强碱性阴离子交换树脂在海水提溴中的应用
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摘要
溴是一种重要的工业原料,在国民经济中应用广泛。地球上99%的溴都存在于海水中,随着现代生活对溴的需求量日益增大,海水提溴工程愈加重要而紧迫。目前采用的海水提溴技术普遍存在耗能高、流程复杂及成本高的缺点,因此寻找高效率、低成本直接从海水中提取溴离子的方法具有重要的意义。本文主要以201×7强碱性苯乙烯系阴离子交换树脂为吸附剂,研究了该树脂对海水中溴离子的吸附性能。
通过对文献报道较多的五种溴离子测定方法进行了比较。从测定结果的准确性、重现性、操作的难易程度及避免使用有毒化学品等方面考虑,选用甲基橙分光光度法,平均加标回收率为99.7%,标准曲线的相关系数R 2 = 0.9998,准确度较高,重现性均较好,操作简便且不使用有毒化学品。
从静态饱和吸附量、饱和吸附时间及抗物理破裂能力等方面,考察了201×4、201×7强碱性阴离子交换树脂和D201大孔强碱性阴离子交换树脂对人工海水中Br -的吸附,结果表明,201×7树脂较另外的两种树脂均有较大的吸附量和较短的吸附时间,且树脂颗粒抗物理破裂能力强,不易破损。该树脂的静态饱和吸附平衡时间为40 min左右,对Br–标准溶液、Br–浓度为128.26 mg·L~(-1)的人工浓海水及Br–浓度为65.03 mg·L~(-1)的人工海水中的静态饱和吸附量分别为33.25 mg·g~(-1)、25.94 mg·g~(-1)和29.42 mg·g~(-1)。
以201×7树脂为吸附剂进行对Br–浓度为128.26 mg·L~(-1)人工海水的静态吸附实验和静态解吸实验,结果表明:树脂质量的增加可提高吸附量,但当树脂质量达1.0 g时吸附量无明显变化,实验中树脂质量选取1.0 g;在288 K~328 K范围内,升高温度对该吸附过程有利,但吸附率的增幅不大,实验中温度选取298 K。在此基础上,根据静态吸附速率曲线,得到298 K时201×7树脂吸附Br–的表观速率常数为: k 298 = 1.7×10-3 s~(-1),液膜扩散是该吸附过程的主控步骤。根据等温吸附曲线确定吸附过程较符合Freundlich吸附等温式。通过红外光谱分析可知,201×7树脂吸附溴离子前后树脂的骨架结构没有发生化学反应,吸附发生的原因主要是Br–与( )—N +CH33之间的静电引力作用,该吸附过程属于离子交换吸附。测得201×7树脂对天然海水的静态饱和吸附量为27.72 mg·g~(-1)。确定了1.5 mol·L~(-1)柠檬酸钠溶液为最佳解吸剂,解吸率达79.68%。
以201×7树脂为吸附剂进行对Br–浓度为128.26 mg·L~(-1)人工海水的动态吸附实验和动态解吸实验,结果表明:低流速有利于该吸附过程。计算流速为2.3 ml·min~(-1)时的动态饱和吸附量为13.42 mg·g~(-1),比静态饱和吸附量小,说明此过程的动态吸附没有静态吸附效果好。解吸剂流速越慢,解吸效果越好,但单位时间解吸量却不随着流速的减慢而升高。解吸流速为3.2 ml·min~(-1)时,解吸Br–总量为49.41 mg,动态解吸率为63.49%,较静态解吸率有所下降,说明动态解吸没有静态解吸效果好。201×7树脂在天然海水中的吸附量在一定时间内随时间延长而增加,但是72 h之后,吸附量反而下降,测得吸附72 h后吸附量为38.57 mg·g~(-1)。
Bromine is one of the important industrial raw materials and has wide application in the national economy. 99% of bromine exists in sea water. With more and more demand of bromine in modern life, bromine extraction engineering from seawater shows importance increasingly. The current technologies of bromine extraction from seawater generally have many defects such as high energy consumption, complex process and high cost. Therefore, searching high efficiency and low cost method to extracted bromine ion directly from seawater has the vital significance. In this thesis, the adsorption properties of bromine ion in seawater are studied mainly using 201×7 strongly basic styrene type anion exchange resin.
In this thesis, five kinds of determination methods of bromine ion in seawater are compared. Considering the accuracy of determination results, reproducibility and the operation difficulty degree as well as avoids using dangerous chemicals and so on, methyl orange spectrophotometry surpasses other four methods. The results of methyl orange spectrophotometry are that Recovery rate is 99.7%, correlation coefficient of standard curve is 0.9998.
According to resins in literatures, 201×7、201×4 and D201 anion exchange resins are selected as adsorbent. Adsorption effects of bromine ion in standard solution and artificial seawater using these resins are researched from the capacity of static saturation adsorption, the time of static saturated adsorption as well as resistance to physical rupture ability. Results show that, the balance time of static adsorption is 40 minutes, static saturation adsorption capacities of bromine ion standard solution、artificially thick seawater with 128.26 mg·L~(-1) Br– and artificially seawater with 65.03 mg·L~(-1) Br– are 33.25 mg·g~(-1)、25.94 mg·g~(-1)and 29.42 mg·g~(-1) respectively.
This thesis studies the adsorption properties of 201×7 resin as adsorbent to remove Br– from artificially thick seawater (128.26 mg·L~(-1) Br–) by static adsorption experiment and static desorption experiment. Results show that, increasing resin mass can improve the adsorption capacity, but when resin mass reaches the 1.0 g, the adsorption capacity is not obviously improved. So, resin mass selected at 1.0 g in this experiment. Between 288 K~ 328 K, elevated temperature is beneficial to this adsorption process, but the growing rate of adsorption rate is not obvious. So, experiments are performed at 298 K. Apparent rate constant of this adsorption process is 1.7×10-3 s~(-1) at 298 K, therefore, the adsorption rate was mainly governed by liquid film diffusion. And the adsorption process fit well to Freundlich model.
Through infrared spectroscopy, chemical reaction of Resin’s skeleton structure doesn't occur. It could be concluded that adsorption mechanism is electrostatic attraction between Br– and ( )—N +CH33. The static saturation adsorption capacity of bromine ion in natural seawater is 27.72 mg·g~(-1). And 1.5 mol·L~(-1) Sodium citrate solution is selected as desorption agent with desorption rate being 79.68%.
By dynamic adsorption experiment and dynamic desorption experiment, results show that, low flow velocity is beneficial to this adsorption process. The capacity of dynamic adsorption is 13.42 mg·g~(-1)at 2.3 ml·min~(-1), less than the capacity of static saturation adsorption, which shows effect of static adsorption is best than dynamic adsorption. Low desorption flow velocity is beneficial to this desorption process, but desorption capacity per minute is not improved with the velocity slower. Dynamic desorption capacity is 49.41 mg and dynamic desorption rate is 63.49% at 3.2 ml·min~(-1), which are less than static desorption. The adsorption capacity in natural seawater increases as time goes on, but after 72 hours, it decreases. The adsorption capacity is 38.57 mg·g~(-1)at 72 h.
通过对文献报道较多的五种溴离子测定方法进行了比较。从测定结果的准确性、重现性、操作的难易程度及避免使用有毒化学品等方面考虑,选用甲基橙分光光度法,平均加标回收率为99.7%,标准曲线的相关系数R 2 = 0.9998,准确度较高,重现性均较好,操作简便且不使用有毒化学品。
从静态饱和吸附量、饱和吸附时间及抗物理破裂能力等方面,考察了201×4、201×7强碱性阴离子交换树脂和D201大孔强碱性阴离子交换树脂对人工海水中Br -的吸附,结果表明,201×7树脂较另外的两种树脂均有较大的吸附量和较短的吸附时间,且树脂颗粒抗物理破裂能力强,不易破损。该树脂的静态饱和吸附平衡时间为40 min左右,对Br–标准溶液、Br–浓度为128.26 mg·L~(-1)的人工浓海水及Br–浓度为65.03 mg·L~(-1)的人工海水中的静态饱和吸附量分别为33.25 mg·g~(-1)、25.94 mg·g~(-1)和29.42 mg·g~(-1)。
以201×7树脂为吸附剂进行对Br–浓度为128.26 mg·L~(-1)人工海水的静态吸附实验和静态解吸实验,结果表明:树脂质量的增加可提高吸附量,但当树脂质量达1.0 g时吸附量无明显变化,实验中树脂质量选取1.0 g;在288 K~328 K范围内,升高温度对该吸附过程有利,但吸附率的增幅不大,实验中温度选取298 K。在此基础上,根据静态吸附速率曲线,得到298 K时201×7树脂吸附Br–的表观速率常数为: k 298 = 1.7×10-3 s~(-1),液膜扩散是该吸附过程的主控步骤。根据等温吸附曲线确定吸附过程较符合Freundlich吸附等温式。通过红外光谱分析可知,201×7树脂吸附溴离子前后树脂的骨架结构没有发生化学反应,吸附发生的原因主要是Br–与( )—N +CH33之间的静电引力作用,该吸附过程属于离子交换吸附。测得201×7树脂对天然海水的静态饱和吸附量为27.72 mg·g~(-1)。确定了1.5 mol·L~(-1)柠檬酸钠溶液为最佳解吸剂,解吸率达79.68%。
以201×7树脂为吸附剂进行对Br–浓度为128.26 mg·L~(-1)人工海水的动态吸附实验和动态解吸实验,结果表明:低流速有利于该吸附过程。计算流速为2.3 ml·min~(-1)时的动态饱和吸附量为13.42 mg·g~(-1),比静态饱和吸附量小,说明此过程的动态吸附没有静态吸附效果好。解吸剂流速越慢,解吸效果越好,但单位时间解吸量却不随着流速的减慢而升高。解吸流速为3.2 ml·min~(-1)时,解吸Br–总量为49.41 mg,动态解吸率为63.49%,较静态解吸率有所下降,说明动态解吸没有静态解吸效果好。201×7树脂在天然海水中的吸附量在一定时间内随时间延长而增加,但是72 h之后,吸附量反而下降,测得吸附72 h后吸附量为38.57 mg·g~(-1)。
Bromine is one of the important industrial raw materials and has wide application in the national economy. 99% of bromine exists in sea water. With more and more demand of bromine in modern life, bromine extraction engineering from seawater shows importance increasingly. The current technologies of bromine extraction from seawater generally have many defects such as high energy consumption, complex process and high cost. Therefore, searching high efficiency and low cost method to extracted bromine ion directly from seawater has the vital significance. In this thesis, the adsorption properties of bromine ion in seawater are studied mainly using 201×7 strongly basic styrene type anion exchange resin.
In this thesis, five kinds of determination methods of bromine ion in seawater are compared. Considering the accuracy of determination results, reproducibility and the operation difficulty degree as well as avoids using dangerous chemicals and so on, methyl orange spectrophotometry surpasses other four methods. The results of methyl orange spectrophotometry are that Recovery rate is 99.7%, correlation coefficient of standard curve is 0.9998.
According to resins in literatures, 201×7、201×4 and D201 anion exchange resins are selected as adsorbent. Adsorption effects of bromine ion in standard solution and artificial seawater using these resins are researched from the capacity of static saturation adsorption, the time of static saturated adsorption as well as resistance to physical rupture ability. Results show that, the balance time of static adsorption is 40 minutes, static saturation adsorption capacities of bromine ion standard solution、artificially thick seawater with 128.26 mg·L~(-1) Br– and artificially seawater with 65.03 mg·L~(-1) Br– are 33.25 mg·g~(-1)、25.94 mg·g~(-1)and 29.42 mg·g~(-1) respectively.
This thesis studies the adsorption properties of 201×7 resin as adsorbent to remove Br– from artificially thick seawater (128.26 mg·L~(-1) Br–) by static adsorption experiment and static desorption experiment. Results show that, increasing resin mass can improve the adsorption capacity, but when resin mass reaches the 1.0 g, the adsorption capacity is not obviously improved. So, resin mass selected at 1.0 g in this experiment. Between 288 K~ 328 K, elevated temperature is beneficial to this adsorption process, but the growing rate of adsorption rate is not obvious. So, experiments are performed at 298 K. Apparent rate constant of this adsorption process is 1.7×10-3 s~(-1) at 298 K, therefore, the adsorption rate was mainly governed by liquid film diffusion. And the adsorption process fit well to Freundlich model.
Through infrared spectroscopy, chemical reaction of Resin’s skeleton structure doesn't occur. It could be concluded that adsorption mechanism is electrostatic attraction between Br– and ( )—N +CH33. The static saturation adsorption capacity of bromine ion in natural seawater is 27.72 mg·g~(-1). And 1.5 mol·L~(-1) Sodium citrate solution is selected as desorption agent with desorption rate being 79.68%.
By dynamic adsorption experiment and dynamic desorption experiment, results show that, low flow velocity is beneficial to this adsorption process. The capacity of dynamic adsorption is 13.42 mg·g~(-1)at 2.3 ml·min~(-1), less than the capacity of static saturation adsorption, which shows effect of static adsorption is best than dynamic adsorption. Low desorption flow velocity is beneficial to this desorption process, but desorption capacity per minute is not improved with the velocity slower. Dynamic desorption capacity is 49.41 mg and dynamic desorption rate is 63.49% at 3.2 ml·min~(-1), which are less than static desorption. The adsorption capacity in natural seawater increases as time goes on, but after 72 hours, it decreases. The adsorption capacity is 38.57 mg·g~(-1)at 72 h.
引文
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