Using organoclays to enhance carbon filtration

Organoclays have found increased acceptance as pre-treatment for activated carbon adsorption systems in both groundwater and wastewater cleanup. The reason is that activated carbon tends to become quickly blinded by large organic molecules of low solubility, particularly oils. However, it is also well established that activated carbon is more efficient at low concentrations of organic contaminants than at higher ones, i.e. at less than 1 ppm. With organoclays it is exactly the opposite, they are better at removing organics at higher concentrations, above 3 ppm. Therefore it is cost effective in these applications to use two or more vessels in series, the first one filled with organoclay, the remainder with activated carbon. The economics make sense, even though the organoclay is not regenerated, because of the reduction in down time every time a carbon vessel has to be changed out. Use of organoclays increases the volume treated by carbon in many applications seven to nine fold. In the case of other organic contaminants, as the aqueous solubility increases, the efficiency decreases, except in the case of methylene chloride, which it removes at far higher efficiency then carbon. This article presents the results of a series of tests, including Kd determinations, jar tests, and mini-column tests. These tests determined the adsorption capacity and efficiency of organoclay and activated carbon for the removal of benzene, toluene, xylene and naphtalene from water. These tests were followed by adding the four compounds into one container to see if the combination of organoclay, followed by carbon, would be more efficient then each sorbent alone. The tests also compared the efficiency of organoclay versus carbon for the removal of various oils from water.     

Use of mixed technologies to remediate chlorinated DNAPL at a Brownfields site

A former chlorofluorocarbon manufacturing facility in northern New Jersey was purchased for redevelopment as a warehousing/distribution center as part of the New Jersey Department of Environmental Protection's Brownfields redevelopment initiative. Soil and groundwater at the site were impacted with dense nonaqueous‐phase liquids (chlorinated organic compounds) and light nonaqueous‐phase liquids (petroleum hydrocarbons). The initial remedial strategy (excavation and offsite disposal) developed by prior site owners would have been cost‐prohibitive to the new site owners and made redevelopment infeasible. Mixed remedial technologies were employed to reduce the cost of remediation while meeting regulatory contaminant levels that are protective of human health and the environment. The most heavily impacted soils (containing greater than 95 percent of the contaminant mass) were excavated and treated onsite by the addition of calcium oxide and lime kiln dust coupled with physical mixing. Treated soils were reused onsite as part of the redevelopment. Residual soil and groundwater contamination was treated via in situ injections of emulsified oil to enhance anaerobic biodegradation, and emulsified oil/zero‐valent iron to chemically reduce residual contaminants. Engineering (cap) and administrative (deed restriction) controls were used as part of the final remedy. The remedial strategy presented in this article resulted in a cost reduction of 50 percent of the initial remedial cost estimate. © 2008 Wiley Periodicals, Inc.     

改性核桃壳滤料对油田含油污水的过滤效果

采用亚硫酸氢镁蒸煮法对核桃壳滤料进行亲水改性,考察了改性核桃壳滤料对油田含油污水的过滤、反洗效果,探讨了改性前后核桃壳滤料的过滤过程及乳化油捕集机理。实验结果表明:在蒸煮温度为95℃、蒸煮时间为5 h、w(MgHSO_3)为5%的条件下,核桃壳滤料接触角由改性前的117.1°降至62.4°;分4批次过滤含油污水,改性核桃壳滤料的平均出水含油量为32.3 mg/L,平均油去除率为78.5%,平均浊度为7.7 NTU,平均浊度去除率为89.7%;改性核桃壳滤料的反洗效果显著改善,反洗水含油量由520 mg/L提高到840 mg/L,核桃壳滤料增重率由4.3%下降到0.2%。     

Literature review: Electrodialytic remediation and potential environmental applications of oil fly ash

Oil fly ash (OFA) contains environmentally toxic heavy metal and substituted polycyclic aromatic hydrocarbons. This review discusses the physical and chemical properties of OFA and presents information from other types of fly ash that can be used as concepts for the remediation and uses of OFA. Electrokinetic remediation is useful to remove some of the heavy metals for broader uses of the fly ash in agriculture, for making construction material, for contaminated wastewater treatment, and also for carbon dioxide sequestration. This review can be useful to develop approaches for the remediation and environmental management of OFA. © 2012 Wiley Periodicals, Inc.     

The Use of Oxygen Release Compound for the Accelerated Bioremediation of Aerobically Degradable Contaminants: The Advent of Time-Release Electron Acceptors

Oxygen Release Compound (ORC®) is a patented formulation of intercalated magnesium peroxide that releases oxygen slowly when hydrated. ORC treatment represents a “low intensity” approach to site remediation. It provides a simple, passive, low-cost and long-term acceleration of aerobic natural attenuation and has been shown to cost-effectively reduce time to site closure. ORC is now a proven technology as evidenced by its five years of use on over 5,000 sites in 50 states and 11 countries, and the existence of a full body of independent, peer reviewed literature on its performance. The first applications of ORC were for the treatment of benzene, toulene, ethylbenzene, and xylene (BTEX) and other light petroleum hydrocarbon fractions. Use has now expanded to the treatment of heavier fractions such as heating oil and some of the Polycyclic aromatic hydrocarbons (PAHs). More recently. ORC has been used to bioremediate the highly mobile and problematic gasoline oxygenate methyl tertiary butyl ether (MTBE) and has been applied to sites impacted with nitroaromatics, chloroaromatics, and some of the lower-order chlorinated hydrocarbons that can be treated aerobically—most notably vinyl chloride. Since ORC is an insoluble powder, it can be packaged in material composed of a specially designed filter fabric. These “filter socks” are then contacted with contaminated groundwater via an array of wells or trenches. ORC can also be mixed directly with water to form a slurry for permanent injection applications in the saturated zone or dispersed in powdered form for the in-situ or ex-situ treatment of soil. A broad array of treatment points, in which ORC slurry is backfilled or injected, can be implemented with low-cost, small-bore push-point technologies to directly treat dissolved phase plumes and moderate levels of sorbed contaminants. Powder or slurry is traditionally used in the remediation of residual contamination at the bottom of contaminated soil excavations. © 1999 John Wiley & Sons, Inc.     

Introduction/Overview to In Situ Burning of Oil Spills

In situ burning is an oil spill response technique or tool that involves the controlled ignition and burning of the oil at or near the spill site on the surface of the water or in a marsh (see Lindau et al., this volume). Although controversial, burning has been shown on several recent occasions to be an appropriate oil spill countermeasure. When used early in a spill before the oil weathers and releases its volatile components, burning can remove oil from the waters surface very efficiently and at very high rates. Removal efficiencies for thick slicks can easily exceed 95% (Advanced In Situ Burn Course, Spiltec, Woodinville, WA, 1997). In situ burning offers a logistically simple, rapid, inexpensive and if controlled a relatively safe means for reducing the environmental impacts of an oil spill. Because burning rapidly changes large quantities of oil into its primary combustion products (water and carbon dioxide), the need for collection, storage, transport and disposal of recovered material is greatly reduced. The use of towed fire containment boom to capture, thicken and isolate a portion of a spill, followed by ignition, is far less complex than the operations involved in mechanical recovery, transfer, storage, treatment and disposal (The Science, Technology, and Effects of Controlled Burning of Oil Spills at Sea, Marine Spill Response Corporation, Washington, DC, 1994).However, there is a limited window-of-opportunity (or time period of effectiveness) to conduct successful burn operations. The type of oil spilled, prevailing meteorological and oceanographic (environmental) conditions and the time it takes for the oil to emulsify define the window (see Buist, this volume and Nordvik et al., this volume). Once spilled, oil begins to form a stable emulsion: when the water content exceeds 25% most slicks are unignitable. In situ burning is being viewed with renewed interest as a response tool in high latitude waters where other techniques may not be possible or advisable due to the physical environment (extreme low temperatures, ice-infested waters), or the remoteness of the impacted area. Additionally, the magnitude of the spill may quickly overwhelm the deployed equipment necessitating the consideration of other techniques in the overall response strategy (The Science, Technology, and Effects of Controlled Burning of Oil Spills at Sea, Marine Spill Response Corporation, Washington, DC, 1994; Proceedings of the In Situ Burning of Oil Spills Workshop. NIST. SP934. MMS. 1998, p. 31; Basics of Oil Spill Cleanup, Lewis Publishers, Washington, DC, 2001, p. 233). This paper brings together the current knowledge on in situ burning and is an effort to gain regulatory acceptance for this promising oil spill response tool.     

离子液体改性活性炭对芳香烃的吸附性能

采用浸渍法和嫁接法分别将1-丁基-3-甲基咪唑双三氟甲烷磺酰亚胺盐（[Bmim]TFSI）、丙基三辛基鏻四氟硼酸盐（[P（C₃H₇）（C₈H₁₇）₃]BF₄）和丙基三辛基鏻双三氟甲烷磺酰亚胺盐（[P（C₃H₇）（C₈H₁₇）₃]TFSI）负载于活性炭上。对产物进行了热重和孔结构分析,并以气相甲苯和二甲苯为代表物,研究了其对芳香烃的静态和动态吸附性能。研究结果表明：活性炭经离子液体改性后,能显著提高其对芳香烃的吸附性能;其中 [P（C₃H₇）（C₈H₁₇）₃]TFSI和[P（C₃H₇）（C₈H₁₇）₃]BF₄）浸渍改性活性炭的甲苯静态吸附量较大,分别为782 mg/g和777 mg/g （25 ℃,0.1 MPa）;[P（C₃H₇）（C₈H₁₇）₃]BF₄浸渍改性活性炭对于3种二甲苯异构体的吸附量最大,且排序依次为邻二甲苯>间二甲苯>对二甲苯。吸附动力学研究表明,在较高的甲苯初始浓度和较低的气体流量下,[P（C₃H₇）（C₈H₁₇）₃]TFSI浸渍改性活性炭具有更好的吸附性能。     

油脂工业废水的回用

以某油脂化工厂排放的达标废水为研究对象,提出了微絮凝-直接过滤、二级活性炭吸附、二氧化氯氧化消毒串连的深度处理工艺,并在小试基础上进行了油脂废水再生回用的工业化试验研究,处理规模为400m^3／d。处理后出水中COD、浊度、色度、阴离子表面活性剂（LAS）含量、细菌总数等均满足市政供水水质标准。回用水可作为碱化车间和油脂预处理车间的生产补充用水。     

Modeling of water quality downgradient of a mulch biowall

Groundwater treatment biowalls may be located close to a surface water body to prevent contaminant discharge from a groundwater plume into the surface water. Groundwater contaminants passing through the biowall are treated within the biowall or immediately downgradient of the biowall. Biowalls designed and constructed for the treatment of chlorinated solvents typically contain either a solid and/or liquid source of organic carbon to promote contaminant degradation by enhanced anaerobic reductive dechlorination. Common solid organic materials in biowalls include wood mulch or similar waste plant material, and common liquid organic materials are vegetable oil (possibly emulsified) or other long‐chain fatty acids. Such biowalls then develop anaerobic conditions in the constructed biowall volume, and potentially downgradient, as dissolved oxygen originally present in the aquifer is consumed. This groundwater condition can lead to the appearance of sulfide if groundwater influent to the biowall contains moderate to high sulfate concentrations. Other researchers have presented evidence for groundwater conditions downgradient of a biowall or a permeable reactive barrier (PRB) that are altered in relation to groundwater quality, besides the desired effect of contaminant degradation or removal by precipitation. The objective of this work was to investigate with modeling the changes in downgradient groundwater species chemistry as a result of a constructed biowall. This was accomplished with a chemical species model to predict levels of sulfate and sulfide present in groundwater in close downgradient proximity to the biowall. The results indicate that downgradient chemical changes could impact a surface water body to which groundwater discharges. The model described could be enhanced by incorporating additional design variables that should be considered in biowall feasibility assessments.     

A design tool for planning emulsified oil‐injection systems

Emulsified oils have been used to stimulate anaerobic bioremediation at hundreds of sites contaminated with chlorinated solvents, perchlorate, heavy metals, and nitrate. A simple spreadsheet‐based tool has been developed to assist in the design of injection‐only systems for distributing emulsified oils in barriers and area treatments. This tool allows users to quickly compare the relative costs and performance of different injection alternatives and identify a design that is best suited to site‐specific conditions. Contact efficiency is estimated using results of prior numerical model simulations and dimensionless scaling factors that relate the volume of oil and water injected to treatment‐zone dimensions. Sensitivity analysis results indicate that maximum oil retention is one of the most important factors controlling system performance and cost. © 2008 Wiley Periodicals, Inc.     

Effective low-temperature thermal aeration of soils

Low-temperature thermal aeration (LTTA) is a remedial technology developed by Canonie Environmental Services Corp. (Canonie) for use on soils containing nonchlorinated hydrocarbons, chlorinated solvents, volatile organic compounds (VOCs), chlorinated pesticides, and low levels of polynuclear aromatic hydrocarbons (PAHs). The LTTA system separates these hazardous constituents from excavated soils and allows the treated soils to be redeposited on-site without restriction. This article describes the various components and operation of LTTA systems for the remediation of soils contaminated with chlorinated and nonchlorinated constituents. The article also details the results of projects completed to date, principally for soil impacted with chlorinated hydrocarbons, and discusses the general characteristics and results of systems used for soils contaminated with nonchlorinated hydrocarbons (gasoline, etc.).     

Leaching behaviour of different scrap materials at recovery and recycling companies: Full-, pilot- and lab-scale investigation

Scrap material recovery and recycling companies are confronted with waste water that has a highly fluctuating flow rate and composition. Common pollutants, such as COD, nutrients and suspended solids, potentially toxic metals, polyaromatic hydrocarbons and poly chlorinated biphenyls can exceed the discharge limits. An analysis of the leaching behaviour of different scrap materials and scrap yard sweepings was performed at full-scale, pilot-scale and lab-scale in order to find possible preventive solutions for this waste water problem. The results of these leaching tests (with concentrations that frequently exceeded the Flemish discharge limits) showed the importance of regular sweeping campaigns at the company, leak proof or covered storage of specific scrap materials and oil/water separation on particular leachates. The particulate versus dissolved fraction was also studied for the pollutants. For example, up to 98% of the polyaromatic hydrocarbons, poly chlorinated biphenyls and some metals were in the particulate form. This confirms the (potential) applicability of sedimentation and filtration techniques for the treatment of the majority of the leachates, and as such the rainwater run-off as a whole.     

Feasibility of a monitoring system for detecting changes in dioxin concentrations of both in flue gas and fly ash in incineration plants

Surrogate measurements should be low in cost and quick to perform. To examine its feasibility, continuous surrogate monitoring was performed using an organic halogen compound (OHC) analyzer. Surrogates for dioxins (DXNs) from waste incinerators were examined by changing the operating conditions such as the atomized volume of activated carbon added and the temperature at the inlet of the dust collector. OHCs were measured along with DXNs in flue gas at the inlet and the outlet of the dust collector of two waste incinerators over five runs; the fly ash was sampled at the same time. Although the final flue gas concentration of DXNs at the incineration plants was below the regulation criteria, this does not mean complete reduction of DXNs. In addition, the de novo synthesis of DXNs inside the dust collectors was studied by analyzing the mass balance for DXNs concentrations in flue gas and fly ash. Semivolatile chlorinated organic compound concentrations at the outlet of the bag filter were basically well correlated with DXNs levels at the inlet of the bag filter in the test runs. When advanced flue gas treatment is applied by using a bag filter and lime/activated carbon adsorbent, DXNs that may be generated during flue gas cooling processes move to the fly ash, and this amount determines the mass balance of the entire system. It may be useful to monitor surrogate organic halogens for detecting changes in DXN concentrations of both flue gas and fly ash in incineration plants.     

The Roles of Photooxidation and Biodegradation in Long-term Weathering of Crude and Heavy Fuel Oils

Although spilled oil is subject to a range of natural processes, only combustion, photooxidation and biodegradation destroy hydrocarbons and remove them from the biosphere. We present laboratory data that demonstrate the molecular preferences of these processes, and then examine some oil residues collected from previously documented releases to confirm the important roles that these processes play in removing spilled oil from both marine and terrestrial environments.     

负载金属改性活性炭纤维的脱硫性能

采用浸渍法将金属负载到活性炭纤维(ACF)上对其进行改性,研究了负载金属改性ACF对模型油(二苯并噻吩-正辛烷)的吸附脱硫效果,对比了不同单金属和复合金属盐改性ACF的脱硫性能。实验结果表明:Ag和Zn复合改性的ACF具有最好的脱硫性能;在吸附温度为40℃,吸附时间为2.5 h,油剂质量比为21.5的优化条件下,脱硫率高达97.55%,且具有良好的重复利用性。     

Pyrolysis of waste tyres: A review

Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence on the product yield, and gas and oil composition, is the type of reactor used which in turn determines the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aromatic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases produced from the pyrolysis of waste tyres are H₂, C₁–C₄ hydrocarbons, CO₂, CO and H₂S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale.     

响应面法优化阴阳极同时作用电化学法处理染料废水

在自制电化学反应器中,以甲基橙模拟染料废水为处理对象,采用Box-Behnken Design响应面法研究了影响阴阳极同时作用电化学法处理染料废水的因素及其交互作用。实验得出各因素对废水脱色率影响的大小顺序为：电流密度> Fe³⁺浓度>Cl^-浓度。各因素之间的交互作用对废水脱色率影响的大小顺序为：电流密度和Fe³⁺浓度>电流密度和Cl^-浓度>Fe³⁺浓度和Cl^-浓度。优化结果表明：Fe³⁺浓度为1.02 mmol/L、Cl^-浓度为10.96 mmol/L、电流密度为11.52 mA/cm²时,最佳脱色率为94.67%。阴阳极同时作用电化学法对甲基橙去除效果显著。     

Dioxin emissions: Possible techniques for maintaining the limit of 0.1 ng TE m−3 (as of 1990/91)

Processes which will achieve up to 100-fold reduction of exhaust gas emissions of dioxin as proposed for the new German Standards are reviewed. A combination of processes which remove fly ash, NO_x, SO_x, HCl and other pollutants will also remove dioxins. Reduction of chlorinated compounds fed to the incinerator is not likely to make any significant difference. Good turbulence with elimination of cold spots in the firebox will ensure initial thermal destruction. Dioxins are synthesized on fly ash particles at temperatures between 200 and 400° C. Rapid temperature reduction across this range by water injection will greatly reduce dioxin levels. Catalytic inhibitors can also be used. Since dioxin is adsorbed on fly ash, efficient scrubbing is essential for high removal efficiency. Sorption on active carbon beds is also being evaluated.     

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.     

Oil and water separation in marine oil spill clean-up operations

This paper discusses the changes in spilled oil properties over time and how these changes affect differential density separation. It presents methods to improve differential density, and operational effectiveness when oil-water separation is incorporated in a recovery system. Separators function because of the difference in density between oil and seawater. As an oil weathers this difference decreases, because the oil density increases as the lighter components evaporate. The density also increases as the oil incorporates water droplets to form a water-in-oil emulsion. These changes occur simultaneously during weathering and reduce the effectiveness of separators. Today, the state-of-the-art technologies have limited capabilities for separating spilled marine oil that has weathered.For separation of emulsified water in an emulsion, the viscosity of the oil will have a significant impact on drag forces, reducing the effect of gravity or centrifugal separation. Since water content in an emulsion greatly increases the clean up volume (which can contain as much as two to five times as much water as the volume of recovered oil), it is equally important to remove water from an emulsion as to remove free water recovered owing to low skimmer effectiveness. Removal of both free water and water from an emulsion, has the potential to increase effective skimming time, recovery effectiveness and capacity, and facilitate waste handling and disposal. Therefore, effective oil and water separation in marine oil spill clean-up operations may be a more critical process than credited because it can mean that fewer resources are needed to clean up an oil spill with subsequent effects on capital investment and basic stand-by and operating costs for a spill response organization.A large increase in continuous skimming time and recovery has been demonstrated for total water (free and emulsified water) separation. Assuming a 200 m³ storage tank, 100 m³ h⁻¹ skimmer capacity, 25% skimmer effectiveness, and 80% water content in the emulsion, the time of continuous operation (before discharge of oil residue is needed), increases from 2 to 40 h and recovery of oil residue from 10 to 200 m³.Use of emulsion breakers to enhance and accelerate the separation process may, in some cases, be a rapid and cost effective method to separate crude oil emulsions. Decrease of water content in an emulsion, by heating or use of emulsion breakers and subsequent reduction in viscosity, may improve pumpability, reduce transfer and discharge time, and can reduce oily waste handling, and disposal costs by a factor of 10. However, effective use of emulsion breakers is dependant on the effectiveness of the product, oil properties, application methods and time of application after a spill.