响应面法优化废聚乙烯农膜制备聚乙烯蜡的工艺研究

采用响应面法对废聚乙烯(PE)农膜催化裂解制备聚乙烯蜡(PEW)的工艺参数进行优化。在单因素试验的基础上,运用Box-Bechken中心组合试验设计,建立了PEW收率与4个因素的二次回归方程,分析了各因素的显著性及交互作用,并对PEW产品进行结构表征和性能测试。结果表明,筛选HZSM-5和重芳烃油分别为废PE农膜催化裂解制备PEW的催化剂和溶剂,此时得到的PEW的滴熔点为104℃,针入度为1.21mm,黏均相对分子质量为1 687;各因素对PEW收率影响为催化剂用量裂解温度裂解时间溶剂用量;催化剂用量和溶剂用量、催化剂用量和裂解温度对PEW收率交互影响较大。以PEW收率最大、性能最佳为目标,获得最佳工艺条件:在100g废PE农膜中,加入0.35g HZSM-5作催化剂、17.00mL重芳烃油作溶剂,在385℃左右下裂解4.10h后,可得浅黄色的PEW,收率平均为98.45%。     

中孔分子筛Al-MCM-41催化裂解聚烯烃反应研究

采用水热合成法制备了不同硅铝比的中孔分子筛A l-MCM-41,将其应用于高密度聚乙烯(HDPE)和聚丙烯(PP)的催化裂解反应。通过改变硅铝比、反应温度和催化剂用量,对A l-MCM-41催化HDPE和PP裂解反应的规律进行了探讨,研究表明,HDPE裂解反应受硅铝比的影响较大;而对于PP裂解反应,硅铝比在一定范围内对催化剂活性的影响不明显。另外,与热裂解和HZSM-5小孔分子筛的催化裂解结果进行了比较,结果证明A l-MCM-41具有较高的催化活性和较高的液体产物收率,尤其适合于空间位阻较大的PP的催化裂解反应。     

粉煤灰和电石渣对聚丙烯塑料裂解的影响研究

研究了粉煤灰和电石渣对聚丙烯塑料裂解的影响,讨论了加入量对裂解速度和裂解产物的影响.结果表明:粉煤灰和电石渣都使裂解产物中的轻质部分(汽油和裂解气)增加、重油降低;粉煤灰比电石渣更能加快反应的进行,而且加入量越多,反应越快,需时越短;粉煤灰比电石渣对聚丙烯塑料的裂解具有明显的催化促进效果.     

中孔分子筛AI-MCM-41催化裂解聚烯烃反应研究

采用水热合成法制备了不同硅铝比的中孔分子筛AI-MCM-41，将其应用于高密度聚乙烯（HDPE）和聚丙烯（PP）的催化裂解反应。通过改变硅铝比、反应温度和催化剂用量，对Al-MCM-41催化HDPE和PP裂解反应的规律进行了探讨，研究表明，HDPE裂解反应受硅铝比的影响较大；而对于PP裂解反应，硅铝比在一定范围内对催化剂活性的影响不明显。另外，与热裂解和HZSM-5小孔分子筛的催化裂解结果进行了比较，结果证明A1-MCM-41具有较高的催化活性和较高的液体产物收率，尤其适合于空间位阻较大的PP的催化裂解反应。     

粉煤灰和电石渣对聚丙烯塑举裂解的影响研究

研究了粉煤灰和电石渣对聚丙烯塑料裂解的影响，讨论了加入量对裂解速度和裂解产物的影响。结果表明：粉煤灰和电石渣都使裂解产物中的轻质部分（汽油和裂解气）增加、重油降低；粉煤灰比电石渣更能加快反应的进行，而且加入量越多，反应越快，需时越短；粉煤灰比电石渣对聚丙烯塑料的裂解具有明显的催化促进效果。     

生物质快速热裂解主要参数对生物油产率的影响

以松木木屑为原料,在自制的小型流化床上,开展了生物质热裂解温度、生物质粒径和进料速率对生物油产率的影响实验研究.结果表明,在热裂解温度分别为450、475、500、525和550℃条件下,当热裂解温度为500℃时,生物油产率最高,平均产率达到53.33%(质量百分比).反应温度越高,炭产量越低,不可冷凝气体产量越高,气体发热值越高;粒径＜1 mm的生物质其粒径对生物油产率影响不大;生物质进料速率增加时,生物油产率增加.本研究为生物能的利用提供了新的途径.     

生物质快速热裂解主要参数对生物油产率的影响

以松木木屑为原料,在自制的小型流化床上,开展了生物质热裂解温度、生物质粒径和进料速率对生物油产率的影响实验研究.结果表明,在热裂解温度分别为450、475、500、525和550℃条件下,当热裂解温度为500℃时,生物油产率最高,平均产率达到53.33%（质量百分比）.反应温度越高,炭产量越低,不可冷凝气体产量越高,气体发热值越高;粒径＜1 mm的生物质其粒径对生物油产率影响不大;生物质进料速率增加时,生物油产率增加.本研究为生物能的利用提供了新的途径.     

基于间歇精馏回收废溶剂中二甲苯/醋酸丁酯

研究采用间歇精馏法从工业废溶剂油中回收二甲苯和醋酸丁酯,对预处理后的原料进行了间歇精馏工艺实验研究.考察了分离温度、时间和回流比等因素对分离效果的影响.结果表明:在最佳的工艺条件下,二甲苯和醋酸丁酯在馏出液中的含量均达到95%以上,收率分别达到62%和99.4%.基于物料衡算和相对挥发度建立了简捷有效间歇精馏数学模型,模型可较准确预测塔顶馏出物浓度变化.     

沉淀法回收聚苯乙烯泡沫塑料的工艺研究

研究沉淀法回收聚苯乙烯泡沫塑料(EPS)的工艺,利用石油裂解副产物为溶剂回收废旧聚苯乙烯泡沫塑料,以废治废,回收利用。溶剂低毒,对聚苯乙烯泡沫塑料溶解速度快,溶解量大,价廉易得。采用转式间歇投料并附加溶剂挥发分回收装置的工艺,溶剂回收率高,无二次污染,可循环使用。聚苯乙烯塑料(PS)回收率可达99%。     

旋转锥生物质裂解反应器裂解工艺的研究

为了研究生物质裂解工艺最佳条件,以木屑为原料,石英砂为热媒,对建立的以旋转锥反应器为主体的生物质快速裂解工艺进行研究,在单因素实验基础上,对4个主要因素(裂解温度、真空度、旋转锥盘转速和木屑粒径)进行正交实验。在木屑含水率为8.2%,热媒量1 200 g,进料速率4 kg/h的条件下,确定了最佳工艺条件为:裂解温度550℃,真空度0.08 MPa,旋转锥盘转速115 r/m in,木屑粒径为30目。最佳条件下生物质转化率为54.83%,实验研究表明,自制旋转锥反应器裂解工艺具有可行性。     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.