对海水中柴油的吸附量均增大。
(4)在试验研究的振荡频率范围内,振荡频率对灯心草的吸附量影响不大。在振荡频率为80-130r/min的范围内,随振荡频率的增大吸油草和钙基膨润土的吸油量随之增大;在振荡频率为130-175r/min的范围内,随振荡频率的增大吸油草和钙基膨润土的吸油量随之降低。在试验研究的振荡频率范围内,随振荡频率的增大三种吸附剂的对柴油的解吸量都随之上升。
(5)灯心草对海水中柴油的吸附过程可用Henry型吸附等温式来描述;吸油草对海水中柴油的吸附过程可用Langmuir和Freundlich等温式来描述;钙基膨润土对海水中柴油的吸附可用Freundlich等温式来描述。热力学研究表明,灯心草、钙基膨润土的吉布斯自由能变?G<0、熵变?S<0、焓变?H<0,吸油草的吉布斯自由能变?G<0、熵变?S>0、焓变?H<0。
(6)通过正交优化试验设计得出,环境因素对灯心草、吸油草和钙基膨润土的试验指标影响的主次顺序分别是:温度>盐度>pH值>振荡频率;盐度>温度>pH值>振荡频率;振荡频率>温度>pH值>盐度。
(7)综合三种材料的吸油效果、使用费用以及后续处理难易程度,吸油草更有实际应用的优势和市场潜力。
Using oil-absorbing materials to control marine oil pollution is a cost-effective way.With the increament of people’s environmental awareness,the environmental characteristics of oil-absorbing materials is also becoming increasingly important.Natural organic oil-absorbing materials because of its biodegradable、cheap and renewable advantages and clay because of its environmental protection、abundant reserves advantages have received extensive attention in recent years.Therefore,the study of environment-friendly oil-absorbing materials in the marine oil pollution control has an important practical significance.
This paper take the 0# diesel oil polluted seawater as the research object,and selected natural organic oil-absorbing materials(Juncus and Spill-sorb)and clay oil-absorbing materials (Ca-bentonite) as adsorbent.First,the adsorption of different viscosity oil and the preferential adsorption between water and oil on oil-absorbing materials are studied;second,the adsorption and desorption characteristics of diesel in seawater on oil-absorbing materials and its influence factors are studied,and its adsorption mechanism is explored.Finally,by comparing the adsorption characteristics of each oil- absorbing material,we can determine its dosing program.Through the above study,we can get the following preliminary conclusions:
(1)The adsorption capacity of Juncus、Spill-sorb and Ca-bentonite increase with the increment of oil viscosity.The adsorption capacity of Juncus for each oil is the largest,and the followed are Spill-sorb and Ca-bentonite.
(2)When polar substances (water) coexists with non-polar substances (oil pollution),the adsorption of Spill-sorb for the both is selective(oil is priority),and the adsorption of Juncus and Ca-bentonite are non-selective.
(3)The sorption kinetic processes of diesel on the three kinds oil-absorbing materials have been proven to follow the Lagergren-pesudo-second-order kinetic.The adsorption capacity of diesel in seawater on each kind adsorbent increases with the increase of initial oil content(0.2ml-0.7ml)and the salinity(20‰、25‰、31‰),and with the decrease of temperature(25℃、15℃、5℃)and pH(9.48、8.09、6.49).
(4)During the range of the trial oscillation frequency,it has little effect on the adsorption capacity of Juncus.Within the range of 80-130r/min,the adsorption capacity of Spill-sorb and Ca-bentonite increases with the increament of oscillation frequency.But within the range of 80-130r/min,the adsorption capacity of Spill-sorb and Ca-bentonite will decrease with the increament of oscillation frequency.During the range of the trial oscillation frequency,the desorption capacity of each kind materials increases with the increament of oscillation frequency.
(5)The isotherms of diesel in seawater on Juncus can be described as Henry’s equation.The isotherms of diesel in seawater on Spill-sorb can be described as Langmuir and Freundlich’s equation . The isotherms of diesel in seawater on Ca-bentonite can be described as Freundlich’s equation.Thermodynamic studies have shown that parameters of Juncus and Ca-bentonite are ?G<0、?S<0、?H<0,and the parameters of Spill-sorb are ?G<0、?S>0、?H<0.
(6)By orthogonal experimental design we can obtain that,the primary→secondary sequence of environmental factors on Juncus、Spill-sorb and Ca-bentonite are as followed respectively:temperature>salinity>pH>oscillation frequency;salinity>temperature>pH>oscillation frequency;oscillation frequency>temperature>pH>salinity.
(7)By integrating the oil-absorbing effect、the cost of use and the difficulty level of follow-up treatment of each kinds materials,we can conclude that Spill-sorb has more advantages on practical applications and market potential.
引文
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