Organic reactions without organic solvents and oils and fats as renewable raw materials for the chemical industry

The use of organic solvents should be minimized as far as possible to reduce atmospheric volatile organic compounds (VOCs). Examples of solvent-free organic syntheses are described. The increasing usage of renewable feedstocks taking advantage of the synthetic potential of nature is another way to avoid organic solvents. Most important is the development of chemical products, i.e., coatings that can be processed without organic solvents.     

几种有机废气吸收液对甲苯吸收效果的对比

采用自行设计的吸收装置,对比研究了国内外文献报道的几种有机废气吸收液(二乙基羟胺、聚乙二醇400、硅油、食用油、废机油、0#柴油)对模拟甲苯废气的吸收效果。结果表明,通过改变吸收液种类、废气中甲苯浓度等条件能够对甲苯废气吸收效果产生显著影响。随着吸收时间的延长,吸收液对甲苯的吸收率逐渐降低,直至达到动态饱和。随甲苯废气中甲苯浓度的增大,吸收液的有效吸收量减小,而饱和吸收量则增大。在相同实验条件下,二乙基羟胺对甲苯的有效吸收量与饱和吸收量均最大,其次是食用油、机油、0#柴油,而聚乙二醇与硅油吸收效果最差。本研究结果为合理选择甲苯废气的高效吸收液提供了理论依据。     

Characterization and adsorption capacity of modified 3D porous aerogel from grapefruit peels for removal of oils and organic solvents

With the rapid industrialization, especially offshore oil exploitation, frequent leakage incidents of oils/organic solvents have adversely affected ecological systems and environmental resources. Therefore, great interest has been shown in developing new materials to eliminate these organic pollutants, which have become worldwide problems. In this study, a cost-effective, environmentally friendly porous aerogel with three-dimensional (3D) structure was prepared from grapefruit peel by a facile hydrothermal method as the adsorbent of oils/organic solvents. The as-prepared modified grapefruit peel aerogel (M-GPA) showed mesoporous structure with high specific surface area of 36.42 m²/g and large pore volume of 0.0371 cm³/g. The excellent hydrophobicity of M-GPA with a water contact angle of 141.2° indicated a strong potential for adsorption of oils and organic solvents. The high adsorption capacity of M-GPA for a series of oils and organic solvents was 8 to 52 times as much as its own weight. Moreover, the M-GPA was easily regenerated and a high adsorption capacity recovery above 97% was maintained after five adsorption–regeneration cycles. Therefore, the M-GPA is a promising recyclable adsorbent for the removal of oils/organic solvents from polluted water.

     

A new approach for estimating emissions of organic solutes and organic solvents under wind speeds

A new approach is developed to predict the volatilization loss of the pure liquid and the volatilization rates of organic solutes with different Henry's law constants (H) under wind speed. The tested compounds include eight volatile organic compounds for pure liquid and the forty-one organic solutes with different H compounds are divided into three groups that span seven H orders. The wind speed is set from 0 to 6.0 ms^?1. A characteristic parameter ε was established to estimate volatilization loss of pure organic compounds. The mass transfer coefficient (K_OL) ratios of the organic solutes, under both wind speed and still conditions, are applied to describe the volatilization characteristics of the selected solutes. The curve profile for K_OL ratios and ε values relative to the selected wind speed can be divided into two stages, the sharp-rise stage and the stable-linearity stage. The critical finding is the ε values for the different organic compounds under a specific wind speed approach a constant. The changes in the curve profile of the K_OL ratios are similar to the ε values of the pure organic compounds. It is also found the relatively lower H compounds exhibit a sensitive wind effect on the K_OL ratios. The K_OL ratios of the relatively higher H compounds indicate a similar linear increase with the increasing wind speed in the two stages. Accordingly, concentrations of the organic compounds at the interface are thought to the primary factor. The obtained results could be a good reference to estimate volatilization loss of the organic solutes or the organic solvents under different wind speed conditions.     

Decomposition of trichloroethylene and 2,4-dichlorophenol by ozonation in several organic solvents

The effects of chemical characteristics of organic solvents on the decomposition rate constants of undissociative trichloroethylene (TCE) and dissociative 2,4-dichlorophenol (2,4-DCP) by ozonation were studied. The TCE and 2,4-DCP decomposition by ozonation in organic solvents followed to the first-order reaction kinetics with respect to TCE or 2,4-DCP concentration. The orders of the rate constants among organic solvents for undissociative TCE and dissociative 2,4-DCP were different indicating that the ozonation rates for undissociative and dissociative compounds were dependent on the chemical property of organic solvent. The decomposition of undissociative TCE by ozonation was a simple electrophilic reaction, which was dependent on acceptor number (AN) of the solvent. On the other hand, the decomposition of dissociative 2,4-DCP was dependent on by the dissociation of the compounds and would be dependent on donor number (DN) of the solvent. Finally, TCE in acetic acid was transformed to chlorinated intermediates and chloride ion and then these intermediates were continuously oxidized to chlorine gas.     

Photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans in aqueous solutions and in organic solvents

Aqueous solutions of selected polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were prepared using a generator column and exposed to UV (300 nm) light in the laboratory and to sunlight in an outdoor environment. In the laboratory, additional exposures were also carried out using 60% acetonitrile/water solutions. At 300 nm di- and tetra PCDDs had higher first-order photodegradation rate constants in 60% acetonitrile/water than in pure water. The solvent effect was reversed for PCDFs. These results may be a reflection of the higher polarity of PCDFs compared to PCDDs. In both the indoor and outdoor exposures photodegradation rates decreased with increasing concentrations of chlorination. However, OCDF exposed to 300 nm light in 60% acetonitrile/water and to sunlight in pure water photodegraded more rapidly than tetra CDF. Photolysis rates in sunlight were considerably slower (t(1/2) of 6.4-23 h) than photolysis rates at 300 nm in the laboratory (t(1/2) of 4.3-680 min), reflecting the lower intensity of sunlight in the 300 nm region of the UV/Vis spectrum. The extent of dechlorination of the PCDDs/PCDFs was less than 20% and reductive dechlorination does not appear to be a major process in the photodegradation of PCDDs/PCDFs in aqueous solutions.     

造粒流化床颗粒污泥对溶解性有机物的吸附机理研究

造粒流化床对污染物的去除是由混凝沉淀和物理吸附协同作用完成的,然而对于溶解性污染物,混凝沉淀的效果不明显,根据作者的实验分析,物理吸附在溶解性污染的去除中发挥了重要的作用。作者利用静态实验的方法对流化床颗粒对葡萄糖的吸附和扩散传质过程进行了分析,并采用Langmuir方程、Freudlich方程和Weber-Morris颗粒扩散模型对实验数据进行了拟合。结果表明,颗粒对葡萄糖的吸附等温过程与Langmuir方程有很好的吻合性;颗粒对葡萄糖的吸附速度与颗粒内部的扩散过程有很好的相关性。     

Stable hydrogen,carbon and chlorine isotope measurements of selected chlorinated organic solvents

Stable hydrogen isotopes of two chlorinated solvents, trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA), provided by five different manufacturers, were determined and compared to their carbon and chlorine isotopic signatures. The isotope ratio for delta2H of different TCEs ranged between +466.9 per thousand and +681.9 per thousand, for delta13C between -31.57 per thousand and -27.37 per thousand, and for delta37Cl between -3.19 per thousand and +3.90 per thousand. In the case of the TCAs, the isotope ratio for delta2H ranged between -23.1 per thousand and +15.1 per thousand, for delta13C between -27.39 per thousand and -25.84 per thousand, and for delta37Cl between -3.54 per thousand and +1.39 per thousand. As well, a column experiment was carried out to dechlorinate tetrachloroethylene (PCE) to TCE using iron. The dechlorination products have completely different hydrogen isotope ratios than the manufactured TCEs. Compared to the positive values of delta2H in manufactured TCEs (between +466.9 per thousand and +681.9 per thousand), the dechlorinated products had a very depleted delta2H (less than -300 per thousand). This finding has strong implications for distinguishing dechlorination products (PCE to TCE) from manufactured TCE. In addition, the results of this study show the potential of combining 2H/1H analyses with 13C/12C and 37Cl/35Cl for isotopic fingerprinting applications in organic contaminant hydrogeology.     

Experimental investigation on CO2 absorption and physicochemical characteristics of different carbon-loaded aqueous solvents

Environmental Science and Pollution Research - The anthropogenic carbon dioxide (CO2) denseness in the earth’s atmosphere is increasing day-to-day by combusting fossil fuels for power...     

Management, disposal and recycling of waste industrial organic solvents in Hong Kong.

An attempt has been made to establish a mass balance of industrial organic solvents in Hong Kong. It is estimated that only a small portion, less than 4%, of all the organic solvents consumed in Hong Kong are collected as waste solvents and properly treated, while the remainder are used either in the formulation of solvent containing products, or are lost to the environment through vapour emissions, leaks and spills, or dumped illegally. It was found that solvent recycling has been a common practice in some industries but the existing level of solvent recycling in Hong Kong is difficult to estimate. About 87.4% of all the waste organic solvents disposed of at the licensed facilities are potentially recyclable although whether they can be recycled in practice depends on many factors. Examples of existing waste organic solvent management and recycling practices from selected industries in Hong Kong are presented. The economic feasibility of current and future potential recycling systems is evaluated for a few selected cases. An integrated waste organic solvent management strategy is proposed to minimize adverse impacts of organic solvents to the environment and human health.     

双波长紫外吸收法有机废水COD测量技术与仪器设计

紫外吸收法直接测定有机废水COD是一种无需化学试剂、无样品前处理、无二次污染的绿色无损检测技术,但在实际应用中发现,有机废水中的悬浮物对测量结果产生较大影响.以实际废水水样为例,详细阐述了双波长紫外吸收法测量有机废水COD的操作方法及其消除悬浮物干扰的原理,并介绍了运用该技术设计开发的COD在线测量仪器.该仪器采用嵌入式计算机系统实时采集和处理数据,根据实际废水在双波长测量条件下的有效紫外吸光度快速推算出其COD值,具有快速、准确、无污染的特点.     

用于处理含油废水的吸油罐的研制

聚丙烯纤维是一种很好的吸油材料 ,以它作为吸油罐内的滤料吸附含油废水中的油 ,使水达标排放 ,再用蒸汽吹扫滤料上的油进行收集 ,使油回收利用     

An absorption model of the gas/aerosol partitioning involved in the formation of secondary organic aerosol

A partitioning model is developed to allow the modeling of the dynamics of secondary organic aerosol (SOA) formation. The gas/aerosol partitioning is assumed to be governed by equilibrium partitioning into an absorptive, well-mixed liquid (or at least amorphous) organic matter (om) phase. The model is represented using a set of coupled linear equations. It may be especially applicable when photochemical smog is being formed in the summer. The model permits (indeed, it requires) partitioning of a given compound i to occur even when i is present at a level below its saturation vapor pressure. During early periods of SOA formation, to determine the partitioning for each compound of interest, the model must be solved iteratively for each time and location of interest. Iteration is required because the partitioning is assumed to be governed by mole fraction concentrations in the om phase, and because prior to solving the problem, one does not know the total number of mols of condensed compounds in the om phase. During later stages of SOA formation, if the amount and general composition of the SOA begin to become constant, the partitioning coefficient of each of the compounds will also stabilize, and an iterative solution will be less needed.     

Evaluation of a novel carbon adsorbent for fractionation and treatment of halogenated organic wastes

A carbon adsorbent obtained by a procedure analogous to reverse burn coal gasification is being evaluated in our laboratory. This low surface area carbon adsorbent shows considerable promise as a fractionation medium for a variety of organics. The performance of the adsorbent compares favorably to the highly specialized carbon adsorbents such as PX-21 (Amoco Corp.). The adsorbent also has considerable potential for treatment of wastes containing organochlorine compounds. The adsorbent shows good adsorption capacity and can hold as much as 50% (w/w basis) of organic sludge while maintaining a relatively dry, granular character. Furthermore, this waste-loaded adsorbent is amenable to highly efficient self-sustained thermal degradation. Degradation efficiencies approaching 99.99 percent have been achieved for such recalcitrant organics as polychlorinated biphenyls and tetrachlorodibenzo-p-dioxins.     

Molecular markers, essential oils and diagnostic parameters as indicators for assessing the origin and constitution of organic matter in atmospheric aerosols

Atmospheric particulate matter was collected at two sites: an Abies boressi forest in central Greece and in Giesta, a coastal-rural site in the centre of Portugal. The extractable organic material consisted primarily of aliphatic hydrocarbons, acids, alcohols, and ketones, with a predominance of molecular weights >C20, derived from vascular plant waxes. Biomarkers for vegetation sources such as phytosterols, triterpenic compounds and essential oils were also detected. Microbial components (>C20), pyrogenic aromatic hydrocarbons and petroleum residues, including hopanes, steranes and cyclic and branched hydrocarbons, were present in the various aerosol extracts. In the apportionment of the various organic fractions to sources, vegetation waxes dominated, contributing to 50–60% of the solvent-extractable material in the aerosols. Petroleum residues and microbial components comprise 25–30% and 15–25% of the organic matter, respectively.     

Development of a database for chemical mechanism assignments for volatile organic emissions

The development of a database for making model species assignments when preparing total organic gas (TOG) emissions input for atmospheric models is described. This database currently has assignments of model species for 12 different gas-phase chemical mechanisms for over 1700 chemical compounds and covers over 3000 chemical categories used in five different anthropogenic TOG profile databases or output by two different biogenic emissions models. This involved developing a unified chemical classification system, assigning compounds to mixtures, assigning model species for the mechanisms to the compounds, and making assignments for unknown, unassigned, and nonvolatile mass. The comprehensiveness of the assignments, the contributions of various types of speciation categories to current profile and total emissions data, inconsistencies with existing undocumented model species assignments, and remaining speciation issues and areas of needed work are also discussed. The use of the system to prepare input for SMOKE, the Speciation Tool, and for biogenic models is described in the supplementary materials. The database, associated programs and files, and a users manual are available online at http://www.cert.ucr.edu/~carter/emitdb.

Implications: Assigning air quality model species to the hundreds of emitted chemicals is a necessary link between emissions data and modeling effects of emissions on air quality. This is not easy and makes it difficult to implement new and more chemically detailed mechanisms in models. If done incorrectly, it is similar to errors in emissions speciation or the chemical mechanism used. Nevertheless, making such assignments is often an afterthought in chemical mechanism development and emissions processing, and existing assignments are usually undocumented and have errors and inconsistencies. This work is designed to address some of these problems.     

基于紫外吸收原理的硝酸盐在线监测传感器研制及应用

基于紫外吸收原理,研制了一种新型硝酸盐在线监测传感器。通过对硝酸钾标准溶液的测试,绘制了该传感器的标准曲线,利用传感器对几种实际水体的硝酸盐含量进行了检测,并和国标法进行对比,同时通过加标回收率、稳定性、重复性及最低检出限等实验,对传感器的性能进行了评估。实验表明,传感器和国标法测量值的相对误差小于10.0%,加标回收率为91.8%~126%,传感器稳定性和重复性实验的CV值(变异系数)分别为3.364%和3.043%,最小检出限为0.074 mg/L。结果表明,该传感器基本满足水体硝酸盐在线监测的需求,并且具有无污染、工作稳定、测量快速和准确的优势。     

膜气体吸收技术分离VOCs/N2混合气性能的研究

以C6H6/N2混合气为代表,疏水性聚丙烯中空纤维膜为气液接触膜,n-甲酰吗啉(NFM,n-formyl morpholine)水溶液为吸收剂,研究了膜气体吸收法分离VOCs/N2混合气性能。考察了吸收剂流量、吸收剂体积分数、进口气流量、进口气浓度和膜组件结构等诸因素对分离性能的影响。结果表明,在吸收剂流量为20～100 mL/min,进口气流量为40～300 mL/min,进口气浓度为10.2 mg/L的条件下,苯的去除率为65.0 % ～ 99.6 %,总体积传质系数为0.0157～0.08412 s-1。实验证明,采用疏水性多孔膜气体吸收法,NFM水溶液吸收分离VOCs/N2混合气具有较高的分离效率和较快的传质速率。     

Essential oils and their bioactive compounds as eco-friendly novel green pesticides for management of storage insect pests: prospects and retrospects

Environmental Science and Pollution Research - The control of storage insect pests is largely based on synthetic pesticides. However, due to fast growing resistance in the targeted insects,...     

Use and validation of novel snow samplers for hydrophobic, semi-volatile organic compounds (SVOCs)

Two novel gas-tight snow samplers (snow-can and snow-tube) are presented and the performance of the snow-can in a field trial was assessed. The methodology for the sampling, extraction and analysis of persistent organic pollutants (POPs) are detailed. These samplers allow the various components of a snow sample to be analysed separately; these included the meltwater (MW), particulate matter (GFF) and vapour in the headspace (HS). Snow samples collected on the Punta Indren glacier in the Italian Alps revealed the occurrence of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OC). Replicate samples of the same snow type were undertaken as a test of sampling precision. Relative standard deviations (RSDs) for SigmaPCBs and SigmaPAHs were approximately 30% and approximately 35% respectively. The lowest precision was found for the particle-laden snow, notably for the heavier PCB homologues. For the chlorinated compounds, the pesticides lindane and endosulfan-I had the highest levels in snow, with mean concentrations of 402 and 103 pgl(-1) (snow meltwater) respectively. The vapour present in the headspace (HS) comprised a minor component of a collected sample for all compounds, but HS concentrations for three lighter PAHs gave good agreement with those calculated based on their dimensionless Henry's law constants. This suggests that volatilisation during melting of aged snow-can be reasonably predicted with knowledge of the temperature-dependent Henry's law constant.