第三代N、O型纤维素基水处理剂的合成及应用研究
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摘要
第三代纤维素基水处理剂是一类新型的纤维素衍生型高分子功能材料。本课题首先以日本Chelest公司提供的硫代苹果酸型纤维素基水处理剂对Cu2+的吸附进行了探索性研究,然后根据其结构特点和国内外相关资料进行了合成研究,通过采用改变功能基团的方法分别制备出阳离子环糊精型双层功能化纤维素基水处理剂、葡萄糖型纤维素基水处理剂和葡萄糖/阳离子复合型单层纤维素基水处理剂三种新型吸附剂。通过一系列分析表征手段从样品的外貌、组成成分及含量、结构、热稳定性等方面进行系统的分析证实。结合振荡吸附实验法和流动柱实验法确定了新型纤维素基水处理剂的最佳吸附/脱附条件及其适用范围。考察了新型纤维素基水处理剂的吸附动力学、吸附分配等温线模型和吸附热力学的类型。课题具体研究内容阐述如下:
1)根据纤维素基水处理剂结构的特点对其进行了分类和划分,并从载体形态、接枝链与载体接枝方法、功能基团选取及功能化方法、吸附/脱附性能的影响因素和脱附方法五个方面综述了国内外在该领域的研究现状。对其发展前景进行了展望。详细论述了课题的背景、意义、研究目的和研究内容。
2)硫代苹果酸型环氧纤维素基水处理剂吸附Cu2+的实验发现:最佳酸度范围为pH3~6,实验选定pH5.0为最佳酸度;最佳吸附时间90分钟;吸附过程符合准二级反应动力学过程,对Cu2+的初始吸附速率可达0.2245mg g-1 min-1;吸附等温曲线为Langmuir型,最大吸附量为15.10mg/g;当溶液中仅含Cu2+时,吸附剂的处理效果满足生活饮用水水质标准铜离子浓度的规定值(1mg/L)。
3)以纤维素为原料分别制备出第三代阳离子环糊精型、第三代葡萄糖型和第三代葡萄糖/阳离子复合型环氧纤维素基水处理剂。通过扫描电子显微镜、元素分析、红外谱图分析、热重分析和差热分析手段对样品进行了证实。
4)阳离子环糊精型纤维素基水处理剂吸附酚酞的实验发现:最佳吸附时间180分钟;吸附过程符合准二级反应动力学过程,对酚酞的初始吸附速率可达1408mg g-1 min-1;最佳酸度范围为pH9~13,实验选定pH12.0为最佳酸度;吸附等温曲线为Langmuir型,最大吸附量为258.4mg/g;吸附热力学研究表明吸附过程为吸热过程。
5)阳离子环糊精型双层功能化纤维素基水处理剂吸附Cr(VI)的实验发现:最佳酸度范围为pH4~6,实验选定pH4.5为最佳酸度;吸附10min时,吸附率高达98.5%,最佳吸附时间90分钟;吸附过程符合准二级反应动力学过程,对Cr(VI)的初始吸附速率可达751.88mg g-1 min-1;最佳吸附剂用量50mg,此时吸附率为99.5%;在吸附率保持95%时,仅50mg/L Mn2+产生干扰;吸附等温曲线为Langmuir型,最大吸附量为61.05mg/g;脱附剂NaOH溶液最佳浓度为0.50 mg/L;重复使用5次时,吸附率及脱附率的变化不大;当溶液中仅含50 mg/L和5 mg/L Cr(VI)时,吸附效果分别达到污水综合排放标准GB8978-1996的规定值(0.5mg/L)和生活饮用水水质标准的规定值(0.05mg/L)的要求。
6)葡萄糖型纤维素基水处理剂吸附Cr(VI)的实验发现:最佳酸度范围为pH3~6,实验选定pH4.0为最佳酸度;吸附10min时,吸附率为97%,最佳吸附时间90分钟;吸附过程符合准二级反应动力学过程,对Cr(VI)的初始吸附速率可达138.10mg g-1 min-1;根据污水综合排放标准GB8978-1996的规定中铬的排放值(0.5mg/L),最佳吸附剂用量为50mg,此时吸附率为99.3%;吸附等温曲线为Langmuir型,最大吸附量为54.59mg/g;在吸附率保持95%时,仅50mg/L Mn2+产生干扰;脱附剂NaOH溶液最佳浓度为0.05mg/L;重复使用6次时,吸附率及脱附率的变化不大;当溶液中仅含5mg/L Cr(VI)时,吸附效果达到生活饮用水水质标准GB8978-1996的规定值(0.05mg/L)的要求。
7)葡萄糖/阳离子复合型单层纤维素基水处理剂吸附Cr(VI)的实验发现:最佳酸度范围为pH2.5~6.5,实验选定pH3.5为最佳酸度;吸附10min时,吸附率为97.6%,最佳吸附时间90分钟;吸附过程符合准二级反应动力学过程,对Cr(VI)的初始吸附速率可达165.84mg g-1 min-1;根据污水综合排放标准GB8978-1996的规定中铬的排放值(0.5mg/L),最佳吸附剂用量为50mg,此时吸附率为99.3%;吸附等温曲线为Langmuir型,最大吸附量为71.79mg/g;在吸附率保持95%时,共存离子未对其产生干扰;脱附剂NaOH溶液最佳浓度为0.05mg/L,其脱附率高达99.7%;重复使用6次时,吸附率及脱附率的变化不大;当溶液中仅含5 mg/L Cr(VI)时,滤液中Cr(VI)的浓度为0.033mg/L达到生活饮用水水质标准GB8978-1996的规定值(0.05mg/L)的要求。
制备的三种新型纤维素基水处理剂无毒、无污染、成本低廉、使用范围广、吸附速度快、吸附性能稳定、可重复使用等优点,具有良好的开发前景,不仅可以满足当前水处理材料需要,而且可以为纤维素的合理利用开辟新的途径,同时得到的水处理剂有望生物降解,符合当今以减量化、再利用、资源化为原则的“循环经济”和以低能耗、低污染为基础的“低碳经济”的发展方向。
The third generation cellulose-based water treatment agent is a new-style cellulose derivative macromolecule functional material. In the first place, the issue was carried out exploratory research on thiomalic acid-type epoxy cellulose-based water treatment agent, which obtained from Chelest Company in Japan, was adsorbed copper ions in aqueous solution. And then, synthesis on new-style adsorbent was based on characteristics of adsorbent structure and combined with relevant information at home and abroad using changed the functional group method. Third generation cationic-modifiedβ-cyclodextrin-type, D-glucose-type, and cationic-modified D-glucose compound type cellulose-based epoxy water treatment agent were prepared, respectively. The appearance, composition and content, structure, thermal stability, and other aspects of sample was characterized and confirmed by a series of analytical method. Using batch adsorption and column adsorption, the best conditions of cellulose-based water treatment agent adsorption/desorption and application were determined. The adsorption kinetics, isotherm model, and thermodynamics of cellulose-based water treatment agent have been studied. The research topics described as following:
1) Cellulose–based water treatment agent was classified and divided according to the structure characteristics of it in this paper. The recent progress was reviewed in five respects: carrier form, grafted method for grafting chain and carrier, selected for adsorption/desorption functional group and technique of functionalization, influencing factors in the performance of adsorption/desorption, and desorption method. The future direction of development was prospected. The context, significance, purpose and content of subject was described in detail.
2) Thiomalic acid-type epoxy cellulose-based water treatment agent has been studied for the adsorption of copper ions in aqueous solution. The experiment data suggest that: the best acidity range of pH3-6, and the best experimental acidity of pH5.0 was selected; 90min was recognized as the optimum adsorption time; The kinetics of the adsorption process indicated that pseudo-second-order kinetics best described the overall process, and the initial sorption rate can be up to 0.2245mg g-1 min-1; The adsorption process was best described by the Langmuir model of adsorption, and the maximum adsorption capacity of Cu2+ was calculated as 15.10mg/g; when the solution was detailed and contained to copper ions, the treatment result by adsorbent does accord with the standard for drinking water(1mg/L).
3) Third generation cationic-modifiedβ-cyclodextrin-type, D-glucose-type, and cationic-modified D-glucose compound type cellulose-based epoxy water treatment agent were prepared by using cellulose as raw material, respectively. Samples were confirmed by scanning electron microscopy, elemental analysis, fourier transform infrared spectroscopy analysis, thermogravimetric analysis and differential thermal analysis.
4) From cationic-modifiedβ-cyclodextrin-type cellulose-based water treatment agent on the adsorption on phenolphthalein experiment can be seen that: selected optimum adsorption time was up to 180min; The kinetics of the adsorption process in line with pseudo-second-order kinetics, and the initial sorption rate should be up to 1408mg g-1 min-1; The best experimental pH12.0 was selected from the optimum pH range of 9 to 13; The adsorption process was best described by the Langmuir model of adsorption, and the maximum adsorption capacity of phenolphthalein was calculated as 258.4mg/g; the adsorption thermodynamics studies has shown that the adsorption is anothermic.
5) The cationic-modifiedβ-cyclodextrin-type double functional cellulose-based water treatment agent was adsorbed Cr (VI) in aqueous solution. Based on the adsorption tests data: the appropriate acidity range of adsorption is pH4~6, from which pH4.5 was selected; The adsorption amounted up to 98.5% when shaking for 10 minutes, and a choice of 90 minutes as the best adsorption time; The kinetics of the adsorption process is fitted in with pseudo-second-order kinetics, and the initial sorption rate should be up to 751.88mg g-1 min-1; the optimum adsorbent dose was 50mg, while percentage removal of Cr(VI) was 99.5%; when the percentage absorption was kept at the rate of 95%, only 50mg/L Mn2+ was interfered; The adsorption process was best described by the Langmuir model of adsorption, and the maximum adsorption capacity of Cr(VI) was determined to 61.05mg/g; 0.50 mol L-1 NaOH as a desorption agent has chosen; after adsorbent was regenerated and reused 5 times in the adsorption and desorption of Cr(VI), the adsorption/desorption rate without obvious loss; When the solution contains only 50 mg/L and 5 mg/L Cr(VI), the adsorption data meet the requirements of the standard for integrated wastewater discharge GB8978-1996 (0.5mg/L) drinking water quality and the standard for drinking water(0.05mg/L), respectively.
6) D-glucose-type cellulose-based water treatment agent was adsorbed on Cr(VI) in aqueous solution. It can be found that: The best acidity range of pH3~6, and selection of the best acidity is pH4.0; The adsorption amounted up to 97% when shaking for 10 minutes, and the adsorption time was made choice of 90 minutes; The kinetics of the adsorption process is fitted in with pseudo-second-order kinetics, and the initial sorption rate was 138.10mg g-1 min-1;According to the standard for integrated wastewater discharge GB8978-1996(0.5mg/L) and the adsorption rate was up to 99.3%, optimum adsorbent dosage is selected 50mg; The adsorption process was best described by the Langmuir model of adsorption, and the maximum adsorption capacity of Cr(VI) was 54.59mg/g; when the absorption rate remained 95% at least for test, only 50mg/L Mn2+ will be affected; the optimal concentration of NaOH solution, as a desorption agent, was opted for 0.05mg/L; when adsorbent was reused for six times, the adsorption/desorption rate haven’t changed; When it contains only 5 mg/L Cr(VI) in the solution, the adsorption data can be reached the requirement of the standard for drinking water(0.05mg/L).
7) Cationic-modified D-glucose compound type cellulose-based water treatment agent for effective separation of Cr(VI) from aqueous solution. Conclusion of experiment is that: experimental selection of the best acidity is pH3.5, which was due to the best pH range from 2.5 to 6.5; The adsorption amounted up to 97.6% when shaking for 10 minutes, and the best adsorption time 90 minutes was determined for the future test; The kinetics of the adsorption process is fitted in with pseudo-second-order kinetics, and the initial sorption rate was 165.84mg g-1 min-1; Based on the Integrated Wastewater Discharge Standard GB8978-1996(0.5mg/L) and adsorption rate can be up to 99.3%, 50mg as a optimum adsorbent dose was chosen; The adsorption process was best described by the Langmuir model of adsorption, and the maximum adsorption capacity of Cr(VI) was 71.79mg/g; if the adsorption rate was maintained 95%, the result for interference test were satisfactory; the desorption rate was up to 99.7% using 0.05mg/L NaOH solution as a desorption agent; desorption was repeated at least six times, and the adsorption/desorption rate without any obvious change; the concentration of Cr(VI) was reduced 0.033mg/L in the filtrate when there is only 5mg/L Cr(VI) contained in the solution. The result can be achieved the requirement of drinking water quality standard (0.05mg/L).
According to the advantage of three new-styles cellulose-based water treatment agents, such as non-toxic, non-polluting, low cost, widely used, rapid absorption, stable adsorption, reusable, etc., it will have a good development prospects. Not only it can be to meet the need of current water treatment material, but also to open up new avenues for the rational use of cellulose, while the water treatment agent is expected to be biodegradable, which can accord with direction of development for the principle of 3R (Reduce, Reuse and Recycle) of "circular economy" and foundation of low energy consumption, low pollution-based "low-carbon economy" in nowadays.
1)根据纤维素基水处理剂结构的特点对其进行了分类和划分,并从载体形态、接枝链与载体接枝方法、功能基团选取及功能化方法、吸附/脱附性能的影响因素和脱附方法五个方面综述了国内外在该领域的研究现状。对其发展前景进行了展望。详细论述了课题的背景、意义、研究目的和研究内容。
2)硫代苹果酸型环氧纤维素基水处理剂吸附Cu2+的实验发现:最佳酸度范围为pH3~6,实验选定pH5.0为最佳酸度;最佳吸附时间90分钟;吸附过程符合准二级反应动力学过程,对Cu2+的初始吸附速率可达0.2245mg g-1 min-1;吸附等温曲线为Langmuir型,最大吸附量为15.10mg/g;当溶液中仅含Cu2+时,吸附剂的处理效果满足生活饮用水水质标准铜离子浓度的规定值(1mg/L)。
3)以纤维素为原料分别制备出第三代阳离子环糊精型、第三代葡萄糖型和第三代葡萄糖/阳离子复合型环氧纤维素基水处理剂。通过扫描电子显微镜、元素分析、红外谱图分析、热重分析和差热分析手段对样品进行了证实。
4)阳离子环糊精型纤维素基水处理剂吸附酚酞的实验发现:最佳吸附时间180分钟;吸附过程符合准二级反应动力学过程,对酚酞的初始吸附速率可达1408mg g-1 min-1;最佳酸度范围为pH9~13,实验选定pH12.0为最佳酸度;吸附等温曲线为Langmuir型,最大吸附量为258.4mg/g;吸附热力学研究表明吸附过程为吸热过程。
5)阳离子环糊精型双层功能化纤维素基水处理剂吸附Cr(VI)的实验发现:最佳酸度范围为pH4~6,实验选定pH4.5为最佳酸度;吸附10min时,吸附率高达98.5%,最佳吸附时间90分钟;吸附过程符合准二级反应动力学过程,对Cr(VI)的初始吸附速率可达751.88mg g-1 min-1;最佳吸附剂用量50mg,此时吸附率为99.5%;在吸附率保持95%时,仅50mg/L Mn2+产生干扰;吸附等温曲线为Langmuir型,最大吸附量为61.05mg/g;脱附剂NaOH溶液最佳浓度为0.50 mg/L;重复使用5次时,吸附率及脱附率的变化不大;当溶液中仅含50 mg/L和5 mg/L Cr(VI)时,吸附效果分别达到污水综合排放标准GB8978-1996的规定值(0.5mg/L)和生活饮用水水质标准的规定值(0.05mg/L)的要求。
6)葡萄糖型纤维素基水处理剂吸附Cr(VI)的实验发现:最佳酸度范围为pH3~6,实验选定pH4.0为最佳酸度;吸附10min时,吸附率为97%,最佳吸附时间90分钟;吸附过程符合准二级反应动力学过程,对Cr(VI)的初始吸附速率可达138.10mg g-1 min-1;根据污水综合排放标准GB8978-1996的规定中铬的排放值(0.5mg/L),最佳吸附剂用量为50mg,此时吸附率为99.3%;吸附等温曲线为Langmuir型,最大吸附量为54.59mg/g;在吸附率保持95%时,仅50mg/L Mn2+产生干扰;脱附剂NaOH溶液最佳浓度为0.05mg/L;重复使用6次时,吸附率及脱附率的变化不大;当溶液中仅含5mg/L Cr(VI)时,吸附效果达到生活饮用水水质标准GB8978-1996的规定值(0.05mg/L)的要求。
7)葡萄糖/阳离子复合型单层纤维素基水处理剂吸附Cr(VI)的实验发现:最佳酸度范围为pH2.5~6.5,实验选定pH3.5为最佳酸度;吸附10min时,吸附率为97.6%,最佳吸附时间90分钟;吸附过程符合准二级反应动力学过程,对Cr(VI)的初始吸附速率可达165.84mg g-1 min-1;根据污水综合排放标准GB8978-1996的规定中铬的排放值(0.5mg/L),最佳吸附剂用量为50mg,此时吸附率为99.3%;吸附等温曲线为Langmuir型,最大吸附量为71.79mg/g;在吸附率保持95%时,共存离子未对其产生干扰;脱附剂NaOH溶液最佳浓度为0.05mg/L,其脱附率高达99.7%;重复使用6次时,吸附率及脱附率的变化不大;当溶液中仅含5 mg/L Cr(VI)时,滤液中Cr(VI)的浓度为0.033mg/L达到生活饮用水水质标准GB8978-1996的规定值(0.05mg/L)的要求。
制备的三种新型纤维素基水处理剂无毒、无污染、成本低廉、使用范围广、吸附速度快、吸附性能稳定、可重复使用等优点,具有良好的开发前景,不仅可以满足当前水处理材料需要,而且可以为纤维素的合理利用开辟新的途径,同时得到的水处理剂有望生物降解,符合当今以减量化、再利用、资源化为原则的“循环经济”和以低能耗、低污染为基础的“低碳经济”的发展方向。
The third generation cellulose-based water treatment agent is a new-style cellulose derivative macromolecule functional material. In the first place, the issue was carried out exploratory research on thiomalic acid-type epoxy cellulose-based water treatment agent, which obtained from Chelest Company in Japan, was adsorbed copper ions in aqueous solution. And then, synthesis on new-style adsorbent was based on characteristics of adsorbent structure and combined with relevant information at home and abroad using changed the functional group method. Third generation cationic-modifiedβ-cyclodextrin-type, D-glucose-type, and cationic-modified D-glucose compound type cellulose-based epoxy water treatment agent were prepared, respectively. The appearance, composition and content, structure, thermal stability, and other aspects of sample was characterized and confirmed by a series of analytical method. Using batch adsorption and column adsorption, the best conditions of cellulose-based water treatment agent adsorption/desorption and application were determined. The adsorption kinetics, isotherm model, and thermodynamics of cellulose-based water treatment agent have been studied. The research topics described as following:
1) Cellulose–based water treatment agent was classified and divided according to the structure characteristics of it in this paper. The recent progress was reviewed in five respects: carrier form, grafted method for grafting chain and carrier, selected for adsorption/desorption functional group and technique of functionalization, influencing factors in the performance of adsorption/desorption, and desorption method. The future direction of development was prospected. The context, significance, purpose and content of subject was described in detail.
2) Thiomalic acid-type epoxy cellulose-based water treatment agent has been studied for the adsorption of copper ions in aqueous solution. The experiment data suggest that: the best acidity range of pH3-6, and the best experimental acidity of pH5.0 was selected; 90min was recognized as the optimum adsorption time; The kinetics of the adsorption process indicated that pseudo-second-order kinetics best described the overall process, and the initial sorption rate can be up to 0.2245mg g-1 min-1; The adsorption process was best described by the Langmuir model of adsorption, and the maximum adsorption capacity of Cu2+ was calculated as 15.10mg/g; when the solution was detailed and contained to copper ions, the treatment result by adsorbent does accord with the standard for drinking water(1mg/L).
3) Third generation cationic-modifiedβ-cyclodextrin-type, D-glucose-type, and cationic-modified D-glucose compound type cellulose-based epoxy water treatment agent were prepared by using cellulose as raw material, respectively. Samples were confirmed by scanning electron microscopy, elemental analysis, fourier transform infrared spectroscopy analysis, thermogravimetric analysis and differential thermal analysis.
4) From cationic-modifiedβ-cyclodextrin-type cellulose-based water treatment agent on the adsorption on phenolphthalein experiment can be seen that: selected optimum adsorption time was up to 180min; The kinetics of the adsorption process in line with pseudo-second-order kinetics, and the initial sorption rate should be up to 1408mg g-1 min-1; The best experimental pH12.0 was selected from the optimum pH range of 9 to 13; The adsorption process was best described by the Langmuir model of adsorption, and the maximum adsorption capacity of phenolphthalein was calculated as 258.4mg/g; the adsorption thermodynamics studies has shown that the adsorption is anothermic.
5) The cationic-modifiedβ-cyclodextrin-type double functional cellulose-based water treatment agent was adsorbed Cr (VI) in aqueous solution. Based on the adsorption tests data: the appropriate acidity range of adsorption is pH4~6, from which pH4.5 was selected; The adsorption amounted up to 98.5% when shaking for 10 minutes, and a choice of 90 minutes as the best adsorption time; The kinetics of the adsorption process is fitted in with pseudo-second-order kinetics, and the initial sorption rate should be up to 751.88mg g-1 min-1; the optimum adsorbent dose was 50mg, while percentage removal of Cr(VI) was 99.5%; when the percentage absorption was kept at the rate of 95%, only 50mg/L Mn2+ was interfered; The adsorption process was best described by the Langmuir model of adsorption, and the maximum adsorption capacity of Cr(VI) was determined to 61.05mg/g; 0.50 mol L-1 NaOH as a desorption agent has chosen; after adsorbent was regenerated and reused 5 times in the adsorption and desorption of Cr(VI), the adsorption/desorption rate without obvious loss; When the solution contains only 50 mg/L and 5 mg/L Cr(VI), the adsorption data meet the requirements of the standard for integrated wastewater discharge GB8978-1996 (0.5mg/L) drinking water quality and the standard for drinking water(0.05mg/L), respectively.
6) D-glucose-type cellulose-based water treatment agent was adsorbed on Cr(VI) in aqueous solution. It can be found that: The best acidity range of pH3~6, and selection of the best acidity is pH4.0; The adsorption amounted up to 97% when shaking for 10 minutes, and the adsorption time was made choice of 90 minutes; The kinetics of the adsorption process is fitted in with pseudo-second-order kinetics, and the initial sorption rate was 138.10mg g-1 min-1;According to the standard for integrated wastewater discharge GB8978-1996(0.5mg/L) and the adsorption rate was up to 99.3%, optimum adsorbent dosage is selected 50mg; The adsorption process was best described by the Langmuir model of adsorption, and the maximum adsorption capacity of Cr(VI) was 54.59mg/g; when the absorption rate remained 95% at least for test, only 50mg/L Mn2+ will be affected; the optimal concentration of NaOH solution, as a desorption agent, was opted for 0.05mg/L; when adsorbent was reused for six times, the adsorption/desorption rate haven’t changed; When it contains only 5 mg/L Cr(VI) in the solution, the adsorption data can be reached the requirement of the standard for drinking water(0.05mg/L).
7) Cationic-modified D-glucose compound type cellulose-based water treatment agent for effective separation of Cr(VI) from aqueous solution. Conclusion of experiment is that: experimental selection of the best acidity is pH3.5, which was due to the best pH range from 2.5 to 6.5; The adsorption amounted up to 97.6% when shaking for 10 minutes, and the best adsorption time 90 minutes was determined for the future test; The kinetics of the adsorption process is fitted in with pseudo-second-order kinetics, and the initial sorption rate was 165.84mg g-1 min-1; Based on the Integrated Wastewater Discharge Standard GB8978-1996(0.5mg/L) and adsorption rate can be up to 99.3%, 50mg as a optimum adsorbent dose was chosen; The adsorption process was best described by the Langmuir model of adsorption, and the maximum adsorption capacity of Cr(VI) was 71.79mg/g; if the adsorption rate was maintained 95%, the result for interference test were satisfactory; the desorption rate was up to 99.7% using 0.05mg/L NaOH solution as a desorption agent; desorption was repeated at least six times, and the adsorption/desorption rate without any obvious change; the concentration of Cr(VI) was reduced 0.033mg/L in the filtrate when there is only 5mg/L Cr(VI) contained in the solution. The result can be achieved the requirement of drinking water quality standard (0.05mg/L).
According to the advantage of three new-styles cellulose-based water treatment agents, such as non-toxic, non-polluting, low cost, widely used, rapid absorption, stable adsorption, reusable, etc., it will have a good development prospects. Not only it can be to meet the need of current water treatment material, but also to open up new avenues for the rational use of cellulose, while the water treatment agent is expected to be biodegradable, which can accord with direction of development for the principle of 3R (Reduce, Reuse and Recycle) of "circular economy" and foundation of low energy consumption, low pollution-based "low-carbon economy" in nowadays.
引文
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[15]Huang M R, Li X G. Thermal degradation of cellulose and cellulose esters[J]. J. Appl. Polym. Sci.. 1998, 68(2): 293–304.
[16]Shukla S R, Athalye A R. Mechanical and thermal properties of glycidyl methacrylate grafted cotton cellulose[J]. J. Appl. Polym. Sci.. 1995, 57(8): 983–988.
[17]Raemy A, Schweizer T F. Thermal behaviour of carbohydrates studied by heat flow calorimetry[J]. J. Therm. Anal. Calorim.. 1983, 28(1): 95–108.
[18]Li H Y, Wang L J, Jacob K, et al. Syntheses and characterizations of thermally degradable epoxy resins. III[J]. J. Polym. Sci. Pol. Chem.. 2002, 40(11): 1796–1807.
[19]Evans R J, Wang D N, Agblevor F A, et al. Mass spectrometric studies of the thermal decomposition of carbohydrates using 13C-labeled cellulose and glucose[J]. Carbohydr. Res.. 1996, 281(2): 219–235.
[20]Britt P F, Buchanan A C, Jr C V O, et al. Does glucose enhance the formation of nitrogen containing polycyclic aromatic compounds and polycyclic aromatic hydrocarbons in the pyrolysis of proline?[J]. Fuel. 2004, 83(11–12): 1417–1432.
[21]Elliott H A, Huang C P. Adsorption characteristics of some Cu(II) complexes on aluminosilicates[J]. Water Research. 1981, 15(7): 849-855.
[22]Bajpai J, Shrivastava R, Bajpai A K. Dynamic and equilibrium studies on adsorption of Cr(VI) ions onto binary bio-polymeric beads of cross linked alginate and gelatin[J].Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2004, 236(1-3):81-90.
[23]Akama Y,Yamada K,Itoh O.Solid phase extraction of lead by Chelest Fiber Iry (aminopolycarboxylic acid-type cellulose)[J]. Analytica Chimica Acta. 2003, 485(1): 19–24.
[24]O’Connell D W, Birkinshaw C, O’Dwyer T F. A modified cellulose adsorbent for the removal of nickel(II) from aqueous solutions[J]. Journal of Chemical Technology and Biotechnology. 2006, 81(11): 1820-1828.
[25]Kara A, Uzun L, Be?irli N, et al. Poly(ethylene glycol dimethacrylate-n-vinyl imidazole) beads for heavy metal removal[J]. Journal of Hazardous Materials. 2004, 106(2-3): 93-99.
[2]Singh K K, Hasan S H, Talat M, et al. Removal of Cr (VI) from aqueous solutions using wheat bran[J]. Chem. Eng. J.. 2009, 151(1-3): 113–121.
[3]Choi H D, Jung W S, Cho J M, et al. Adsorption of Cr(VI) onto cationic surfactant-modified activated carbon[J]. J. Hazard. Mater.. 2009, 166(2-3): 642–646.
[4]O’Connell D W, Birkinshaw C, O’Dwyer T F. Heavy metal adsorbents prepared from the modification of cellulose: A review[J]. Bioresour. Technol.. 2008, 99(15): 6709–6724.
[5]Sahiner N, Godbey W T, McPherson G L, et al. Microgel, nanogel and hydrogel–hydrogel semi-IPN composites for biomedical applications:synthesis and characterization[J].Colloid. Polym. Sci.. 2006, 284(10): 1121–1129.
[6]Sahiner N. Colloidal nanocomposite hydrogel particles[J]. Colloid Polym Sci.. 2007, 285(4): 413–421.
[7]Levy N, Garti N, Magdassi S. Flocculation of bentonite suspensions with cationic guar[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 1995, 97(2): 91-99.
[8]Chauhan G S, Lal H. Novel grafied cellulose-based hydrogels for water technologies[J]. Desalination. 2003, 159(2): 131-138.
[9]Atia A A. Synthesis of a quaternary amine anion exchange resin and study its adsorption behaviour for chromate oxyanions[J]. J. Hazard. Mater.. 2006, 137(2): 1049-1055.
[10]Hradil J, ?vec F. Reactive polymers.61. Synthesis of strongly basic anion exchange meth-acrylate resins[J]. Reactive Polymers, 1990, 13(1-2): 43-53.
[11]Liu M H, Zhan H, Zhang X S, et al. Removal and recovery of chromium(III) from aqueous solutions by a spheroidal cellulose adsorbent[J]. Water Environmental Research. 2001, 73(3): 322–328.
[12]Liu M H, Deng Y, Zhan H Y, et al. Adsorption and desorption of copper(II) from solutions on new spherical cellulose adsorbent[J]. J. Appl. Polym. Sci.. 2002, 84(3): 478-485,.
[13]Navarro R R, Sumi K, Matsumura M. Improved metal affinity of chelating adsorbents throughgraft polymerization[J]. Water Res.. 1999, 33(9): 2037–2044.
[14]Yang P Y, Kokot S. Thermal analysis of different cellulosic fabric[J]. J. Appl. Polym. Sci.. 1996, 60(8): 1137–1146.
[15]Huang M R, Li X G. Thermal degradation of cellulose and cellulose esters[J]. J. Appl. Polym. Sci.. 1998, 68(2): 293–304.
[16]Shukla S R, Athalye A R. Mechanical and thermal properties of glycidyl methacrylate grafted cotton cellulose[J]. J. Appl. Polym. Sci.. 1995, 57(8): 983–988.
[17]Raemy A, Schweizer T F. Thermal behaviour of carbohydrates studied by heat flow calorimetry[J]. J. Therm. Anal. Calorim.. 1983, 28(1): 95–108.
[18]Li H Y, Wang L J, Jacob K, et al. Syntheses and characterizations of thermally degradable epoxy resins. III[J]. J. Polym. Sci. Pol. Chem.. 2002, 40(11): 1796–1807.
[19]Evans R J, Wang D N, Agblevor F A, et al. Mass spectrometric studies of the thermal decomposition of carbohydrates using 13C-labeled cellulose and glucose[J]. Carbohydr. Res.. 1996, 281(2): 219–235.
[20]Britt P F, Buchanan A C, Jr C V O, et al. Does glucose enhance the formation of nitrogen containing polycyclic aromatic compounds and polycyclic aromatic hydrocarbons in the pyrolysis of proline?[J]. Fuel. 2004, 83(11–12): 1417–1432.
[21]Elliott H A, Huang C P. Adsorption characteristics of some Cu(II) complexes on aluminosilicates[J]. Water Research. 1981, 15(7): 849-855.
[22]Bajpai J, Shrivastava R, Bajpai A K. Dynamic and equilibrium studies on adsorption of Cr(VI) ions onto binary bio-polymeric beads of cross linked alginate and gelatin[J].Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2004, 236(1-3):81-90.
[23]Akama Y,Yamada K,Itoh O.Solid phase extraction of lead by Chelest Fiber Iry (aminopolycarboxylic acid-type cellulose)[J]. Analytica Chimica Acta. 2003, 485(1): 19–24.
[24]O’Connell D W, Birkinshaw C, O’Dwyer T F. A modified cellulose adsorbent for the removal of nickel(II) from aqueous solutions[J]. Journal of Chemical Technology and Biotechnology. 2006, 81(11): 1820-1828.
[25]Kara A, Uzun L, Be?irli N, et al. Poly(ethylene glycol dimethacrylate-n-vinyl imidazole) beads for heavy metal removal[J]. Journal of Hazardous Materials. 2004, 106(2-3): 93-99.