Development of a catalytic dehalogenation (Cl,Br) process for municipal waste plastic-derived oil

Dehalogenation is a key technology in the feedstock recycling of mixed halogenated waste plastics. In this study, two different methods were used to clarify the effectiveness of our proposed catalytic dehalogenation process using various carbon composites of iron oxides and calcium carbonate as the catalyst/sorbent. The first approach (a two-step process) was to develop a process for the thermal degradation of mixed halogenated waste plastics, and also develop dehalogenation catalysts for the catalytic dehydrochlorination of organic chlorine compounds from mixed plastic-derived oil containing polyvinyl chloride (PVC) using a fixed-bed flow-type reactor. The second approach (a single-step process) was the simultaneous degradation and dehalogenation of chlorinated (PVC) and brominated (plastic containing brominated flame retardant, HIPS–Br) mixed plastics into halogen-free liquid products. We report on a catalytic dehalogenation process for the chlorinated and brominated organic compounds formed by the pyrolysis of PVC and brominated flame retardant (HIPS–Br) mixed waste plastics [(polyethylene (PE), polypropylene (PP), and polystyrene (PS)], and also other plastics. During dehydrohalogenation, the iron- and calcium-based catalysts were transformed into their corresponding halides, which are also very active in the dehydrohalogenation of organic halogenated compounds. The halogen-free plastic-derived oil (PDO) can be used as a fuel oil or feedstock in refineries.     

Kinematics of the unrestrained vehicle occupants in side-impact crashes

A test series involving direct right-side impact of a moving wall on unsupported, unrestrained cadavers with no arms was undertaken to better understand human kinematics and injury mechanisms during side impact at realistic speeds. The tests conducted provided a unique opportunity for a detailed analysis of the kinematics resulting from side impact. Specifically, this study evaluated the 3-dimensional (3D) kinematics of 3 unrestrained male cadavers subjected to lateral impact by a multi-element load wall carried by a pneumatically propelled rail-mounted sled reproducing a conceptual side crash impact. Three translations and 3 rotations characterize the movement of a solid body in the space, the 6 degrees of freedom (6DoF) kinematics of 15 bone segments were obtained from the 3D marker motions and computed tomography (CT)-defined relationships between the maker array mounts and the bones. The moving wall initially made contact with the lateral aspect of the pelvis, which initiated lateral motion of the spinal segments beginning with the pelvis and moving sequentially up through the lumbar spine to the thorax. Analyzing the 6DoF motions kinematics of the ribs and sternum followed right shoulder contact with the wall. Overall thoracic motion was assessed by combining the thoracic bone segments as a single rigid body. The kinematic data presented in this research provides quantified subject responses and boundary condition interactions that are currently unavailable for lateral impact.     

Systematic Biases in Measured PM10 Values with U.S. Environmental Protection Agency-Approved Samplers at Owens Lake,California

ABSTRACT

From 1993 through 1998, Wedding or Graseby high-volume PM₁₀ samplers were collocated with tapered element oscillating microbalance (TEOM) samplers at three sites at Owens Lake, CA. The study area is heavily impacted by windblown dust from the dry Owens Lake bed, which was exposed as a result of water diversions to the city of Los Angeles. A dichotomous (dichot) sampler and three collocated Partisol samplers were added in 1995 and 1999, respectively. U.S. Environmental Protection Agency (EPA) operating procedures were followed for all samplers, except for a Wedding sampler that was not cleaned for the purpose of this study. On average, the TEOM and Partisol samplers agreed to within 6%, and the dichot, Graseby, and Wedding samplers measured lower PM₁₀ concentrations by about 10, 25, and 35%, respectively. Surprisingly, the “clean” Wedding sampler consistently measured the same concentration as the “dirty” Wedding sampler through 85 runs without cleaning. The finding that the Graseby and Wedding high-volume PM₁₀ samplers read consistently lower than the TEOM, Partisol, and dichot samplers at Owens Lake is consistent with PM₁₀ sampler comparisons done in other fugitive dust areas, and with wind tunnel tests showing that sampler cut points can be significantly lower than 10 um under certain conditions. However, these results are opposite of the bias found for TEOM samplers in areas that have significant amounts of volatile particles, where the TEOM reads low due to the vaporization of particles on the TEOM's heated filter. Coarse particles like fugitive dust are relatively unaffected by the filter temperature. This study shows that in the absence of volatile particles and in the presence of fugitive dust, a different systematic bias of up to 35% exists between samplers using dichot inlets and high-volume samplers, which may cause the Graseby and Wedding PM₁₀ samplers to undermeasure PM₁₀ by up to 35% when the PM₁₀ is predominantly from coarse particulate sources.     

Individual and simultaneous degradation of brominated high impact polystyrene and brominated acrylonitrile-butadiene-styrene and removal of heteroelements (Br,N, and O) from degradation oil by multiphase catalytic systems

Brominated high-impact polystyrene (HIPS-Br), which contained decabromodiphenyl ether flame retardant, and brominated acrylonitrile butadiene styrene (ABS-Br), which contained bromine-containing epoxy-type flame retardant, were degraded at 450°C individually and in a 1/1 mixture by a thermal and catalytic procedure using folded sheet mesoporous (FSM) and ZSM-5 zeolite in liquid phase contact mode. The two polymers produced similar degradation oils but at a higher yield for HIPS-Br. However, the composition and distribution of Br-, N-, and O-containing compounds depended on the type of flame retardant in HIPS-Br and ABS-Br. Multiphase catalytic systems consisting of FSM in liquid phase contact mode and various CaH-, FeO-, CoMo-, and NiMo-based catalysts, or combinations of these catalysts, in vapor phase contact mode were used to decrease the amount of heteroatoms (Br, N, and O) in the degradation oils. Each system gave particular results in terms of mass balance and concentrations of heteroatoms. A FSM (liquid phase contact)/CaHC (vapor phase contact) combination was the best catalytic system to remove Br-, N-, and O-containing compounds from degradation oils.     

Cervical vertebral motions and biomechanical responses to direct loading of human head

There is little known data characterizing the biomechanical responses of the human head and neck under direct head loading conditions. However, the evaluation of the appropriateness of current crash test dummy head-neck systems is easily accomplished. Such an effort, using experimental means, generates and provides characterizations of human head-neck response to several direct head loading conditions. Low-level impact loads were applied to the head and face of volunteers and dummies. The resultant forces and moments at the occipital condyle were calculated. For the volunteers, activation of the neck musculature was determined using electromyography (EMG). In addition, cervical vertebral motions of the volunteers have been taken by means of X-ray cineradiography. The Ethics Committee of Tsukuba University approved the protocol of the experiments in advance. External force of about 210 N was applied to the head and face of five volunteers with an average age of 25 for the duration of 100 msec or so, via a strap at one of four locations in various directions: (1) an upward load applied to the chin, (2) a rearward load applied to the chin without facial mask, (3) a rearward load applied to the chin with the facial mask, and (4) a rearward load applied to the forehead. The same impact force as those for the human volunteers was also applied to HY-III, THOR, and BioRID. We found that cervical vertebral motions differ markedly according to the difference in impact loading condition. Some particular characteristics are also found, such as the flexion or extension of the upper cervical vertebrae (C0, C1, and C2) or middle cervical vertebrae (C3-C4), showing that the modes of cervical vertebral motions are markedly different among the different loading conditions. We also found that the biofidelity of dummies to neck response characteristics of the volunteers at the low-level impact loads is in the order of BioRID, THOR, and HY-III. It is relevant in this regard that the BioRID dummy was designed for a low-severity impact environment, whereas THOR and HY-III were optimized for higher-severity impacts.     

Voltammetric response of ferroceneboronic acid to diol and phenolic compounds as possible pollutants

A voltammetric determination of possible organic pollutants such as diol and phenolic compounds in water was studied using ferroceneboronic acid (FBA) as a redox-active marker. A cyclic voltammogram of FBA exhibited a pair of oxidation and reduction peaks at 230 and 170 mV at pH 7.0, respectively, while another pair of redox peaks was observed in the presence of diol or phenolic compounds tested. The results were rationalized based on the formation of boronate esters of FBA with the added compounds. The changes in the redox peak currents were dependent on the concentration of the additives, suggesting a usefulness of FBA in the electrochemical determination of these compounds in water.     

Point-of-use water disinfection using UV light-emitting diodes to reduce bacterial contamination

The treatment process described in this research explores the impact of exposing water samples containing fecal coliforms to the radiation produced by single ultraviolet (UV) light-emitting diodes (LEDs) operating at 265 nm. UV LEDs are long lasting, compact in size and produce more efficient light output than traditional mercury-vapour bulbs, making them ideal for application in point-of-use disinfection systems, such as in remote areas. In this study, contaminated water samples containing either a pure culture of Escherichia coli or tertiary effluent from the City of Regina Wastewater Treatment Plant were used to study the application and efficiency of using UV LEDs for water disinfection. The results indicate that bacterial inactivation was achieved in a time-dependent manner, with 1- and 2.5-log E. coli reductions in water following 20 and 50 min of UV LED exposure, respectively. Ultraviolet radiation was less effective in reducing coliform bacteria in wastewater samples due to the elevated turbidity levels. Further work remains to be completed to optimize the application of UV LEDs for point-of-use disinfection systems; however, the results from this study support that bacterial inactivation using UV LEDs is possible, meriting further future technological development of the LEDs.     

Study on dechlorination technology for municipal waste plastics containing polyvinyl chloride and polyethylene terephthalate

It is necessary to remove chlorine efficiently from municipal waste plastics (MWP) that contain polyvinyl chloride (PVC) and other plastics containing chlorine. In this article we consider thermal degradation liquefaction technology. In Japan, the chlorine content of reclamation oil products must be kept below 100 ppm owing to the quality standard for pyrolysis oil. Liquefaction dechlorination technology for MWP is still an important issue to study. The twin-screw extruder that has been developed as dechlorination technology for blast furnaces and coke ovens has a shorter residence time for dechlorination than other dechlorination technologies. In this article, we used a single-screw extruder for the dechlorination process because it also has a short residence time. Experiments on the dechlorination process were carried out by using a single-screw extruder to assess its dechlorination performance. Practical use of the single-screw was demonstrated by the operation of a commercial oil reclamation plant operated by Sapporo Plastic Recycle Co., Ltd. (SPR). Moreover, an investigation of cascade recycling was carried out in 2008 in which material recycle wastes were mixed with MWP and processed by chemical recycling (liquefaction). It was demonstrated that cascade recycling is an efficient recycling combination and contributes to local feedstock recycling. However, it was shown that MR wastes affect the quality of the reclamation oil when they make up more than 40% of the feed mix. If the quantity of MR wastes is kept below 40%, the reclamation oil is able to meet the quality standard. The SPR plant can be operated safely and in a stable manner.