Agents Which Promote and Stabilize Water-in-Oil Emulsions

A number of research groups have investigated the formation and stabilization of water-in-oil emulsions. A variety of compounds and mixtures have been shown to promote and stabilize these emulsions, including sea water particulates, as well as fractions or compounds found in crude oil. Asphaltenes, resins and waxes in crude oil contribute to the formation of stable oil-in-water emulsions. Within the asphaltene fraction, the nickel porphyrins appear to play an essential role in emulsion formation. The vanadium porphyrins, although more abundant than nickel porphyrins in most crude oils, do not play an important role in emulsion formation, possibly because of their higher polarity. It appears that compounds with higher solubility in the oil phase than in the aqueous phase are the emulsifying agents that can promote stable water-in-oil emulsions. Crude oils that form very unstable emulsions, e.g. Gullfaks crude oil from the North Sea, require weathering as well as the addition of nickel porphyrins before a stable emulsion will form. The weathering may cause the formation of colloidal asphaltene particles and highly polar compounds that contributes to emulsion stabilization. Essential to the formation of stable water-in-oil emulsions are sufficient amounts of certain polar compounds. If there are insufficient amounts of these compounds, then even the presence of particles and waxes will not lead to the formation of stable emulsions.     

Heat and chemical treatment of mechanically recovered w/o emulsions

Nearly all crude oils and some heavier refined products form stable water-in-oil (w/o) emulsions when spilled and weathered at sea. Breaking these emulsions and discarding the separated water allow more oil to be recovered and stored by OSRVs (Oil Spill Recovery Vessels) and make the handling of oily waste easier due to viscosity reduction. This study was conducted to determine whether a combination of heat and emulsion breaker is more effective than either technique used alone. The results will be used to prepare guidelines for treatment of w/o emulsions and planning of large-scale tests.A bench-scale laboratory study was carried out using emulsions prepared from different crude oil residues (BCF-17, Alaskan North Slope and Bonny Light) and a Bunker C fuel oil/gas oil blend (IF-80). Tubes containing w/o emulsions, with or without emulsion breaker added, were partially submerged in a water bath at different temperatures to simulate the heating system of the recovered oil tanks onboard the OSRVs. The effectiveness of the emulsion breaking was measured by recording settled water over a 24 h period. The results showed that:

• •• The stability of a w/o emulsion and its response to heat and emulsion breaker is highly dependent on different characteristics of the oil from which it is formed.
• •• Stable w/o emulsions that can be slowly broken by heat alone were, in general, broken much more rapidly if emulsion breaker was added in addition to heat.
• •• The w/o emulsions formed from relatively paraffinic crude oil (e.g. ANS) exhibit faster breaking rates than w/o emulsions formed from crude oils with high asphaltene content, such as BCF-17.
• •• All w/o emulsions formed from the crude oil residues could be broken by the application of moderate amounts of heat. W/o emulsions produced from Bunker C/Diesel oil blend were not broken at all by relatively high heat inputs (up to 100°C) and required both the addition of heat and emulsion breaker to obtain partially breaking.

     

Determination of the Thermal Efficiency of Pre-boilover Burning of a Slick of Oil on Water

The burning rate of a slick of oil on a water bed is calculated by a simple expression derived from a one-dimensional heat conduction equation. Heat feedback from the flame to the surface is assumed to be a constant fraction of the total energy released by the combustion reaction. The constant fraction (χ) is named the burning efficiency and represents an important tool in assessing the potential of in situ burning as a counter-measure to an oil-spill. The total heat release, as a function of the pool diameter, is obtained from an existing correlation. It is assumed that radiative heat is absorbed close to the fuel surface, that conduction is the dominant mode of heat transfer in the liquid phase and that the fuel boiling temperature remains constant. By matching the characteristic thermal penetration length scale for the fuel/water system and an equivalent single layer system, a combined thermal diffusivity can be calculated and used to obtain an analytical solution for the burning rate. Theoretical expressions were correlated with crude oil and heating oil, for a number of pool diameters and initial fuel layer thickness. Experiments were also conducted with emulsified and weathered crude oil. The simple analytical expression describes well the effects of pool diameter and initial fuel layer thickness permitting a better observation of the effects of weathering, emulsification and net heat feedback to the fuel surface. Experiments showed that only a small fraction of the heat released by the flame is retained by the fuel layer and water bed (of the order of 1%). The effect of weathering on the burning rate decreases with the weathering period and that emulsification results in a linear decrease of the burning rate with water content.     

Determination of the Burning Characteristics of a Slick of Oil on Water

The burning rate of a slick of oil on a water bed is characterized by three distinct processes, ignition, flame spread and burning rate. Although all three processes are important, ignition and burning rate are critical. The former, because it defines the potential to burn and the latter because of the inherent possibility of boilover. Burning rate is calculated by a simple expression derived from a one-dimensional heat conduction equation. Heat feedback from the flame to the surface is assumed to be a constant fraction of the total energy released by the combustion reaction. The constant fraction (χ) is named the burning efficiency and represents an important tool in assessing the potential of in situ burning as a counter-measure to an oil spill. By matching the characteristic thermal penetration length scale for the fuel/water system and an equivalent single layer system, a combined thermal diffusivity can be calculated and used to obtain an analytical solution for the burning rate. Theoretical expressions were correlated with crude oil and heating oil, for a number of pool diameters and initial fuel layer thickness. Experiments were also conducted with emulsified and weathered crude oil. The simple analytical expression describes well the effects of pool diameter and initial fuel layer thickness permitting a better observation of the effects of weathering, emulsification and net heat feedback to the fuel surface. Experiments showed that only a small fraction of the heat released by the flame is retained by the fuel layer and water bed (of the order of 1%). Ignition has been studied to provide a tool that will serve to assess a fuels ease to ignite under conditions that are representative of oil spills. Two different techniques are used, piloted ignition when the fuel is exposed to a radiant heat flux and flash point as measured by the ASTM D56 Tag Closed Cup Test. Two different crude oils were used for these experiments, ANS and Cook Inlet. Crude oils were tested in their natural state and at different levels of weathering, showing that piloted ignition and flash point are strong functions of weathering level.     

The Long Term Weathering of Water-in-Oil Emulsions

This paper summarizes studies to determine the long-term stability of water-in-oil emulsions in the laboratory and in large tanks. The long-term stability of emulsions was investigated in the laboratory for up to 9 years and by studying emulsion formation in a large test tank over a period of 2-10 days.Two stable emulsions, formed in the laboratory, had been preserved for 5 and 9 years and remained stable despite a small water loss. The long-term stability appears to be similar to that for the short-term stability. Stable emulsion breakdown processes remain poorly understood, because these emulsions do not generally breakdown, but the primary processes may be mechanical break-up and water evaporation.The water-in-oil states produced were found to have analogous properties between the laboratory and two sets of experiments at a large test tank. No fundamental differences in states or properties were observed over the time periods studied (up to 222 h). The state of the oil was found to correlate well with a stability index as defined by the complex modulus divided by the oil viscosity. It is shown that this stability index becomes more useful when the viscosity of the oil is taken at the same time as the complex modulus measurement.The studies show that meso-stable emulsions will break down within 3 days, generally within 1 day and that those emulsions classified as stable remain up to 9 years under laboratory conditions. These studies also show that meso-stable emulsions do not reform, once broken.     

Studies of water-in-oil emulsions: Stability studies

Rheological studies were conducted on the water-in-oil emulsions of three crude oils: Arabian Light; Green Canyon; and Sockeye. The emulsions were found to fall into three categories on the basis of both rheological properties and visual appearance: stable; mesostable; and unstable. Stable emulsions are characterized by high viscosities and elasticities and are indefinitely stable. In this study stable emulsions showed true viscosities (viscosity with elasticity separated) approximately 700 times that of the starting oil and mesostable emulsions approximately 50 times that of the starting oil. Mesostable emulsions break into water, oil and sometimes emulsion within about 3 d.     

Water-in-oil emulsion formation: A review of physics and mathematical modelling

A literature review of the physics and modelling of water-in-oil emulsification is presented. The understanding of the physics of emulsion formation is still incomplete, but developing. The formation of emulsions is due to the surfactant-like action of polar compounds (resins) and asphaltenes in oil. These compounds act to maintain small (1–20 μm) droplets of water in oil. Volatile aromatic compounds in crude oils solubilize asphaltenes and resins. Crude oils containing lower quantities of these volatile compounds or BTEX (benzene, toluene, ethylbenzene, xylenes) will form emulsions given sufficient turbulent sea energy. Oils may lose the BTEX component by weathering before being capable of forming stable emulsions. The kinetics and energy of formation of emulsions is not well understood. Emulsions are often reported to form rapidly after the necessary chemical conditions are achieved and where there is significant wave action or other turbulent energy. Oil spill models generally employ a first-order rate law (exponential) to predict emulsion formation.     

Mathematical modelling of sewage sludge incineration in a bubbling fluidised bed with special consideration for thermally-thick fuel particles

Fluidised bed combustor (FBC) is one of the key technologies for sewage sludge incineration. In this paper, a mathematical model is developed for the simulation of a large-scale sewage sludge incineration plant. The model assumes the bed consisting of a fast-gas phase, an emulsion phase and a fuel particle phase with specific consideration for thermally-thick fuel particles. The model further improves over previous works by taking into account throughflow inside the bubbles as well as the floating and random movement of the fuel particles inside the bed. Validation against both previous lab-scale experiments and operational data of a large-scale industrial plant was made. Calculation results indicate that combustion split between the bed and the freeboard can range from 60/40 to 90/10 depending on the fuel particle distribution across the bed height under the specific conditions. The bed performance is heavily affected by the variation in sludge moisture level. The response time to variation in feeding rate is different for different parameters, from 6min for outlet H(2)O, 10min for O(2), to 34min for bed temperature.     

Utilization and treatment of exhausted cooling oil-emulsions

The subject of investigation was exhausted cooling oil-emulsions coming from copper wire drawing. The summary content of the organic substances in emulsions expressed as COD, ranged from 200 to 300 gO₂/dm³. The total amount of copper was about 7 g/dm³. The suggested method of treatment was based on separation of emulsion, thermocatalytic oxidation of the oil phase and electrochemical reduction of copper. The method allows oxidation of 99% organic substances in an autothermic way and over 90% recovery of metallic copper contained in emulsion with energy consumption at 2.2 kWh/kg.     

Bioconversion of industrial wastes: paint sludge from automotive manufacturing

The compostability of water-based paint sludge originating from the automotive industry was investigated. Six reactors were operated. Wastewater treatment sludge from the same industry was used as additional substrate, and corncob was used as a bulking agent. The level of paint sludge within the compost mixtures varied between 55 and 85%. All reactors yielded a temperature increase up to thermophilic phase levels (>?40 °C) for a minimum of 5 days, and organic matter and C/N losses were observed. BTEX concentrations decreased during composting. Nickel and tin levels in the final product exceeded the legal compost limits. The calorific value of the compost mixtures increased from 9532 to 18774 kJ/kg at the end of the composting process. It was seen that the process applied in this study can be utilized as a biodrying step before the usage of paint sludge at cement kilns as additional fuel.     

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.     

液膜法处理含硝基酚废水试验研究

采用液膜法对含硝基酚废水进行了处理试验研究。对低浓度废水选取了适宜的工艺条件：油相中表面活性剂的质量分数为2％；内水相中NaOH的质量分数为2％；乳液中油相与内水相的质量比为2：1；外水相：pH为2；乳液与外水相的体积比为1：3。在进水总酚质量浓度分别为1050、6700mg／L的条件下，出水总硝基酚的去除率均高达99．9％以上，同时废水中的硝基苯和COD也有较好的去除效果。     

Enhanced anaerobic bioremediation of chlorinated solvents utilizing vegetable oil emulsions

The use of vegetable oil as an electron donor to enhance the reductive dechlorination of chlori‐nated solvents as an in situ remediation technology is gaining significant traction. Vegetable oil is a cost‐effective slow‐release electron donor with greater hydrogen‐release efficiency than other electron‐donor products. However, neat vegetable oil can inhibit distribution in aquifers due to the oil droplets blocking the flow of groundwater through the smaller pore spaces in the aquifer materials. This issue has been partially overcome by applying the vegetable oil as an oil‐water emulsion, which typically is created in the field. However, the field preparation results in a mixture of droplet sizes, including larger droplets that can make the emulsions unstable and reduce the soil permeability by blocking soil‐pore throats with oil. RNAS, Inc., has developed a kinetically sta‐ble soybean oil emulsion (“Newman Zone”) consisting of submicron droplets with less droplet‐size variation than field‐prepared emulsions. This product is composed of a blend of fast‐release (sodium lactate) and slow‐release (soybean oil) electron donors. The emulsion is produced in a stable factory environment in which it is pasteurized and packaged in sterile packaging. This ma‐terial can be utilized as an electron donor without further treatments or amendments in the field. This article discusses factors associated with selecting electron donors and the development of vegetable oil–based products. A case study of an application of Newman Zone at a former adhe‐sives manufacturing facility is then presented. The case study demonstrates the effect of Newman Zone in reducing chlorinated solvent concentrations in groundwater by both rapidly stimulating initial microbial activity and supporting long‐term reductive dechlorination with a slow‐release electron donor. © 2006 Wiley Periodicals, Inc.     

Analysis of the Structure-Properties Relationships of Different Multiphase Systems Based on Plasticized Poly(Lactic Acid)

Poly(lactic acid) is one of the most promising biobased and biodegradable polymers for food packaging, an application which requires good mechanical and barrier properties. In order to improve the mechanical properties, in particular the flexibility, PLA plasticization is required. However, plasticization induces generally a decrease in the barrier properties. Acetyl tributyl citrate (ATBC) and poly(ethylene glycol) 300 (PEG), highly recommended as plasticizers for PLA, were added up to 17 wt% in P(D,L)LA. In the case of PEG, a phase separation was observed for plasticizer contents higher than 5 wt%. Contrary to PEG, the T_g decrease due to ATBC addition, modelled with Fox’s law, and the absence of phase separation, up to 17 wt% of plasticizer, confirm the miscibility of PLA and ATBC. Contents equal or higher than 13 wt% of ATBC yielded a substantial improvement of the elongation at break, becoming higher than 300%. The effect of PLA plasticization on the barrier properties was assessed by different molecules, with increasing interaction with the formulated material, such as helium, an inert gas, and oxygen and water vapour. In comparison to the neat sample, barrier properties against helium were maintained when PLA was plasticized with up to 17 wt% of ATBC. The oxygen permeability coefficient and the water vapour transmission rate doubled for mixtures with 17 wt% ATBC in PLA, but increased five-fold in the PEG plasticized samples. This result is most likely caused by increased solubility of oxygen and water in the PEG phase due to their mutual miscibility. To conclude, ATBC increases efficiently the elongation at break of PLA while maintaining the permeability coefficient of helium and keeping the barrier properties against oxygen and water vapour in the same order of magnitude.     

Pervaporation of ethanol produced from banana waste

Banana waste has the potential to produce ethanol with a low-cost and sustainable production method. The present work seeks to evaluate the separation of ethanol produced from banana waste (rejected fruit) using pervaporation with different operating conditions. Tests were carried out with model solutions and broth with commercial hollow hydrophobic polydimethylsiloxane membranes. It was observed that pervaporation performance for ethanol/water binary mixtures was strongly dependent on the feed concentration and operating temperature with ethanol concentrations of 1–10%; that an increase of feed flow rate can enhance the permeation rate of ethanol with the water remaining at almost the same value; that water and ethanol fluxes was increased with the temperature increase; and that the higher effect in flux increase was observed when the vapor pressure in the permeate stream was close to the ethanol vapor pressure. Better results were obtained with fermentation broth than with model solutions, indicated by the permeance and membrane selectivity. This could be attributed to by-products present in the multicomponent mixtures, facilitating the ethanol permeability. By-products analyses show that the presence of lactic acid increased the hydrophilicity of the membrane. Based on this, we believe that pervaporation with hollow membrane of ethanol produced from banana waste is indeed a technology with the potential to be applied.     

乳状液膜提取废汞触媒浸出液中的汞及 乳状液破乳

采用乳状液膜法分离提取废汞触媒浸出液中的Hg~(2+)。考察了影响乳状液膜体系分离富集汞的主要因素,并对分离提取后的乳液相进行了破乳研究。分离提取实验结果表明:乳状液膜体系的最佳配方为流动载体磷酸三丁酯体积分数10%、表面活性剂失水山梨糖醇脂肪酸酯体积分数4%、膜溶剂磺化煤油体积分数86%、内水相HCl溶液浓度0.10mol/L、油相与内水相的体积比1∶1;在乳状液与外水相的体积比为1∶10的条件下Hg~(2+)提取率达78.50%。破乳实验结果表明:加热破乳、离心破乳、加热离心联合破乳3种方法的破乳率分别为29.0%,54.0%,85.7%;采用加热离心联合法破乳后,Hg~(2+)富集倍数达8.5。     

Quality assessment of composts prepared with olive mill wastewater and agricultural wastes

The co-composting of solid residue from olive oil production process, exhausted olive cake (EOC), with poultry manure (PM) watered with olive mill wastewater (OMW) was considered as an efficient method for the treatment of olive oil extraction effluent having high organic content including phenolic polluting compounds. The process was carried out by using three aerated windrows of variable compositions. OMW was used continuously during the bio-oxidative period, which lasted three months, to replace water for windrow moistening. The main process parameters (temperature, pH, humidity and C/N) were monitored over four months to ascertain the maturity of the compost. The composting process lasted four months during which 26 moistenings of the mixtures were performed with OMW or water to keep moisture within the ideal range of 45-60% (w/w). At the maturity stage, the C/N ratios were less than 16, pH of the resulting products were slightly alkaline (pH=8) and electrical conductivity was relatively high in the OMW mixtures (5.46-5.48 Sm(-1)) when compared with water application. Nitrates increased (0.16-0.42%) and phenol contents were reduced by more than 49%. Mature composts were then used as an amendment for potato production in a field where no inhibitory effect was observed. Potato productivity increased 10-23% as a result of compost application. No noticeable negative impact of OMW on the soil system was observed. Phenolic compound concentrations in the stabilised composts were comparable in the three studied mixtures (different sites) and averaged 0.24%. Considering previous results and this three year study, it has been observed that the benefit of these composts demonstrated the potential sustainable agronomic production of potato while using locally available recycled organic materials.     

Combustion characteristics of paper mill sludge in a lab-scale combustor with internally cycloned circulating fluidized bed

After performing a series of batch type experiments using a lab-scale combustor, consideration was given to the use of an internally cycloned circulating fluidized bed combustor (ICCFBC) for a paper mill sludge. Operation parameters including water content, feeding mass of the sludge, and secondary air injection ratio were varied to understand their effects on combustion performance, which was examined in terms of carbon conversion rate (CCR) and the emission rates of CO, C(x)H(y) and NO(x). The combustion of paper mill sludge in the ICCFBC was compared to the reaction mechanisms of a conventional solid fuel combustion, characterized by kinetics limited reaction zone, diffusion limited reaction zone, and transition zone. The results of the parametric study showed that a 35% water content and 60 g feeding mass generated the best condition for combustion. Meanwhile, areal mass burning rate, which is an important design and operation parameter at an industrial scale plant, was estimated by a conceptual equation. The areal mass burning rate corresponding to the best combustion condition was approximately 400 kg/hm(2) for 35% water content. The secondary air injection generating swirling flow enhanced the mixing between the gas phase components as well as the solid phase components, and improved the combustion efficiency by increasing the carbon conversion rate and reducing pollutant emissions.     

有机磷阻燃剂生产废水预处理工艺研究

采用液膜萃取—酸析沉降—络合萃取组合工艺对有机磷阻燃剂生产废水进行预处理.最佳工艺条件为:液膜萃取时,液膜油相(表面活性剂与煤油的混合液)与内水相(H2SO4溶液)的体积比2∶1、乳化液膜与废水的体积比1∶8、废水pH 13.0,硫酸体积分数10％、煤油中表面活性剂质量浓度30 g/L、液膜萃取时间 15 min;酸析沉降时,废水pH l.0,酸析沉降时间30 min;络合萃取时,络合萃取剂(烷基叔胺N235与煤油的混合液)中烷基叔胺N235体积分数30％,络合萃取剂与废水的体积比1∶4,废水pH l.0,络合萃取时间30 min.在此最佳处理条件下,废水COD总去除率可达93％,吡啶去除率达99.9％以上,总磷去除率可达97％,BOD5/COD提高至0.32,有利于后续生化处理.