Sampling and Analysis of Volatile Organic Compounds Evolved During Thermal Processing of Acrylonitrile Butadiene Styrene Composite Resins

Abstract

The evaluation of emissions of volatile organic compounds (VOCs) during processing of resins is of interest to resin manufacturers and resin processors. An accurate estimate of the VOCs emitted from resin processing has been difficult due to the wide variation in processing facilities. This study was designed to estimate the emissions in terms of mass of emitted VOC per mass of resin processed.

A collection and analysis method was developed and validated for the determination of VOCs present in the emissions of thermally processed acrylonitrile butadiene styrene (ABS) resins. Four composite resins were blended from automotive, general molding, pipe, and refrigeration grade ABS resins obtained from the manufacturers. Emission samples were collected in evacuated 6-L Summa canisters and then analyzed using gas chromatography/flame ionization detection/mass selective detection (GC/FID/MSD). Levels were determined for nine target analytes detected in canister samples, and for total VOCs detected by an inline GC/FID. The emissions evolved from the extrusion of each composite resin were expressed in terms of mass of VOCs per mass of processed resin. Styrene was the principal volatile emission from all the composite resins. VOCs analyzed from the pipe resin sample contained the highest level of styrene at 402 μg/g. An additional collection and detection method was used to determine the presence of aerosols in the emissions. This method involved collecting particulates on glass fiber filters, extracting them with solvents, and analyzing them using gas chromatography/mass spectrometry (GC/MS). No significant levels of any of the target analytes were detected on the filters.     

Characterization of semi-volatile organic compounds emitted during heating of nitrogen-containing plastics at low temperature

Because of recent volume increases, appropriate management of plastic recycling, which generates various organic compounds, is required to ensure the chemical safety of the processes. The processing temperature and resin type are the important factors determining both the efficiency of the processes and the emission of chemicals. Therefore, we studied the thermal degradation of various plastics at various temperatures from 70 to 300 °C under oxygen-present conditions to identify the semi-volatile organic compounds (SVOCs) emitted and to understand their thermal behaviors. The plastics examined were nitrogen-containing resins, such as polyamide 6, polyurethane, melamine formaldehyde, urea formaldehyde and acrylonitrile-butadiene-styrene. Major commodity plastics were also investigated for comparison. In total, more than 500 SVOCs were detected as emissions from plastics. While various nitrogen-containing SVOCs were detected from nitrogen-containing resins, the major commodity plastics released only these, which possibly were included as additives. These results indicate that the nitrogen atoms in the SVOCs emitted originated from the resins and additives, and not from ambient air at low temperature. As a result of the detection of raw materials, degradation chemicals and by-products of the polymers in the emissions, we found that the variation in chemical species is dependent on the resins. Additives were also emitted from all the resins, meaning that these chemicals were also released to the environment at the temperature examined. In most cases, the numbers and concentrations of SVOCs increased with increasing heating temperature. The variation of thermal behaviors of SVOCs was related to the origins and chemical species of SVOCs.     

离子交换法选择性回收污泥厌氧消化液中的磷

为探讨高效选择性回收污泥厌氧消化液中磷的离子交换方法,采用静态实验和动态实验研究了4种阴离子交换树脂（D213、D202、D301和DSQ）的磷回收性能,筛选了适合富磷污泥厌氧消化液选择性磷回收的高交换容量树脂。实验结果表明,D213、D202、D301和DSQ 4种树脂对正磷浓度为70 mg/L的厌氧消化液进行动态处理时,其最大穿透体积分别为3、7、17和90 BV;DSQ树脂磷交换容量远高于其他3种树脂,达到6 860 mg P/L湿树脂,是目前报道的高磷交换容量树脂的3~4倍;DSQ树脂能有效地抵抗厌氧消化液中有机质和硫酸根等阴离子的干扰;用NaOH溶液再生DSQ树脂并回收磷,磷洗脱率超过96%,洗脱液是高浓度含磷液,可作为磷矿石的优质替代品。研究表明,DSQ树脂是一种高效选择性分离磷的树脂,适用于污泥厌氧消化液的磷回收。     

Origins and biological accumulation of small plastic particles in fur seals from Macquarie Island

One hundred and sixty four plastic particles (mean length 4.1 mm) recovered from the scats of fur seals (Arctocephalus spp.) on Macquarie Island were examined. Electron micrographs of 41 of the plastic particles showed that none could be identified as plastic pellet feedstock from their shapes. Commonly, such pellets are cylindrical and spherical. Instead, all the 164 plastic particles from the seal scats were angular particles of 7 colors (feedstock particles are normally opaque or white) and could be classified into 2 categories: i) fragmented along crystal lines and likely to be the result of UV breakdown; and ii) worn by abrasion (where striations were clearly visible) into irregular shapes with rounded corners. White, brown, green, yellow and blue were the most common colors. In composition, they came from 5 polymer groups; polyethylene 93%, polypropylene 4%, poly(1-Cl-1-butenylene) polychloroprene 2%, melamine-urea (phenol) (formaldehyde) resin 0.5%, and cellulose (rope fiber) 0.5%. The larger groups are buoyant with a specific gravity less than that of seawater. These small plastic particles are formed from the breakdown of larger particles (fragments). Their origin seems to be from the breakdown of user plastics washed ashore and ground down on cobbled beaches. Certainly most particles (70%) had attained their final form by active abrasion. It is hypothesized that the plastic particles were washed out to sea and then selected by size and consumed by individuals of a pelagic fish species, Electrona subaspera, who in turn were consumed by the fur seals. Thus, the particles were accumulated both by the fish and the seals in the usual process of their feeding.     

Evaluation of heavy metal lability in polluted soils by a cation exchange batch procedure

A new extraction procedure with cationic exchange resins is proposed for the assessment of heavy metal lability in polluted soils. This method classifies soluble metal compounds in three levels according to their lability: very labile, moderately labile and non-labile. The concept of lability is based on the use of resins with different ability to interact with metals. The proposed procedure was applied to five samples of polluted soils. In the five soils, soluble Cd was found to be very labile, soluble Ni and Pb were mostly non-labile, Mn and Zn lability depended on the soil, while Cu had a fraction of moderately labile forms in four of the five soils. The resin extraction procedure was compared with the DTPA and CaCl2 extractions.     

Industrial plastic on the southern beaches of the Arabian Gulf and the western beaches of the Gulf of Oman

The increasing production and use of plastic in the Arabian Gulf combined with shipping and waste disposal practices, have increased the concentration of plastic particles on the sea's surface and beaches. The objective of this investigation was to provide an assessment of the abundance, distribution, potential sources and significance of industrial plastic on the western beaches of the United Arab Emirates on the Arabian Gulf and on the eastern beaches on the Gulf of Oman. The abundance of stranded plastic pellets was highly uneven. By early 1992 alarming levels of fresh plastic pellets were noticed on the Arabian Gulf beaches of the UAE. Large numbers of 25 kg sacks of white plastic spherules manufactured by (SABIC) in Jubail, Saudi Arabia were washed ashore. When compared to the west coast on the Arabian Gulf, the east coast on the Gulf of Oman exhibited much lower levels of plastic pellets. When compared to other parts of the world, the beaches of the UAE on the Arabian Gulf are considered to be heavily polluted with industrial plastic.     

带长链烷基季铵盐杀菌活性官能团树脂的合成

以强酸型阳离子交换树脂作载体 ,合成磺酰氯树脂后固载乙二胺并胺基叔胺化 ,最后加卤代烷合成带长链烷基季铵盐杀菌活性官能团树脂 ,确定了合成路线中的各步反应条件。对异养菌的杀菌性能测定结果表明 ,合成的杀菌树脂的杀菌率在测定条件下都达到了 90 %以上 ,有望用于工业和民用水的杀菌消毒     

Sorption of polycyclic aromatic hydrocarbons (PAHs) to low and high density polyethylene (PE)

Background, aim, and scope

According to their high sorption capacity polyethylene (PE) passive samplers are often used for the analysis of polycyclic aromatic hydrocarbons (PAHs) in the aquatic environment. PE is also one of the primary synthetic polymers found in oceans, and sorption of PAHs to marine PE debris may determine PAH exposure and therefore hazards in marine ecosystems. Thus, an understanding of the sorption process is of great importance. In the present study, the sorption of several PAHs with different polarities to low density polyethylene (LDPE) and high density polyethylene (HDPE) was studied in order to improve our understanding of the influence of material properties on the Fickian diffusion of PAHs into PE.

Materials and methods

Batch sorption experiments were performed with aqueous solutions containing acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, and LPDE or HDPE pellets. Samples were shaken in the dark at 20?±?1°C for 16 time intervals within one week. Concentrations of PAHs were determined in the aqueous samples using solid-phase microextraction coupled with gas chromatography–mass spectrometry. The distribution coefficients (K _PE) between PE and water were estimated from different models reported in the literature. Kinetic sorption of the PAHs into the plastic pellets was described by a diffusion model based on Fick’s second law in spherical coordinates.

Results and discussion

A comparison between different models describing the equilibrium distribution of PAHs between PE and water revealed that the sorption equilibrium seemed to be driven by parameters other than, or in addition to, organic carbon. For both plastic types, diffusion coefficients decreased while the molecular weight of the PAHs increased which indicates a hindered diffusion through the matrix as a result of a larger molecule size. Higher diffusion coefficients were derived for LPDE than for HDPE indicating a greater sorption velocity for LPDE according to the lower polymer density.

Conclusions

Our results revealed that equilibrium time could be shortened during passive sampling as polymer membranes of lower density are used. In some areas, marine ecosystems may not be in equilibrium with respect to concentrations of organic contaminants and abundance of marine plastic debris. In such cases, different polymer densities should be taken into account in risk assessments.

     

Extraction of mercury from groundwater using immobilized algae.

Bio-Recovery Systems, Inc. conducted a project under the Emerging Technology portion of the United States Environmental Protection Agency's (EPAs) Superfund Innovative Technology Evaluation (SITE) Program to evaluate the ability of immobilized algae to adsorb mercury from contaminated groundwater in laboratory studies and pilot-scale field tests. Algal biomass was incorporated in a permeable polymeric matrix. The product, AlgaSORB, packed into adsorption columns, exhibited excellent flow characteristics, and functioned as a "biological" ion exchange resin. A sequence of eleven laboratory tests demonstrated the ability of this product to adsorb mercury from groundwater that contained high levels of total dissolved solids and hard water components. However, use of a single AlgaSORB preparation yielded nonrepeatable results with samples collected at different times of the year. The strategy of sequentially extracting the groundwater through two columns containing different preparations of AlgaSORB was developed and proved successful in laboratory and pilot-scale field tests. Field test results indicate that AlgaSORB could be economically competitive with ion exchange resins for removal of mercury, with the advantage that hardness and other dissolved solids do not appear to compete with heavy metals for binding capacity.     

Extraction of Mercury from Groundwater Using Immobilized Algae

Bio-Recovery Systems, Inc. conducted a project under the Emerging Technology portion of the United States Environmental Protection Agency’s (EPAs) Superfund Innovative Technology Evaluation (SITE) Program to evaluate the ability of immobilized algae to adsorb mercury from contaminated groundwater in laboratory studies and pilot-scale field tests. Algal biomass was incorporated in a permeable polymeric matrix. The product, AlgaSORB, packed into adsorption columns, exhibited excellent flow characteristics, and functioned as a “biological” ion exchange resin. A sequence of eleven laboratory tests demonstrated the ability of this product to adsorb mercury from groundwater that contained high levels of total dissolved solids and hard water components. However, use of a single AlgaSORB preparation yielded nonrepeatable results with samples collected at different times of the year. The strategy of sequentially extracting the groundwater through two columns containing different preparations of AlgaSORB was developed and proved successful in laboratory and pilot-scale field tests. Field test results indicate that AlgaSORB could be economically competitive with ion exchange resins for removal of mercury, with the advantage that hardness and other dissolved solids do not appear to compete with heavy metals for binding capacity.     

Adsorption of branched alkylbenzene sulfonate onto styrene and acrylic ester resins

In this study, a series of acrylic ester resins were prepared and characterized. The adsorption behaviors of sodium 6-dodecyl benzenesulfonate (6-NaDBS) on styrene resin XAD-4 and acrylic ester resins have been studied. As compared to commercial acrylic ester resins Amberlite XAD-7 and Diaion HP2MG, YWB-38, one of the as-prepared resins, exhibits better adsorption properties toward 6-NaDBS. The experimental equilibrium data were fitted to the Langmuir and double-Langmuir models. The two models provide very good fit for all acrylic ester resins over the temperature range studied, whereas fitted results for styrene resin XAD-4 are less accurate. The investigation indicates that the adsorbate molecules are directly adsorbed on acrylic ester resins as a bi-layer, while the molecules are adsorbed on XAD-4 as monolayer formation followed by the establishment of bi-layer. Adsorption kinetics and elution processes were also investigated for further exploring the adsorption behavior and mechanism on styrene resin XAD-4 and YWB-38.     

Evaluation of ion exchange resins for the removal of dissolved organic matter from biologically treated paper mill effluent

In this study, the efficiency of six ion exchange resins to reduce the dissolved organic matter (DOM) from a biologically treated newsprint mill effluent was evaluated and the dominant removal mechanism of residual organics was established using advanced organic characterisations techniques. Among the resins screened, TAN1 possessed favourable Freundlich parameters, high resin capacity and solute affinity, closely followed by Marathon MSA and Marathon WBA. The removal efficiency of colour and lignin residuals was generally good for the anion exchange resins, greater than 50% and 75% respectively. In terms of the DOM fractions removal measured through liquid chromatography–organic carbon and nitrogen detector (LC–OCND), the resins mainly targeted the removal of humic and fulvic acids of molecular weight ranging between 500 and 1000 g mol^?1, the portion expected to contribute the most to the aromaticity of the effluent. For the anion exchange resins, physical adsorption operated along with ion exchange mechanism assisting to remove neutral and transphilic acid fractions of DOM. The column studies confirmed TAN1 being the best of those screened, exhibited the longest mass transfer zone and maximum treatable volume of effluent. The treatable effluent volume with 50% reduction in dissolved organic carbon (DOC) was 4.8 L for TAN1 followed by Marathon MSA – 3.6 L, Marathon 11 – 2.0 L, 21K-XLT – 1.5 L and Marathon WBA – 1.2 L. The cation exchange resin G26 was not effective in DOM removal as the maximum DOC removal obtained was only 27%. The resin capacity could not be completely restored for any of the resins; however, a maximum restoration up to 74% and 93% was achieved for TAN1 and Marathon WBA resins. While this feasibility study indicates the potential option of using ion exchange resins for the reclamation of paper mill effluent, the need for improving the regeneration protocols to restore the resin efficiency is also identified. Similarly, care should be taken while employing LC–OCND for characterising resin-treated effluents, as the resin degradation is expected to contribute some organic carbon moieties misleading the actual performance of resin.     

风量对高频气力分选机分选效率及金属分布规律的影响——以废弃印刷电路板粉末为例

以金属高富集粒级0.5～0.125 mm的废弃电路板为分选物料,通过ICP-AES测定分选产品,研究了风量对高频气力分选机分选效率及金属分布规律的影响.结果表明,风量变化对分选效率及金属分布规律影响显著,当风量为200m3/h时分选效率达到最大值78.23％,铜品位为86.745％,相比原料中铜品位13.96％,富集约6.2倍.随着风量的变化,金属的分布呈现规律性变化:密度比铜大或与铜相差不多的金属颗粒(铅、铂和锌等),其变化规律与铜相似,回收率在85％左右变化;密度比铜小很多的金属颗粒(铝、镁等),由于其密度与分选物料中的非金属非常接近,在分选过程中会随非金属带人轻产物中去,从而造成重产物中铝和镁品位最低,甚至低于其在原料中的品位.所以若要分离富集铝和镁,须对分选后的物料进行二次分选.     

污泥中重金属的去除及回收试验

论述了利用离子交换技术循环使用柠檬酸去除污泥中重金属,并置换回收重金属的适宜工艺条件.经柠檬酸处理后,污泥中90%以上的重金属被去除;柠檬酸处理液中的重金属用离子交换法回收,考察了树脂种类、流速、操作方式等因素对离子交换、再生效果的影响;在适宜工艺条件下,重金属的交换率均为100%,而洗脱率均接近90%;柠檬酸及离子交换树脂循环使用,重金属也得到回收,降低了处理成本.     

Development of a packed-bed reactor for the recovery of metals from industrial wastewaters

Affinity separation is becoming well established for the purification and recovery of metals from industrial wastewaters. Although the method has been successfully applied on a bench-scale, there is a need for reaction engineering studies to scale-up the process for use in large-scale wastewater purification and recovery of valuable metals. In this study, a pilot-scale packed-bed reactor has been developed in order to investigate influences of process parameters and their interactions on the recovery of metals from process wastewaters using diatomaceous material. The material was formed into a packed configuration to provide a high adsorbent area-to-aqueous solution volume ratio. Activated carbon and ion-exchange resin were tested for comparison. The results obtained show that the flow-rate, residence time, metal concentration loading and packed-bed geometry significantly influenced the efficiency of the reactor system metal recovery and have to be considered in the design of large-scale system. An optimum residence time of 2 h was found to give metal recovery capacities of 60%, 76% and 80% for the ion-exchange resin, diatomaceous material and activated carbon, respectively, which confirmed the bench-scale studies. The sequestered metals were efficiently eluted from the diatomaceous material using different elution solutions for different metals. The selectivity of the adsorbent for specific metals can be manipulated on the uptake and elution sides of the process. The study also revealed that diatomaceous material can be regenerated and used many times over, just like conventional adsorbents or ion-exchange resins in process wastewater purification as well as in metal recovery processes. The application of the packed-bed reactor using the locally available diatomaceous material is therefore recommended for economical and cost-effective small-scale purification and recovery of metals from industrial wastewaters loaded with metals in Nigeria.     

Alkaline hydrothermal treatment of brominated high impact polystyrene (HIPS-Br) for bromine and bromine-free plastic recovery

A method to recover both Br and Br-free plastic from brominated flame retardant high impact polystyrene (HIPS-Br) was proposed. HIPS-Br containing 15% Br was treated in autoclave at 280 degrees C using water or KOH solution of various amounts and concentrations. Hydrothermal treatment (30 ml water) leads to 90% debromination of 1g HIPS-Br but plastic is strongly degraded and could not be recovered. Alkaline hydrothermal treatment (45 ml or 60 ml KOH 1M) showed similar debromination for up to 12 g HIPS-Br and plastic was recovered as pellets with molecular weight distribution close to that of the initial material. Debromination occurs at melt plastic/KOH solution interface when liquid/vapour equilibrium is attained inside autoclave (280 degrees C and 7 MPa in our experimental conditions) and depends on the plastic amount/KOH volume ratio. The antimony oxide synergist from HIPS-Br remains in recovered plastic during treatment. A pictorial imagination of the proposed debromination process is presented.     

Chemical and Biological Characterization of Products of Incomplete Combustion from the Simulated Field Burning of Agricultural Plastic

Chemical and biological analyses were performed to characterize products of Incomplete combustion emitted during the simulated open field burning of agricultural plastic. A small utility shed equipped with an air delivery system was used to simulate pile burning and forced-air-curtain incineration of a nonhalogenated agricultural plastic that reportedly consisted of polyethylene and carbon black. Emissions were analyzed for combustion gases; volatile, semi-volatile, and particulate organics; and toxic and mutagenlc properties. Emission samples, as well as samples of the used (possibly pesticide-contaminated) plastic, were analyzed for the presence of several pesticides to which the plastic may have been exposed. Although a variety of alkanes, alkenes, and aromatic and polycyclic aromatic hydrocarbon (PAH) compounds were identified in the volatile, seml-volatlle, and particulate fractions of these emissions, a substantial fraction of higher molecular weight organic material was not identified. No pesticides were Identified in either combustion emission samples or dlchloromethane washes of the used plastic. When mutagenlcity was evaluated by exposing Salmonella bacteria (Ames assay) to whole vapor and vapor/partlculate emissions, no toxic or mutagenlc effects were observed. However, organic extracts of the particulate samples were moderately mutagenlc. This mutagenlcity compares approximately to that measured from residential wood heating on a revertant per unit heat release basis. Compared to pile burning, forced air slightly decreased the time necessary to burn a charge of plastic. There was not a substantial difference, however, in the variety or concentrations of organic compounds Identified In samples from these two burn conditions. This study highlights the benefits of a combined chemical/biological approach to the characterization of complex, multi-component combustion emissions. These results may not reflect those of other types of plastic that may be used for agricultural purposes, especially those containing halogens.     

Adsorption Characteristics of Activated Carbon and XAD4 Resin for the Removal of Hazardous Organic Solvents

A comparative study has been conducted on adsorption/desorption of six hazardous organic vapors on synthetic resin (XAD4) and activated carbon, using a differential reactor involving the expansion of a quartz spring. While both sorbents can effectively remove the organic vapors, it was observed that at low concentrations activated carbon adsorbed more organic vapor than synthetic resin. At higher, industrial concentrations, the resins adsorbed more vapor as demonstrated by the slopes of the equilibrium isotherms. The resin also showed much higher desorptlon.

The effective Intraparticle diffusion coefficients (D_e) were observed to be strongly dependent on solute concentration. Pore diffusion dominated the adsorption/desorption of the six organic vapors on XAD4 resin. For the carbon system, pore diffusion dominated the adsorption but surface diffusion contributed to the desorptlon process. This is believed to be due to higher Interaction of the adsorbates with activated carbon.     

湿法再生吸附剂制备及用于大气CO2的直接捕集

基于湿法再生吸附技术,利用强碱性季铵盐树脂材料制备了异相吸附剂薄膜,应用于大气中极低CO2的直接分离,以对抗全球变暖。通过滴定法分析吸附剂材料的电荷密度和吸附容量,利用SEM分析不同工况下制备出来的膜材料的表观结构,并对膜材料进行CO2吸附性能的测试。结果发现,热处理能够明显提高膜材料的吸附性能,还研究吸附剂制备对吸附速率,吸附量和机械强度等性能的影响,发现粒径小于43μm的树脂粉末,按60％质量分数制成的500μm厚膜材料具有较优的综合性能。     

Plastic pellets, tar, and megalitter on Beirut beaches, 1977-1988

In the spring of 1988, five beaches along the coast of Beirut were surveyed for the presence of plastic pellets, tar, and megalitter--a follow-up to the studies conducted on the coast of Lebanon in 1977 for plastic pellet and tar occurrence, and in 1978 for containers and other megalitter on Beirut beaches. Plastic pellets were more abundant than they were in 1977 on three beaches and less so on two. Tar, however, seemed to occur much more abundantly on all five beaches. Megalitter, chiefly plastic but also paper, metal, and glass, had increased greatly compared with that seen 10 years ago. As in 1977, the unrestricted waste disposal practices of the plastic manufacturers, plus the possible loss of cargo from ships loading and unloading raw materials, are the most likely sources of plastic pellets. The abundance of tar is not surprising, considering that the Mediterranean Sea is tar-polluted and that two oil terminals occur on Lebanon's coast. Further, local gas stations frequently dump oil and grease onto the beaches, and numerous fires have occurred at coastal refineries over the past 10-15 years. All of these factors are likely to contribute to the presence of tar on the beaches. The main source of the vast quantities of megalitter on the beaches is undoubtedly the Lebanese people themselves, due to numerous population shifts and the lack of order and regulatory enforcement as a result of the civil chaos in the country. In addition, the ships docking or waiting for days, and sometimes weeks, to get into the Lebanese ports probably affect the abundance of megalitter (and tar) on the beaches.