Synthesis, Characterization, and Hydrolytic Degradation of Copolymers of 2-Methylene-1,3-dioxepane with Ethylene and with Styrene

2-Methylene-1,3-dioxepane (MDP) was copolymerized with ethylene (E) at a pressure of approximately 1000 psi and a temperature of approximately 70°C with AIBN as the free radical initiator. The copolymers obtained, poly(MDP-co-E), were characterized by elemental analysis, IR, ¹H-NMR and ¹³C-NMR spectroscopy, DSC, and GPC. The copolymers contained 2–15 mol% ester units. MDP was also copolymerized with styrene (S) at 120°C with di-t-butyl peroxide as the initiator to prepare the copolymer, poly(MDP-co-S). The number-average molecular weights of both types of copolymers were in the range of 6000 to 11,000, and the weight-average molecular weights were in the range of 9000 to 17,000. The melting temperatures of poly(MDP-co-E) decreased with increasing ester unit content in the copolymer. For the MDP-S copolymers, the glass transition temperatures decreased with increasing ester unit content. Both poly(MDP-co-E) and poly(MDP-co-S) were degraded by methanolysis, and their molecular weights decreased by the expected amounts based on the ester unit content.     

Risk assessment method of polyethylene dust explosion based on explosion parameters

The explosion characteristic parameters of polyethylene dust were systematically investigated. The variations in the maximum explosion pressure (P_max), explosion index (K_st), minimum ignition energy (MIE), minimum ignition temperature (MIT), and minimum explosion concentration (MEC) of dust samples with different particle sizes were obtained. Using experimental data, a two-dimensional matrix analysis method was applied to classify the dust explosion severity based on P_max and K_st. Then, a three-dimensional matrix was used to categorize the dust explosion sensitivity based on three factors: MIE, MIT, and MEC. Finally, a two-dimensional matrix model of dust explosion risk assessment was established considering the severity and sensitivity. The model was used to evaluate the explosion risk of polyethylene dust samples with different particle sizes. It was found that the risk level of dust explosion increased with decreasing particle size, which was consistent with the actual results. The risk assessment method can provide a scientific basis for dust explosion prevention in the production of polyethylene.     

Co-pyrolysis of oil sludge with hydrogen-rich plastics in a vertical stirring reactor: Kinetic analysis,emissions, and products

● Collaborative treatment of plastics and OS was established to improve oil quality. ● PE addition successfully improved OS pyrolysis process by deploying H/C_eff ratio. ● Higher H/C_eff ratio promoted cracking to obtain more gas and light oil fractions. ● The degradation of PE and OS was promoted each other under their temperature range. Pyrolysis is an effective method to treat oily sludge (OS) due to its balance between oil recovery and nonhazardous disposal. However, tank bottom OS contains a high content of heavy fractions, which creates obstacles for pyrolysis due to the high activation energy. The incomplete cracking of macromolecules and secondary polymerization decreases the oil quality and causes coking during the operation process. This study introduced polyethylene (PE) into OS to deploy the H/C_eff ratio of feedstocks for pyrolysis. A strong interaction between OS and PE during copyrolysis could be observed from the TG/DTG curves. PE tightly participated in OS degradation, while OS also promoted PE degradation at high temperature. Apparent pits were generated in solid residues from copyrolysis, which was attributed to the uniform and violent gas release. In addition to HCN, other nitrogenous and sulphurous pollutants were inhibited. Accordingly, more gas products were attained after PE addition with more value-added compositions of alkanes and alkenes. Although the oil yield decreased after PE addition, the oil products from copyrolysis possessed higher heating values and higher contents of light fractions with short chains as well as paraffins. Consequently, copyrolysis of OS and PE significantly improved the pyrolysis process and resulted in high oil quality.     

聚乙烯塑料类固体废弃物热裂化研究

在反应温度455-495℃,氢气压力0.1～4.0MPa和反应时间2～12h的范围内,就聚乙烯塑料类固体废弃物热裂化时温度、压力和反应时间的影响以及不同反应条件下产物的碳数分布、馏程变化进行了探讨,得出适合于生产柴油馏分的反应条件是温度475℃,常压或低压,反应时间4h等。     

Engine Performance and Emission Characteristics of Plastic Oil Produced from Waste Polyethylene and Its Blends with Diesel Fuel

The overall objective of this study was to explore the utility of waste plastics as a potential source of diesel fuel. An experimental study was conducted to evaluate the use of various blends of plastic oil produced from waste polyethylene (WPE) with diesel fuel (D). WPE was degraded thermally and catalytically using sodium aluminum silicate as a catalyst. The oil collected at optimum conditions (414°C–480°C range and 1 h reaction time) was fractionated at different temperatures and fuel properties of the fractions were measured. Plastic oil was blended with diesel fuel at the volumetric ratios of 5%, 10%, 15%, 20%, and 100%. Fuel properties of blends are found comparable with those of diesel fuel within the EN 590 Diesel Fuel standard and they can also be used as fuel in compression ignition engines without any modification. Engine performance and exhaust emission studies of 5% WPE-D (WPE5) blend were performed. Experimental results showed that carbon monoxide (CO) emission is decreased by 20.63%, carbon dioxide (CO₂) emission is increased by 3.34%, and oxides of nitrogen (NO_x) emission is increased by 9.17% with WPE-D (WPE5) blend compared to diesel fuel.     

Microtox assay to determine the toxicity of degradation products from degradable plastics

Six types of starch-polyethylene degradable plastics were evaluated for the release of water-soluble toxic compounds under accelerated degradation conditions. A plastic strip (2.5×15.2 cm) was placed in a 250-ml Erlenmeyer flask with 100 ml of ASTM type I water with or without trace element solutions and shaken at 65°C and 110 rpm for 20 weeks in replicates of two. High temperature was used to accelerate the oxidative degradation of polyethylene. Plastic degradation was measured by loss of tensile strength, percentage elongation, strain energy, and weight-average molecular weight. The most rapid period of polyethylene thermal degradation was complete for most materials by day 28. Ten-milliliter aqueous samples were removed from each flask at days 1, 7, 28, 56, 84, and 140 (water volumes were maintained at 100 ml with fresh type I water), filtered through glass filters, then evaluated by using the Microtox Toxicity Analyzer (Microbics Corporation, Carlsbad, CA). No water-soluble toxic compounds were detected during the period of rapid film degradation. Toxicity was observed at day 28 for one film and at day 84 for all films, which could possibly correlate with the release of small oxidative compounds such as formaldehyde and acetaldehyde. Because of the sensitivity of this assay, positive results must be confirmed by otherin vitro studies.Journal Paper No. J-14851 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa. Projects No. 2889 and 0178.     

Solid phase microextraction (SPME) as an effective means to isolate degradation products in polymers

A new sample preparation technique, solid phase microextraction (SPME), was compared with direct headspace-GC-MS with respect to the type and amount of identified compounds. Three types of LDPE films containing photosensitising additives according to the Scott-Gilead patents and pure LDPE were used as model substances. The polyethylene films were thermally aged at 80‡C after the induction period was surpassed by subjecting the materials to 100 h of UV radiation. The new SPME method was developed using nonpolar poly(dimethylsiloxane) and polar carbowax fibers to extract the low molecular weight products formed in the polyethylene films during aging. Many more products were identified after SPME followed by GC-MS than after direct headspace-GC-MS of the samples. The SPME method allowed the identification of homologous series of carboxylic acids, ketones, and furanones, while direct headspace-GC-MS identified only a few carboxylic acids (C1-C6) and small amounts of some ketones and furanones. In general, SPME was more effective in extracting less volatile products, and in particular, the polar carbowax fiber identified also C7-C12 carboxylic acids and 4-oxopentanoic acid. By SEC and FTIR we confirmed that the number and amount of former degradation products correlated well with the decrease in molecular weights and the amount of formed carbonyl compounds.     

Thermal analysis of polyethylene glycol: evolved gas analysis with ion attachment mass spectrometry

The thermal decomposition of polyethylene glycol was investigated by using a technique combining evolved gas analysis (time-resolved pyrolysis) with ion-attachment mass spectrometry. This technique allows the detection of intact pyrolysis products and, therefore, offers the opportunity for direct real-time monitoring of thermal by-products. Unstable products can thus be detected; for instance, many highly reactive organic peroxides, such as CH₃OOH and HOCH₂OOH, were found in this study. Classification analysis revealed 10 major compositional formulas among the product species: C_nH_2n+2O, C_nH_2n+2O₂, C_nH_2n+2O₃, C_nH_2n+2O₄, C_nH_2n+2O₅, C_nH_2n+2O₆, C_nH_2n+2O₇, C_nH_2nO, C_nH_2nO₂, and HO(CH₂CH₂O)_nH ethylene glycol oligomers. The Li⁺ ion adduct mass spectra showed a characteristic profile in terms of both the appearance of unique components and the distribution of pyrolysis products. Among the products of the thermal decomposition of PEG, formaldehyde (HCHO) and organic peroxides were particularly interesting. Formaldehyde, one of the 10 most abundant products, is a known human carcinogen. The detection of peroxides suggests that they may form during the incineration of PEG, which may have important environmental implications. The existence of peroxide products may have implications for chemical evolution in incinerator systems.     

配水管网中卤乙酸的研究

液氯消毒导致给水输配管网中产生消毒副产物对人体健康造成危害的问题引起了人们越来越多的关注。在对北方某城市配水管网水质大量调查的基础上,分析了卤乙酸与温度、余氯、氨氮、UV254等主要水质指标在配水管网中的变化规律。     

Integrating industrial ecology principles into a set of environmental sustainability indicators for technology assessment

This paper focuses on the environmental component of sustainability of technology, taking into account the role of industrial ecology. Assessment of environmental sustainability of technology traditionally focuses on immediate impact of technology on the environment through quantifying resource extraction and generated emissions. However, technology does not only exchange materials with the environment but also with the industrial society as a whole, the so-called industrial metabolism. A higher compatibility of a specific technology with the industrial system, as studied in industrial ecology, can result in lower resource extraction and reduced waste emission, indirectly contributing to a better environmental sustainability.Starting from the considerations above and based on the second law of thermodynamics, the paper presents a set of five environmental sustainability indicators for the assessment of products and production pathways, integrating industrial ecology principles. The indicators, all scaled between 0 and 1, take into account: (1) renewability of resources; (2) toxicity of emissions; (3) input of used materials; (4) recoverability of products at the end of their use; (5) process efficiency.The applicability of the elaborated set of indicators is illustrated for different production pathways of alcohols (petrochemical and oleochemical based), polyethylene end-of-life options and electricity production from non-renewable (natural gas and fossil oil) and renewable resources (hydropower, photovoltaic conversion of solar irradiation).