废聚酯材料化学解聚研究进展

综述了近年来国内外废聚酯材料的酸性水解法、碱性水解法、中性水解法、甲醇醇解法、乙二醇醇解法、异辛醇醇解法、超临界水解法、超临界醇解法和离子液体环境下的废聚酯化学解聚的研究进展.对离子液体化学解聚废聚酯的前景进行了展望.     

从副产物和废水中回收和纯化乙二醇

正GlyEco公司开发出从多种工业副产品和废水中回收提纯乙二醇的工艺,生产出的乙二醇符合用于生产纯净级防冻液的ASTM国际标准组织规格。目前的乙二醇回收工艺使用的原料是废弃防冻液,来源紧缺且相对昂贵,且回收得到的乙二醇一般不具有顶级牌号所需的纯度。GlyEco公司的工艺不仅能从废弃防冻液中回收乙二醇,也可以利用几种低成本工业副产品和废水。这些废水含有聚对苯二甲酸乙二醇酯塑料、环氧乙烷医用灭菌剂、飞机除冰液及其他产品生产中产生的副产品。     

废聚酯用品回收技术获成功

日本帝人公司研制成功从废聚酯用品回收高纯度对苯二甲酸二甲酯(DMT)和乙二醇(EG)的化学回收技术。 该技术可回收利用与其他材料混合的制成品或使用了添加剂、加工剂的制成品,得到的产品与未用过的DMT、EG产品纯度相同。 据报道,该公司目前正在改造其德山事业所的旧DMT设备,以建成年生产能力为3万吨的回收专用设备。预计这些设备可在2002年度投产。 帝人公司称,它目前主要以聚对苯二甲酸乙二醇酯)PET)瓶为回收对象,并将继续考虑利用聚酯纤维、聚酯薄膜等,公司用该技术回收的DMT等将全部自用消化。 据介绍,这项技术是将使用后的聚酯瓶粉碎、洗净,经解聚工序分离工序后,进入酯交换和重结晶工序、DMT分离工序及精制工序,精制后的DMT再经反应,得到高纯度对苯二甲酸(PTA),再生DMT纯度达99.99%,与未曾用过的纯品质量相同。 (汪硕)     

聚乳酸解聚方法研究进展

综述了近年来国内外关于聚乳酸的热解聚法和酸性水解法、碱性水解法、中性水解法、高温高压水解法、酶催化法、甲醇醇解法、正丁醇醇解法等化学解聚法的研究进展,并对聚乳酸在离子液体环境中进行化学解聚的可行性进行了探讨和展望。     

用废聚酯塑料制品生产1730聚酯绝缘漆

1730聚酯绝缘漆最早由西德 Beck公司研制成功 ,并用于 B级漆包线 (使用温度低于 1 30℃ ) ,现已有 5 0多年的使用历史。我国于 1 962年后将 B级绝缘材料大量用于机电工业 ,至今仍在使用。目前 ,国内外普遍以对苯二甲酸二甲酯单体为原料 ,经过与多元醇醇解、缩聚的工艺路线生产 1 730聚酯绝缘漆。我们以废聚酯塑料制品 (主要是废弃的矿泉水瓶 ,其化学成分是聚对苯二甲酸乙二醇酯 )为原料 ,经醇解、解聚一步完成 ,然后进行缩聚等工艺制得1 730聚酯绝缘漆。研究了原料配比、醇解温度和反应时间、缩聚反应温度、真空度等工艺参数对产品质量的…     

水解法去除氯提咖啡因废水中氯仿的研究

介绍了用水解法去除氯提咖啡因废水中氯仿的实验方法和结果。存 pH12.54和95℃恒温条件下水解1小时,可使氯仿浓度由16.08毫克/升降至0.5毫克/升以下。通过对氯仿水解反应过程的动力学研究,为有效地去除氯提咖啡因废水中的氯仿,提供了适宜的工艺条件。     

废铜催化剂的综合利用

研究了以湿法回收利用废铜催化剂中的铜、锌制取氧化亚铜和氧化锌的原理以及最佳工艺条件。该工艺可同槽进行浸取、蒸氨、还原、中和水解等操作,生产成本低,产品质量好,工艺过程中无三废排放,具有很好的综合效益。     

氮肥工业中氨氮废水治理技术进展

介绍了氮肥厂对合成氨低温变换工艺冷凝液和尿素解吸废水的回收处理方法。认为选用热力水解法处理尿素吸废水是可行的。     

利用耐高温高pH微生物处理聚酯废水

日本Ｔｏｒａｙ工业公司开发出一种新方法,用于处理聚酯纤维碱处理过程产生的废水。进行碱处理是为了改善聚酯的表观和柔软性。通过将其与氢氧化钠一起加热,聚酯纤维的表面水解。此过程产生的废水含有较高浓度的对苯二甲酸和乙二醇,且水量很大,在某些工厂,其水量要占总水量的９０％。目前这种废水的处理方法通常为活性污泥法。Ｔｏｒａｙ公司开发出的新方法是使用２种自然界存在的可在高温（５０℃）和高ｐＨ（ｐＨ９．０）条件下分解对苯二甲酸盐的细菌。进一步的研究还发现了另一种可在同样条件下降解乙二醇的细菌。在生物反应器中,…     

废旧聚酯织物原位反应增粘制备再生聚酯单丝研究

针对废旧聚酯织物杂质含量高、粘度波动大、再生产品附加值低的问题,采用原位反应增粘技术,通过“微醇解-自缩聚”工艺实现了废旧聚酯织物再生制备聚酯单丝。以聚酯泡泡料为原料,整个工艺过程包括熔融过滤、反应增粘、熔体输送和纺丝等工序,可实现再生聚酯单丝的连续化生产。研究对比了“微醇解-自缩聚”工艺过程各个阶段再生料的特性粘度和热性能,结果表明该工艺可提升泡泡料的特性粘度达到0.65 dL/g,热性能良好,满足纺丝要求,再生聚酯单丝可应用于生产聚酯拉链,产品性能满足标准QB/T 2173—2014要求。     

Evaluation of Poly(ethylene-terephthalate) Products of Chemical Recycling by Differential Scanning Calorimetry

Poly (ethylene-terephthalate), (PET) bottles waste was chemically recycled by glycolysis and hydrolysis. The depolymerization processes were carried out in different time intervals from 5 to 360 min, in two different molar ratios of PET/EG, 1:5 and 1:18 and at different temperatures. The PET glycolysis leads to formation of bis(2-hydroxy-ethyl)terephthalate (BHET) monomer and PET oligomers with hydroxyl and carboxyl end groups while PET hydrolysis is followed by formation of monomers terephthalic acid (TPA) and ethylene glycol (EG). Fractions of monomers and oligomers were further characterized by FTIR spectroscopy and by differential scanning calorimetry (DSC). The results show that DSC is successful method to describe the different structures of oligomers formed during chemical recycling of PET.     

The Chemical Recycling of PET in the Framework of Sustainable Development

In this investigation, all the techniques used in the chemical recycling of polyethylene terephthalate (PET) are critically reviewed according to the overall benefits together with the environmental surcharge that they cause. Those, which are consistent with the principles of sustainable development, are indicated. Experimental data are presented for the acid hydrolysis of PET and compared with previous results on the alkaline hydrolysis of PET with, or without, the use of a phase transfer catalyst. Overall material balances are carried out for the hydrolysis of PET. Finally, it can be postulated that recycling according to the scheme: is the only one within the framework of sustainable development. Therefore, the recycling of PET does not only serve as a partial solution to the solid waste problem but also contributes to the conservation of raw petrochemical products and energy.     

Chemical depolymerisation of PET complex waste: hydrolysis vs. glycolysis

The huge increase in the generation of post-consumer plastic waste has produced a growing interest in eco-efficient strategies and technologies for their appropriate management and recycling. In response to this, PROQUIPOL Project is focused on developing, optimizing and adapting feedstock recycling technologies as an alternative for management for the treatment of complex plastic waste. Among the different plastic wastes studied, PROQUIPOL Project is working on providing a suitable treatment to the highly colored and complex multilayered post-consumer waste fractions of polyethylene terephthalate (PET) by chemical depolymerisation methods. Glycolysis and alkali hydrolysis processes have been studied with the aim of promoting the transformation of PET into the bis(2-hydroxyethyl) terephthalate monomer and terephthalic acid, respectively. In both cases operational conditions such as temperature, reaction time, catalyst to PET rate and solvent to PET rate have been considered to optimize product yield, achieving values near to 90 % and monomer purities over 95 % in both processes. This paper presents results obtained for each treatment as well as a simplified comparison of technical, economic and environmental issues.     

Pet Waste Management by Chemical Recycling: A Review

The paper reviews the problem due to the use and disposal of synthetic polymers to the environment and its solutions; in particular poly (ethylene terphthalate). Wide spread application and non-biodegradability of the PET creates huge amounts of waste and disposal, tend to a serious problem. The most important cause for recycling and reprocessing the waste PET has arisen from the awareness and concern for environmental pollution. To manage this various methods of polymer recycling has been proposed. Among them chemical recycling, i.e. hydrolysis, methanolysis, glycolysis and aminolysis are reviewed in detail. Appropriate technology and waste disposal procedures based on the socio-economic aspect to solve this problem are suggested.     

Supercritical methanol for polyethylene terephthalate depolymerization: observation using simulator

To apply PET depolymerization in supercritical methanol to commercial recycling, the benefits of supercritical methanol usage in PET depolymerization was investigated from the viewpoint of the reaction rate and energy demands. PET was depolymerized in a batch reactor at 573 K in supercritical methanol under 14.7 MPa and in vapor methanol under 0.98 MPa in our previous work. The main products of both reactions were the PET monomers of dimethyl terephthalate (DMT) and ethylene glycol (EG). The rate of PET depolymerization in supercritical methanol was faster than that of PET depolymerization in vapor methanol. This indicates supercritical fluid is beneficial in reducing reaction time without the use of a catalyst. We depicted the simple process flow of PET depolymerization in supercritical methanol and in vapor methanol, and by simulation evaluated the total heat demand of each process. In this simulation, bis-hydroxyethyl terephthalate (BHET) was used as a model component of PET. The total heat demand of PET depolymerization in supercritical methanol was 2.35 x 10(6)kJ/kmol Produced-DMT. That of PET depolymerization in vapor methanol was 2.84 x 10(6)kJ/kmol Produced-DMT. The smaller total heat demand of PET depolymerization in supercritical methanol clearly reveals the advantage of using supercritical fluid in terms of energy savings.     

Alkaline hydrolysis of photovoltaic backsheet containing PET and PVDF for the recycling of PVDF

Recovering fluorine from end-of-life products is crucial for the sustainable production and consumption of fluorine-containing compounds because fluorspar, an important natural resource for fluorine, is currently at a supply risk. In this study, we investigated the feasibility of chemically recycling a fluorine-containing photovoltaic (PV) backsheet for fluoropolymer recycling. Herein, a PV backsheet consisting of laminated polyethylene terephthalate (PET) and polyvinylidene fluoride (PVDF) was treated with different concentrations of sodium hydroxide (NaOH) to hydrolyze the PET layer to water-soluble sodium terephthalate (Na₂TP) and to separate pure PVDF layer as a solid material. Optimized alkaline conditions (up to 10 M NaOH at 100 °C for 2 h) were determined, under which 87% of the PET layer could be decomposed without any significant deterioration of the PVDF layer. The hydrolysis kinetics of PET layer in NaOH could be explained by the modified shrinking-core model. Considering that the mass of end-of-life PV panels in Japan is estimated to increase to approximately 280,000 tons per year by 2036, PV backsheets are attractive candidates for fluoropolymer recycling, which can be effectively achieved using chemical recycling approach demonstrated in this study.

     

Effect of Recycling on Material Properties of Glass-filled Polyethylene Terephthalate

Recycled plastics are considered low performance materials because their properties are expected to decrease drastically with recycling. The objective of this study was to characterize a 15 wt.% glass filled polyethylene terephthalate (rPET-15GF) using six recycle generations and four recycle ratios. Mechanical properties such as tensile strength, elastic modulus, and percent elongation to failure of the PET composite were determined for various recycle generations and recycle ratios. Results show that the mechanical properties of rPET-15GF decrease slightly per recycle generation. In contrast, thermal properties of rPET-15GF were not at all affected by the recycling process. This data demonstrates that recycled glass filled PET can be used effectively to fabricate components without significantly affecting their mechanical performance.     

压裂返排液循环使用技术综述

综述了传统处理方法和深度处理方法两大类压裂返排液处理方法的特点和处理效率。介绍了对氧化破胶的压裂返排液和非氧化破胶的压裂返排液进行处理的方法和机理,以及返排液循环使用效果和性能检测的标准。指出研发含有高分子聚合物稠化剂的返排液循环使用工艺、高效便捷的压裂返排液循环使用工艺和新型可循环使用的压裂液体系等将是未来压裂返排液循环使用的发展方向。     

Synthesis of unsaturated polyester resin from glycolysed postconsumer PET wastes

The purpose of this study was to explore ways to extend the chemical recycling of poly(ethylene terephthalate) (PET) as a valuable feedstock for chemical processes. First, PET wastes were depolymerised using a glycolysis method in the presence of sodium carbonate, which is considered to be a less environmentally damaging option for a catalyst. Good yields of the monomer bis(2-hydroxyethyl) terephthalate (BHET) were obtained (80 %). Second, to develop an economically viable recycling programme for the reclaimed BHET, the conversion of purified BHET into unsaturated polyester resins (UPR) was studied. The recovered monomer was thus polyesterified with maleic anhydride and subsequently mixed with styrene monomer to prepare UPRs. The resins were casted by a crosslinking reaction using methyl ethyl ketone peroxide and cobalt 2-ethylhexanoate as the initiator and catalyst, respectively. The polyesterification reaction was followed by gel permeation chromatography. The curing process was studied by differential scanning calorimetry and infrared spectroscopy. The cured resin was subjected to various characterisation methods in order to determine its chemical, physical and mechanical properties. Resins with suitable properties for commercial application were obtained.     

The consumption and recycling collection system of PET bottles: A case study of Beijing,China

After studying the recycling collection system of polyethylene terephthalate (PET) bottles worldwide, the authors conducted an intercept survey in Beijing. Two separate questionnaires were issued, one questionnaire to PET bottle consumers and one to PET bottle recyclers. In this study, consumers are defined as people that consume PET-bottled beverages in their daily life. Recyclers were defined as those involved in the collection and recycling of PET bottles. These include scavengers, itinerant waste buyers, small community waste-buying depots, medium/large redemption depots, and recycling companies. In total, 580 surveys were completed, including 461 by consumers and 119 by recyclers. The authors found that consumption of PET bottles in Beijing was nearly 100,000 tonnes in 2012. Age, occupation, gender, and education were identified as significant factors linked to PET-bottled beverage consumption, while income was not a significant factor. 90% Of post-consumed PET bottles were collected by informal collectors (i.e., scavengers and itinerant waste buyers). The survey also found that nearly all PET bottles were reprocessed by small factories that were not designed with pollution control equipment, which allows them to offer higher prices for waste recyclable bottles. As Beijing is trying to build a formal recycling collection system for recyclables, subsidies should be given to the formal recycling sector rather than being charged land use fees, and attention should also be given to informal recyclers that make their living from the collection of recyclables. Informal and formal sectors may work together by employing the scavengers and itinerant waste buyers for the formal sectors. In addition to the recycling of PET bottles, concern should also be allocated to reduce consumption, especially among young people, as they, compared to other groups, have a stronger demand for PET-bottled beverages and will be the main body of society.