The Autothermal Pyrolysis of Waste Tires

Abstract

The growing amount of rubber waste, such as that from tires and cables, has resulted in serious environmental problems. Since rubber waste is not easily biodegradable even after a long period of landfill treatment, material and energy recovery is the preferable alternative to disposal. The potential offered by waste tire pyrolysis for solving both energy and waste treatment problems is widely recognized. Pyrolysis is one method of inducing thermal decomposition without using any oxidizing agent, or using such a limited supply of the agent that oxidization does not proceed to an appreciable extent. The latter may be described as autothermal pyrolysis and will be studied in the present work.

The main objective of this research was to study the operating parameters of autothermal pyrolysis of scrap tires in a laboratory-scale fluidized bed reactor with a 100-cm bed height (10 cm I.D.) and a 100-cm freeboard (25 cm I.D.). Scrap tires were pyrolyzed in a limited oxygen supply, so that the heat for pyrolysis of the scrap tires was provided by combustion of some portion of the scrap tires. The operating parameters evaluated included the effect on the pyrolysis oil products and their relative proportions of (1) the air factor (O.O7–O35); (2) the pyrolysis temperature (370–570 °C); and (3) the catalyst added (zeolite and calcium carbonate). The results show that: (1) the composition of the liquid hydrocarbon obtained is affected significantly by the air factor; (2) the higher operating temperature caused a higher yield of gasoline and diesel; (3) the yield of gasoline increased due to the catalyst zeolite added, and the yield of diesel increased due to the addition of the catalyst calcium carbonate; (4) the principal constituents of gasoline included dipentene and diprene.     

Application and Evaluation of Two Air Quality Models for Particulate Matter for a Southeastern U.S. Episode

Abstract

The Models-3 Community Multiscale Air Quality (CMAQ) Modeling System and the Particulate Matter Comprehensive Air Quality Model with extensions (PMCAMx) were applied to simulate the period June 29–July 10, 1999, of the Southern Oxidants Study episode with two nested horizontal grid sizes: a coarse resolution of 32 km and a fine resolution of 8 km. The predicted spatial variations of ozone (O₃), particulate matter with an aerodynamic diameter less than or equal to 2.5 μm (PM_2.5), and particulate matter with an aerodynamic diameter less than or equal to 10 μm (PM₁₀) by both models are similar in rural areas but differ from one another significantly over some urban/suburban areas in the eastern and southern United States, where PMCAMx tends to predict higher values of O₃ and PM than CMAQ. Both models tend to predict O₃ values that are higher than those observed. For observed O₃ values above 60 ppb, O₃ performance meets the U.S. Environmental Protection Agency's criteria for CMAQ with both grids and for PMCAMx with the fine grid only. It becomes unsatisfactory for PMCAMx and marginally satisfactory for CMAQ for observed O₃ values above 40 ppb.

Both models predict similar amounts of sulfate (SO₄ ^2?) and organic matter, and both predict SO₄ ^2? to be the largest contributor to PM_2.5. PMCAMx generally predicts higher amounts of ammonium (NH₄ ⁺), nitrate (NO₃ ^?), and black carbon (BC) than does CMAQ. PM performance for CMAQ is generally consistent with that of other PM models, whereas PMCAMx predicts higher concentrations of NO₃ ^?,NH₄ ⁺, and BC than observed, which degrades its performance. For PM₁₀ and PM_2.5 predictions over the southeastern U.S. domain, the ranges of mean normalized gross errors (MNGEs) and mean normalized bias are 37–43% and –33–4% for CMAQ and 50–59% and 7–30% for PMCAMx. Both models predict the largest MNGEs for NO₃ ^? (98–104% for CMAQ, 138–338% for PMCAMx). The inaccurate NO₃ ^? predictions by both models may be caused by the inaccuracies in the ammonia emission inventory and the uncertainties in the gas/particle partitioning under some conditions. In addition to these uncertainties, the significant PM overpredictions by PMCAMx may be attributed to the lack of wet removal for PM and a likely underprediction in the vertical mixing during the daytime.     

Anthropogenic impacts on suspended sediment load in the Upper Yangtze river

Climate change and human disturbance drive catchment erosion and increase riverine sediment load sensitively in small and medium-sized watersheds. This is not always true in large basins, where aggregation and buffering effects have dampen the ability to determine the driving forces of sedimentation. Even though there are significant responses to sedimentation in large river basins, it is difficult to get a precise quantitative assessment of specific drivers. This paper develops a methodology to identify driving forces that change suspended sediment load in the Upper Yangtze river. Annual runoff and sediment load data from 1954 to 2005 at the Yichang gauging station in the Upper Yangtze basin, daily precipitation data from 60 meteorological stations, and survey data on reservoir sediment were collected for the study. Sediment load/rainfall erosivity (S/R), is a new proxy indicator introduced to reflect human activities. Since the mid-1980s, S/R in the Upper Yangtze has dramatically declined from 0.21 to 0.03 (×10¹⁰ t ha h MJ⁻¹ mm⁻¹), indicating that human activity has played a key role in the decline of the suspended sediment load. Before the mid-1980s, a higher average S/R is attributed to large-scale deforestation and land reclamation. A significant sediment decrease occurred from 1959 to 1961 during an extreme drought condition, and an increase in sedimentation in 1998 coincided with an extreme flood event, which was well recorded in the S/R curve. This indicates that the S/R proxy is able to distinguish anthropogenic from climate impacts on suspended sediment load, but is not necessarily indicatory in extreme climate events. In addition, typical drivers of riverine sediment load variation including soil conservation projects, reservoirs construction, and land use/cover change are discussed.     

The influence of mariculture on mercury distribution in sediments and fish around Hong Kong and adjacent mainland China waters

To study the influence of mariculture on mercury (Hg) speciation and distribution in sediments and cultured fish around Hong Kong and adjacent mainland China waters, sediment samples were collected from six mariculture sites and the corresponding reference sites, 200-300 m away from the mariculture sites. Mariculture activities increased total mercury, organic matter, carbon, nitrogen and sulfur concentrations in the surface sediments underneath mariculture sites, possibly due to the accumulation of unconsumed fish feed and fish excretion. However, methylmercury (MeHg) concentrations and the ratio of MeHg to THg (% MeHg) in sediments underneath mariculture sites were lower than the corresponding reference sites. The % MeHg in sediments was negatively correlated (r = −0.579, p < 0.05) with organic matter (OM) content among all sites, indicating that OM may have inhibited Hg methylation in surface sediments. Three mariculture fish species were collected from each mariculture site, including red snapper (Lutjanus campechanus), orange-spotted grouper (Epinephelus coioides) and snubnose pompano (Trachinotus blochii). The average MeHg concentration in fish muscle was 75 μg kg⁻¹ (wet weight), and the dietary intake of MeHg through fish consumption for Hong Kong residents was 0.37 μg kg⁻¹ week⁻¹, which was lower than the corresponding WHO limits (500 μg kg⁻¹ and 1.6 μg kg⁻¹ week⁻¹).     

Residues and dynamics of pymetrozine in rice field ecosystem

The fate of pymetrozine was studied in rice field ecosystem, and a simple and reliable analytical method for determination of pymetrozine in soil, rice straw, paddy water and brown rice was developed. Pymetrozine residues were extracted from samples, cleaned up by solid phase extraction (SPE) and then determined by high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS). The average recovery was 81.2-88.1% from soil, 83.4-88.6% from rice straw, 87.3-94.1% from paddy water and 82.9-85.3% from brown rice. The relative standard deviation (RSD) was less than 15%. The limits of detection (LODs) of pymetrozine calculated as a sample concentration were 0.0003 mg kg⁻¹ (mg L⁻¹) for soil and paddy water, 0.001 mg kg⁻¹ for brown rice and rice straw. The results of kinetics study of pymetrozine residue showed that pymetrozine degradation in water, soil, and rice straw coincided with C = 0.194e^−0.986t, C = 0.044e^−0.099t, and C = 0.988e^−0.780t, respectively; the half-lives were about 0.70 d, 7.0 d and 0.89 d, respectively. The degradation rate of pymetrozine in water was the fastest, followed by rice straw. The highest final pymetrozine residues in brown rice were 0.01 mg kg⁻¹, which was lower than the EU’s upper limit of 0.02 mg kg⁻¹ in rice. Therefore, a dosage of 300-600 g a.i.hm⁻² was recommended, which could be considered as safe to human beings and animals.     

The dissipation rates of trichlorfon and its degradation product dichlorvos in cabbage and soil

The residual levels and dissipation rate of trichlorfon, and its degradation product, dichlorvos, in cabbage crops and the soil in which these were grown, were determined by gas chromatography at two geographically distant experimental sites, one in Kunming and one in Beijing, China. Trichlorfon was applied at two dosages (900 g ai ha⁻¹ and 1350 g ai ha⁻¹). Maximum final residues of trichlorfon in soil and cabbage were 1.23 mg kg⁻¹ and 1.81 mg kg⁻¹ respectively at Kunming, and 0.35 mg kg⁻¹ and 0.70 mg kg⁻¹ respectively at Beijing. However, the final residues of dichlorvos in both cabbage and soil was only 0.04 mg kg⁻¹ at Kunming, and only 0.03 mg kg⁻¹, or “not detectable”, at Beijing. The mean half-life of trichlorfon in cabbage was 1.80 d with a dissipation rate of 90% over 5 d, while that in soil was 3.05 d with a dissipation rate of 90% over 14 d at one experimental site. The dissipation rates of trichlorfon and its degradation product dichlorvos at the two experimental sites were different, suggesting that degradation of these pesticides was affected by local soil characteristics and climate. When applied at both the recommended dosage and at 1.5 times this, no detectable residues of either trichlorfon or dichlorvos were found in soil or cabbage at harvest. Although trichlorfon can easily degrade into dichlorvos, which is highly toxic to humans and other animals, the observed low residual levels of dichlorvos suggest that trichlorfon is safe when applied at the recommended dosage.     

Polybrominated diphenyl ethers (PBDEs) and indicator polychlorinated biphenyls (PCBs) in marine fish from four areas of China

The levels of polybrominated diphenyl ethers (PBDEs) and indicator polychlorinated biphenyls (PCBs) were determined in marine fish from four areas of China (South China Sea, Bohai Sea, East China Sea, and Yellow Sea) using GC/NCI-MS and GC/ITMS, respectively. Total concentrations of eight PBDEs (BDE-28, 47, 99, 100, 153, 154, 183 and 209) in all samples ranged from 0.3 ng g⁻¹ ww (wet weight) to 700 ng g⁻¹ ww, with median and mean values of 85 ng g⁻¹ ww and 200 ng g⁻¹ ww, respectively. BDE-209 and BDE-47 were the major congeners in all samples, contributing 54% and 19% to the total concentration, respectively. The sum of seven indicator PCB levels (CB-28, 52, 101, 118, 138, 153, and 180) ranged from 0.3 ng g⁻¹ ww to 3.1 μg g⁻¹ ww, with median and mean values of 6.4 ng g⁻¹ ww and 398 ng g⁻¹ ww, respectively. High contributions of CB-138 (32%) and CB-153 (25%) were found in all samples. In general, pollutants measured in this study were at high levels when compared with previous studies from other regions in the world. The relative abundance of BDE-209 may suggest that deca-BDE sources existed in studied area. And principal component analysis (PCA) showed that there were other PBDE sources in Yellow Sea. The pattern and PCA showed that PCB pollutions came from similar sources in the studied areas. In addition, concentrations of ∑₇PBDEs (u/209) were strongly correlated with those of ∑₇PCBs in all fish (r = 0.907, n = 44).     

Reversed association between levels of prostate specific antigen and levels of blood cadmium and urinary cadmium

Prostate cancer associated with cadmium exposure may indicate a link between prostate specific antigen (PSA) and levels of blood cadmium (BCd) and urinary cadmium (UCd). Thus, these associations were investigated. We recruited 295 men, 50 years of age and above from a health check-up program at a health center as subjects of the study. They completed a self-reported questionnaire and provided fasting samples of blood and urine for cadmium assay. The assay was performed using atomic absorption spectrophotometry. Blood samples were also collected for the assays of total cholesterol and high-density lipoprotein measures. The means of BCd and UCd increased with age and the means of all subjects were 1.19 ± 1.04 μg L⁻¹ and 1.37 ± 1.76 μg g⁻¹ creatinine, respectively. The PSA levels were positively associated with the lipid levels, but reversely associated with BCd and UCd levels. The multivariate logistic regression analysis showed that men with PSA ? 4.0 ng mL⁻¹ had an odds ratio (OR) of 0.4 (95% CI = 0.1-0.9) to have BCd > 0.49 μg L⁻¹, and an OR of 0.4 (95% CI = 0.2-1.0) to have UCd > 0.45 μg g⁻¹ creatinine. In conclusion, the PSA levels are reversely associated with BCd and UCd levels.     

基于产业链的区域环境污染物排放的产业贡献

区域经济增长与环境质量之间的关系研究是目前学者们探讨的重要学术议题之一.其中较多的是对EKC曲线的验证,近几年部分学者从国民经济各部门中的产业自身特征、产业结构、技术进步、FDI效应等方面考察产业发展对污染物排放的影响.然而以上研究议题中学者均没有讨论污染物的发生主体-各产业部门与排污的直接关系.故本文将从宏观尺度下的综合水平测度区域经济发展与环境质量关系、中观尺度下的产业属性特征与排污关系的研究视角转移至分析具体产业部门的污染物排放效应,同时将产业置于产业链的结构形式中,研究产业链上产业发展与污染物排放的关系.发现:第一,通过借助复杂网络思想的社区划分方法,将山东省39个产业部门分为3个社团.其中社团I主要由制造业部门组成,共有18个产业部门,社团II包括了15个部门,主要是第三产业,杜团III由6个产业部门组成且内部异质性高.第二,选择其中以制造业为主的社团I,并在社团I内识别出一条彼此间联系最为紧密的产业链,包括农林牧渔业、食品制造及烟草加工业、化学工业、纺织工业、服装皮革羽绒及其制品业、通用/专用设备制造业和交通运输设备制造业.以一种定量的方法获取了通过价值流传递而串在一起的产业链条.该产业链的经济规模、污染物规模在山东省均有重要地位.第三,采用岭回归分析方法,构建了6个制造业与产业链工业废水、固体废弃物排放的关系模型,6个制造业中对工业废水、固体废弃物排放相对贡献度最大的部门分别为服装皮革羽绒及其制品业、食品制造及烟草加工业.这是由于上游产业排污的链式传递效应与产业自身污染物排放效应的共同叠加作用.