Thermal Degradation Mechanism of Low-Density Polyethylene Plastic Wastes in Cyclohexane

The thermal LDPE degradation mechanism harnessing a high-pressure autoclave surrounded by a furnace was investigated in this work. Rates of formation of gas, liquid, and solid during degradation of PE plastic wastes in cyclohexane as solvent at 400 and 425°C have been experimentally determined. Four reaction mechanisms have been proposed and tested to estimates of gas, liquid, and solid. Proposed mechanisms are based on the assumption that the reactions are pseudo-first-order with respect to the reacting species. Pseudo-first-order rate constants for each of the indicated mechanistic steps have been calculated by nonlinear regression analysis. The best fit was obtained by model 2 (pure parallel reaction mechanism), and its activation energy was determined.     

Catalytic upgrading of higher 1-alkenes from polyethylene thermal cracking by modified Wacker oxidation

The economic success of feedstock recycling procedures for plastic wastes is increasingly demanding the conversion of the starting residue into more valuable chemicals. Thermal cracking of polyethylenes leads to the preparation of equimolar mixtures of n-paraffins and 1-alkenes within the C₂–C₁₀₀ range. These 1-olefins can be catalytically upgraded by selective oxidation processes to more valuable products (e.g., ketones and fatty acids) with different uses such as polar waxes, cetane improvers, varnishes, and printer inks. The results obtained on oxidation in a modified Wacker system of a model 1-olefin (1-dodecene) as well as of a distillate cut (C₁₀–C₂₅) of the product from the thermal cracking of urban polyethylene waste are described.     

Characterization of post-consumer polyolefin wastes by hyperspectral imaging for quality control in recycling processes

In this paper new analytical inspection strategies, based on hyperspectral imaging (HSI) in the VIS–NIR and NIR wavelength ranges (400–1000 and 1000–1700 nm, respectively), have been investigated and set up in order to define quality control logics that could be applied at industrial plant level for polyolefins recycling. The research was developed inside the European FP7 Project W2Plastics “Magnetic Sorting and Ultrasound Sensor Technologies for Production of High Purity Secondary Polyolefins from Waste”. The main aim of the project is the separation of pure polyethylene and polypropylene adopting an innovative process, the magnetic density separation (MDS). Spectra of plastic particles and contaminants resulting from post-consumer complex wastes and of virgin polyolefins have been acquired by HSI and by Raman spectroscopy. The classification results obtained applying principal component analysis (PCA) on HSI data have been compared with those obtained by Raman spectroscopy, in order to validate the proposed innovative methodology. Results showed that HSI sensing techniques allow to identify both polyolefins and contaminants. Results also demonstrated that HSI has a great potentiality as a tool for quality control of feed (identification of contaminants in the plastic waste) and of the two different pure polypropylene and polyethylene flow streams resulting from the MDS-based recycling process.     

Analysis of Products Generated from the Thermal and Catalytic Degradation of Pure and Waste Polyolefins using Py-GC/MS

The possibility of transforming waste plastics into valuable hydrocarbons via catalytic cracking and reforming is attracting increasing interest. Pyrolysis coupled with Gas Chromatographic separation and Mass Spectrometry detection (Py-GC/MS) has been used in this work to study the product selectivity of various catalysts in the conversion of pure and residual polyethylene samples into hydrocarbon products. Five acid solids of comparable aluminium contents but different textural and acid properties were tested as catalysts, including three zeolites (standard ZSM-5, nanocrystalline n-ZSM-5 and Beta) and two mesostructured solids (Al-MCM-41 and Al-SBA-15). Thermal cracking of the pure and residual polymers generated a similar range of products to each other, with a high proportion of linear paraffins and olefins of varying lengths. The presence of zeolitic materials resulted in complete elimination of heavy linear products, an increase in the light hydrocarbon fraction and a marked selectivity towards the formation of single-ring aromatic species, particularly benzene, toluene and xylene. Aromatic formation was particularly notable with the small crystal size n-ZSM-5 (aromatic selectivity up to 53.9%) and less marked in the case of standard ZSM-5 (up to 36.4%) and Beta zeolite (up to 35.0%). Mesostructured catalysts like Al-MCM-41 and Al-SBA-15 favoured the production of light C₂–C₅ hydrocarbons (up to 57.9%) while the formation of aromatic products was significantly lower than with zeolitic materials. The paper examines the extent and the causes for this product selectivity and discusses its connection with the acid and textural properties of each catalyst. It was also observed that, under the experimental conditions employed, the products generated were not significantly affected by the nature and origin of the polymers employed.     

Deactivation and regeneration of ZSM-5 zeolite in catalytic pyrolysis of plastic wastes

In this work, a study of the regeneration and reuse of ZSM-5 zeolite in the pyrolysis of a plastic mixture has been carried out in a semi-batch reactor at 440 °C. The results have been compared with those obtained with fresh-catalyst and in non-catalytic experiments with the same conditions. The use of fresh catalyst produces a significant change in both the pyrolysis yields and the properties of the liquids and gases obtained. Gases more rich in C3-C4 and H₂ are produced, as well as lower quantities of aromatic liquids if compared with those obtained in thermal decomposition. The authors have proved that after one pyrolysis experiment the zeolite loses quite a lot of its activity, which is reflected in both the yields and the products quality; however, this deactivation was found to be reversible since after regeneration heating at 550 °C in oxygen atmosphere, this catalyst recovered its initial activity, generating similar products and in equivalent proportions as those obtained with fresh catalyst.     

甲苯对铁屑降解三氯乙烯的影响

为了探讨甲苯仔任时铁屑降解三氯乙烯（TCE）的有效性及影响因素,考察了铁屑粒径、铁屑预处理方法及甲苯初始质量浓度对TCE降解效果的影响。实验结果表明：选用粒径0．35—0．83mm的铁屑较好;用0．05mol／L的盐酸清洗后的铁屑对TCE的降解效果好于未进行酸洗的铁屑对TCE的降解效果;当m（甲苯）：m（TCE）分别为0,1．2,10．3,18．6时,TCE降解的反应速率常数分别为0．0691,0．0595,0．0458,0．0361h^-1,半衰期分别为10．03,11．65,15．13,19．20h,即随着甲苯初始质量浓度的提高,TCE降解的反应速率常数变小,半衰期变长;铁屑对甲苯具有吸附作用,甲苯的初始质量浓度越高,甲苯吸附量越大。     

电气石对脱氯菌降解三氯乙烯的影响

以电气石作为环境微生物强化介质材料,协同以Dehalococcoides spp.为主体的脱氯混合菌群(简称脱氯菌)对水中的三氯乙烯(TCE)进行降解,探讨了电气石对降解效果的影响。实验结果表明:电气石可调节水溶液的p H使之趋向于中性并提高水溶液的电导率;在脱氯菌接种量为8%、电气石加入量为5.0 g/L的条件下降解20mg/L的TCE,84 h时TCE已全部降解,而未加电气石体系只降解了54.7%;外加电子供体甲醇和外加电气石均可明显提高脱氯菌对TCE的降解速率,且外加电气石的降解效果更好,说明电气石可能在促进微生物生长繁殖的同时也能为其提供合适的电子供体,这对降解地下水中的TCE具有重要意义。     

Effect of Degree of Substitution of Octenyl Succinate Starch on Enzymatic Degradation

Octenyl succinate starch of degree of substitution (ds) 0.03, 0.07, and 0.11 was synthesized in an aqueous medium. These compounds were then tested for the susceptibility to enzymatic degradation. The multiple-enzyme regime of -amylase, amyloglucosidase, and pullulanase was chosen for the evaluation. This combination of enzymes had been proven to degrade 99.5% of unmodified starch to glucose and hence was chosen for this study. It was found that even small amounts of subsituent caused a considerable decrease in the extent of degradation. The net extent of degradation decreased with increasing ds. Surprisingly, the amount of glucose from all three substituted substrates was quite similar, suggesting the effect small amounts of subtituent had on the enzymatic activity.     

二氧化钛的改性及其对降解水中有机污染物的促进作用

综述了TiO2光催化剂的改性方法及其对光催化降解水中有机污染物的促进作用,介绍了复合物、煅烧温度、掺杂量、掺杂金属离子的种类和浓度对TiO2光催化性能的影响。     

高频超声波降解4-氯酚的反应机理及试验研究

探讨了高频超声波（1.7MHz)降解4-氯酚的反应过程和反应机理，研究了高频超声波降解4-氯酚的效果及4-氯酚的初始浓度，高级氧化方法（AOPs)等因素对降解效果的影响。试验结果表明，高频超声波降解4-氯酚为一级反应，超声波空化效应在降解过程中起主导作用。超声波与其他氧化方法联用可大大提高降解效率。具有良好的工业应用前景。     

An accelerated laboratory study evaluating the disintegration rates of plastic films in simulated aquatic environments

Six plastic films were exposed to accelerated sunlight while in simulated aquatic environments to determine the effects of chemical composition and environment on the disintegration rates. An environment of UV light/no water was used as a control to determine if the microorganisms in the aquatic systems enhanced the breakdown of the plastic films. The disintegration rate of the plastics was determined by monitoring changes in selected physical properties. The plastics included two conventional plastics commonly used in packaging (LDPE and polystyrene) and four plastics enhanced to have more rapid breakdown in the environment (2% ECO, 10% ECO, PE with ketone graft, and PE with starch). The two ECO copolymers had a significantly faster loss of physical properties than the other plastics evaluated in this study. Degradation was influenced by environmental conditions. Those plastics that showed a change in physical properties had a greater change faster in the UV light/no water than in the environments where water was present. Plastics on the surface of the water showed a more rapid loss of properties than those samples partially or completely submerged. This can be attributed to decreased light intensity and the lack of heat buildup.     

微生物降解重油的初步研究

丛石油污染的土壤中筛选出一株假单胞菌,考察了其对重油的降解效果。降解18d,重油的降解率达到42．8％,饱和烃、芳香烃、胶质、沥青质的降解率分别为42．95％,43．85％,44．5％,5．55％;质量浓度2．5g／L的表面活性剂Tween-80可使重油的18d降解率达到51．0％;弱碱性条件有利于重油的生物降解;生物泥浆法处理重油污染的土壤,1kg土壤中重油质量100g,降解45d,重油的降解率达到38．85％。     

二氧化钛光催化降解甲醛反应动力学研究

以钛酸丁酯为前驱体，应用溶胶一凝胶法制备TiO2粉体和负载TiO2薄膜，考察了不同活化温度和活化时间对TiO2光催化降解甲醛性能的影响，并对TiO2薄膜光催化降解甲醛的反应动力学进行了研究。试验结果表明，在活化温度450℃、活化时间5h条件下，所得TiO2粉体及薄膜的光催化活性较好。不同初始浓度下甲醛光催化降解率与时间关系的动力学研究表明，一级反应动力学模型与试验数据拟合较好，方差R^2大于或等于0．99。     

催化臭氧氧化法降解2,4-二氯苯酚的研究

用自制的V—O型催化剂进行催化臭氧氧化2,4-二氯苯酚的实验。实验表明,臭氧发生器的放电功率为5200W、氧化时间为30min,较为有利于历程分析;以TiO2,SiO2,ZrO2作载体在氮气或氧气中焙烧制得的6种催化剂中,V-O／SiO2／O2型催化剂显示了较好的催化性能和活性;反应体系的pH越大,越利于氧化反应。通过催化剂吸附实验和在反应体系中加入一定量的自由基猝灭剂,初步探讨了其催化机理,即催化剂和臭氧反应生成了氧化性极强的羟基自由基。     

镰刀菌HJ01对对氯苯酚的降解特性

采用实验室分离的一株镰刀菌HJ01,以对氯苯酚(4-CP)为降解底物,以蔗糖为外加碳源,考察了蔗糖质量浓度、降解温度、初始pH对4-CP降解效果的影响,初步探讨了镰刀菌HJ01对4-CP的降解动力学和降解机理.实验结果表明:该菌株能以4-CP为惟一碳源和能源生长;在外加蔗糖为碳源,蔗糖质量浓度为3 g/L、降解温度为30℃、初始pH为8的条件下,50 mg/L4-CP能在6 d内被完全降解.以4-CP为惟一碳源和外加蔗糖下的降解动力学分别符合Haldane模型和一级动力学方程.     

Effects of Temperature and Relative Humidity on Polylactic Acid Plastic Degradation

Three high molecular weight (120,000 to 200,000 g mol^–1) polylactic acid (PLA) plastic films from Chronopol (Ch-I) and Cargill Dow Polymers (GII and Ca-I) were analyzed for their degradation under various temperature and relative humidity (RH) conditions. Two sets of plastic films, each containing 11 samples, were randomly hung in a temperature/humidity-controlled chamber by means of plastic-coated paper clips. The tested conditions were 28, 40, and 55°C at 50 and 100% RH, respectively, and 55°C at 10% RH. The three tested PLA films started to lose their tensile properties when their weight-average molecular weight (M _w) was in the range of 50,000 to 75,000 g mol^–1. The average degradation rate of Ch-I, GII, and Ca-I was 28,931, 27,361, and 63,025 M _w/week, respectively. Hence, GII had a faster degradation rate than Ch-I and Ca-I under all tested conditions. The degradation rate of PLA plastics was enhanced by the increase in temperature and relative humidity. This trend was observed in all three PLA plastics (Ca-I, GII, and Ch-I). Of the three tested films, Ch-I was the first to lose its mechanical properties, whereas Ca-I demonstrated the slowest loss, with mechanical properties under all tested conditions.     

Catalytic decomposition of hydrocarbon into hydrogen and carbon in a spouted-bed reactor as the second-stage reactor of a plastic recycling process

A two-stage process for the chemical recycling of plastics is proposed. In this process, which consists of two reactors, plastics are converted into hydrogen and carbon. In the first reactor, plastic chips are thermally decomposed into hydrocarbons. In the second reactor, the hydrocarbons formed in the first reactor are catalytically decomposed into carbon and hydrogen. In this study, in order to obtain basic data for the second reactor, propene was catalytically decomposed in a laboratory-scale spouted-bed reactor (600mm high, 21.6mm internal diameter, made of SUS304). The effect of the type of spouting medium used on the decomposition behavior of propene was investigated using four types of spouting medium (nickel-plated -alumina, palladium-plated -alumina, nickel-impregnated -alumina, and -alumina). The nickel-impregnated -alumina gave the best propene conversion and hydrogen yield.     

太阳能光催化降解法去除水中罗丹明染料的研究

在太阳光的紫外线辐射下，应用载有ＴｉＯ２薄层的平板式光催化反应器，进行了光催化降解法去除水中罗丹明染料的试验，结果表明，当紫外线辐射强度平均为３３Ｗ／ｍ＾２，反应时间为１８ｍｉｎ时，水中罗丹明染料浓度由１０ｍｇ／Ｌ降至０．０１ｍｇ／Ｌ，在室国家排放标准，探讨了太阳能光催化反应系统的改进方向及工业化应用的有关问题。     

两株柴油降解菌的性能研究

以0#柴油为惟一碳源,对两株柴油降解菌DS-Ⅰ菌和DS-Ⅲ菌降低液体表面张力的能力、柴油降解动力学及表面活性物质成分进行了研究。实验结果表明:DS-Ⅰ菌和DS-Ⅲ菌在生长过程中均可产生糖脂类生物表面活性物质,使发酵液表面张力降低;在11d的发酵时间内,DS-Ⅰ菌和DS-Ⅲ菌使发酵液中柴油的质量浓度从48.72m g/L分别降至16.64m g/L和9.17m g/L,柴油降解率分别为65.84%和81.18%,柴油降解速率分别为5.16m g/(L.d)和5.96m g/(L.d)。发酵液表面张力的降低与柴油的降解效果有显著的相关性。DS-Ⅲ菌在疏水性、对柴油的生长适应性和柴油降解速率等方面比DS-Ⅰ菌更好。     

超声光催化降解酸性粒子元青染料的研究

对超声波作用下的纳米TiO2光催化氧化法降角酸性粒子元青染料进行了研究。结果表明，超声波的引入提高了纳米TiO2光催化降解酸性粒子元青染料的降解率；降解率受反应时间、坡声波功率、空气流量的影响；添加少量的H2O2能够明显地提高酸性粒子元青染料的降解率。