废弃聚酯醇解液的回收与循环利用
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摘要
为实现聚酯资源的可再生循环应用,采用乙二醇醇解法对废弃聚酯(PET)面料进行降解,得到产物对苯二甲酸乙二醇酯(BHET)。为了达到乙二醇(EG)的最大化利用率,在产物重结晶前后减压蒸馏回收醇解液,并用其代替EG再次用于废弃聚酯的降解。借助红外光谱、差示扫描量热法和热重分析法对醇解产物和醇解液进行测定。结果表明:重结晶前回收的醇解液可循环使用4～5次,EG回收率在57.1%～89.2%之间,BHET产率在58.9%～70.3%之间,醇解液使用的循环上限主要取决于醇解液中EG自聚程度;重结晶后回收的醇解液可循环使用1～2次,达到使用上限后,EG回收率由91.3%降至23.7%,BHET产率由71.2%降至50.2%。
In order to realize the recycling of polyester resources, waste polyester(PET) fabrics were degraded with ethylene glycol to produce bis(2-hydroxyethyl) terephthalate(BHET). In order to maximize the utilization ratio of ethylene glycol(EG) in the degradation process, the alcoholysis solution was recovered by vacuum distillation before and after BHET recrystallization, and reused in the degradation of waste polymers instead of fresh EG. The alcoholysis solution and alcoholysis products were determined by infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis. The results show that alcoholysis solution recovered before BHET recrystallization can be recycled for 4-5 times. The EG recovery rate is 57.1%-89.2%, the BHET yield is 58.9%-70.3%. The recycling upper limit of the alcoholysis solution depends on the self-polymerization degree of EG. The alcoholysis solution recovered after BHET recrystallization can be recycled for 1-2 times. After reaching the use upper limit of the alcoholysis solution, the EG recovery ratio is reduced from 91.3% to 23.7%, and the BHET yield is reduced from 71.2% to 50.2%.
In order to realize the recycling of polyester resources, waste polyester(PET) fabrics were degraded with ethylene glycol to produce bis(2-hydroxyethyl) terephthalate(BHET). In order to maximize the utilization ratio of ethylene glycol(EG) in the degradation process, the alcoholysis solution was recovered by vacuum distillation before and after BHET recrystallization, and reused in the degradation of waste polymers instead of fresh EG. The alcoholysis solution and alcoholysis products were determined by infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis. The results show that alcoholysis solution recovered before BHET recrystallization can be recycled for 4-5 times. The EG recovery rate is 57.1%-89.2%, the BHET yield is 58.9%-70.3%. The recycling upper limit of the alcoholysis solution depends on the self-polymerization degree of EG. The alcoholysis solution recovered after BHET recrystallization can be recycled for 1-2 times. After reaching the use upper limit of the alcoholysis solution, the EG recovery ratio is reduced from 91.3% to 23.7%, and the BHET yield is reduced from 71.2% to 50.2%.
引文
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[9] 陈世明, 余天石, 葛明桥. 废弃聚酯醇解液中乙二醇回收工艺的研究[J]. 化工新型材料, 2015,43(2):40-42.CHEN Shiming, YU Tianshi, GE Mingqiao. Study on the recycling process of ethylene glycol in waste polyester alcoholysis liquid [J]. New Chemical Materials, 2015,43(2):40-42.
[10] 范金龙, 龚敏, 侯肖,等. 3A21铝合金在乙二醇水溶液中的腐蚀行为[J]. 腐蚀与防护, 2014, 35(11):1116-1121.FAN Jinlong, GONG Min, HOU Xiao, et al. Corrosion behavior of 3A21 aluminum alloy in ethylene glycol-water solution [J]. Corrosion & Protection, 2014, 35(11):1116-1121.
[11] LI M, HUANG Y, YU T, et al. Chemical recycling of waste poly(ethylene terephthalate) fibers into azo disperse dyestuffs [J]. Rsc Advances, 2014, 4:46476-46480.
[12] GHAEMY M, MOSSADDEGH K. Depolymerisation of poly(ethylene terephthalate) fibre wastes using ethylene glycol[J]. Polymer Degradation & Stability, 2005, 90(3):570-576.
[13] 陈世明, 余天石, 吕亚淑,等. 回收利用聚酯醇解废液降解PET聚酯研究[J]. 化工新型材料, 2016(1):244-246.CHEN Shiming, YU Tianshi, Lü Yashu, et al. Study on the degradation of PET polyester by using the waste polyester alcoholysis liquid [J]. New Chemical Materials, 2016(1):244-246.
[14] 李梦娟, 胡正勇, 陈亮,等. 不同废弃聚酯醇解产物分析与表征[J]. 化工新型材料, 2017(2):216-218.LI Mengjuan, HU Zhengyong, CHEN Liang, et al. Analysis and characterization of alcohol products of different waste polyesters [J]. New Chemical Materials, 2017(2):216-218.
[15] CHEN L, CHEN J. Kinetics of diethylene glycol formation from bishydroxyethyl terephthalate with zinc catalyst in the preparation of poly(ethylene terephthalate) [J]. Journal of Applied Polymer Science, 2015, 75(10):1229-1234.
[2] 吴宝宅, 武志云, 汪少朋,等. DMF在聚酯纺织品脱色中的应用研究[J]. 染整技术, 2013(6):11-14.WU Baozhai, WU Zhiyun, WANG Shaopeng,et al. Research on application of DMF for decolorization of polyester textiles [J]. Textile Dyeing and Finishing Journal, 2013(6):11-14.
[3] 甘胜华,严宏明,李现顺,等.废PET纺织品回收再利用技术工业化研究[J]. 聚酯工业,2012,25(1): 18 -20.GAN Shenghua, YAN Hongming, LI Xianshun, et al. Industrialization of waste PET textile recycling technology [J]. Polyester Industry,2012,25(1): 18 -20.
[4] 王少博. PET聚酯的乙二醇解聚与再生共聚研究[D]. 上海:东华大学, 2016:2-17.WANG Shaobo. Study on the poly(ethylene terephthalate) recycling via glycolysis and copolycondensation [D]. Shanghai: Donghua University, 2016:2-17.
[5] CAPELETTI M R, PASSAMONTI F J. Optimization of reaction parameters in the conversion of PET to produce BHET [J]. Polymer Engineering & Science, 2018, 58(9): 1500-1507.
[6] SHARMA V, PARASHAR P, SRIVASTAVA P, et al. Recycling of waste PET-bottles using dimethyl sulfoxide and hydrotalcite catalyst[J]. Journal of Applied Polymer Science, 2013, 129(3):1513-1519.
[7] 吕亚淑, 余天石, 郑佳,等. 回收利用涤纶中试醇解废液再降解聚酯PET[J]. 功能材料, 2016, 47(2):2258-2262.LV Yashu, YU Tianshi, ZHENG Jia, et al. Recycling polyester alcohol solution waste liquid to degrade polyester PET [J]. Function Materials, 2016, 47(2):2258-2262.
[8] 赵明宇, 张晨曦, 赵国樑,等. 废旧涤棉混纺织物的循环醇解工艺研究[J]. 合成纤维工业, 2016, 39(1):15-18.ZHAO Mingyu, ZHANG Chenxi, ZHAO Guoliang, et al. Study on cyclic alcoholysis of waste polyester/cotton blend fabric [J]. China Synthetic Fiber Industry, 2016, 39(1):15-18.
[9] 陈世明, 余天石, 葛明桥. 废弃聚酯醇解液中乙二醇回收工艺的研究[J]. 化工新型材料, 2015,43(2):40-42.CHEN Shiming, YU Tianshi, GE Mingqiao. Study on the recycling process of ethylene glycol in waste polyester alcoholysis liquid [J]. New Chemical Materials, 2015,43(2):40-42.
[10] 范金龙, 龚敏, 侯肖,等. 3A21铝合金在乙二醇水溶液中的腐蚀行为[J]. 腐蚀与防护, 2014, 35(11):1116-1121.FAN Jinlong, GONG Min, HOU Xiao, et al. Corrosion behavior of 3A21 aluminum alloy in ethylene glycol-water solution [J]. Corrosion & Protection, 2014, 35(11):1116-1121.
[11] LI M, HUANG Y, YU T, et al. Chemical recycling of waste poly(ethylene terephthalate) fibers into azo disperse dyestuffs [J]. Rsc Advances, 2014, 4:46476-46480.
[12] GHAEMY M, MOSSADDEGH K. Depolymerisation of poly(ethylene terephthalate) fibre wastes using ethylene glycol[J]. Polymer Degradation & Stability, 2005, 90(3):570-576.
[13] 陈世明, 余天石, 吕亚淑,等. 回收利用聚酯醇解废液降解PET聚酯研究[J]. 化工新型材料, 2016(1):244-246.CHEN Shiming, YU Tianshi, Lü Yashu, et al. Study on the degradation of PET polyester by using the waste polyester alcoholysis liquid [J]. New Chemical Materials, 2016(1):244-246.
[14] 李梦娟, 胡正勇, 陈亮,等. 不同废弃聚酯醇解产物分析与表征[J]. 化工新型材料, 2017(2):216-218.LI Mengjuan, HU Zhengyong, CHEN Liang, et al. Analysis and characterization of alcohol products of different waste polyesters [J]. New Chemical Materials, 2017(2):216-218.
[15] CHEN L, CHEN J. Kinetics of diethylene glycol formation from bishydroxyethyl terephthalate with zinc catalyst in the preparation of poly(ethylene terephthalate) [J]. Journal of Applied Polymer Science, 2015, 75(10):1229-1234.
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