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.     

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.     

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.     

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.     

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.

     

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.     

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.     

The weathering properties of four unique crude oils from Australia

This paper reports on the results of weathering studies conducted on four light crude oils from production platforms on the northwest shelf of Australia. The laboratory weathering included both evaporative weathering and emulsification studies. The fresh oils and their topped residues were subjected to a battery of physical and chemical characterization analyses. Detailed analyses were performed for n-alkanes by GC/FID and for mono- and polycyclic aromatic hydrocarbons and phenols by GC/MS. The water-in-oil emulsion formation properties of these oils and their topped residues were investigated at two environmentally significant temperatures (13 and 20°C). The results of the analyses indicate that these oils are very different compositionally and have a wide range of physical and chemical properties. The emulsification properties of these oils and their weathered residues ranged from oils that have very rapid water uptake to oils having no water uptake. Unexpectedly, the very waxy oils had very little water uptake and did not form stable water-in-oil emulsions.     

聚合物驱采油污水稳定性的影响因素

研究了聚合物质量浓度、分子量及原油族组分对模拟含油污水油水界面性质的影响。实验结果表明：聚合物驱采油污水的稳定性不但与聚合物含量、分子量有关,还与原油中沥青质、胶质的含量有关;随着含油污水中阴离子型聚丙烯酰胺（APAM）质量浓度的增加,油水界面张力逐渐下降,Zeta电位绝对值和油水界面剪切黏度逐渐上升;APAM分子量越小,油水界面张力降低的程度越大;随剪切速率的增加,油水界面剪切黏度均逐渐降低;当剪切速率小于0.30 s-1时,4种原油族组分对污水稳定性影响的大小顺序为沥青质>胶质>芳香分>饱和分;随沥青质、胶质含量的增加,油水界面张力明显降低,Zeta电位的绝对值显著增大。     

Oil/Suspended Particulate Material Interactions and Sedimentation

The interactions of physically dispersed oil droplets with suspended particulate material (SPM) can be important for the transport of bulk quantities of spilled crude oil and polycyclic aromatic hydrocarbons (PAH) to subtidal sediments. The literature regarding oil/SPM interactions is reviewed, and results from whole-oil droplet/SPM interaction kinetics and pure-component (Prudhoe Bay crude oil distillate cut) equilibrium partitioning experiments are presented. The effects of oil type, SPM characteristics, and salinity on the interaction rates are examined, and the importance of whole-oil droplet/SPM interactions on particle agglomeration and settling behavior are discussed. Whole-oil droplet/SPM interactions are retarded as oil droplet dispersion into the water column is inhibited by oil viscosity increases due to evaporation weathering and water-in-oil emulsification. Compared to whole oil droplet/SPM interactions, dissolved-component/SPM adsorption is not as significant for transport of individual components to sediments. The information presented in this paper can be used to augment computer-based models designed to predict oil-spill trajectories, oil-weathering behavior, and spilled oil impacts to the marine environment.     

In situ burning of emulsions R&D in Norway

SINTEF Applied Chemistry has been working in the field of in situ burning since 1988, beginning with the first open water testing of the 3M fire proof boom which took place on Spitsbergen. In recent years, the focus of SINTEF's research activities in this area has been on the burning of emulsions. An experimental programme was initiated by NOFO in 1990 to study the in situ burning of water-in-oil (w/o) emulsions, as part of a wider NOFO programme ‘Oil spill contingency in Northern and Arctic waters’ (ONA). The research conducted under this programme has addressed many areas of in situ burning including:

• •• study of processes governing burning emulsions
• •• development of ignition techniques for emulsions
• •• effect of environmental conditions on burning
• •• burning crude oil and emulsions in broken ice
• •• uncontained burning of crude oil and emulsions.

     

Flame Propagation Across Gelled Alkane-In-Water Emulsions

Flame propagation rates were measured for flames spreading across surfaces of gel-like alkane-in-water emulsions. A long, slender, water-cooled trough was used to contain the mixtures. Abrupt changes in the flame propagation velocities - of nearly two orders of magnitude - were observed to occur near ‘critical’ concentrations of certain alkane/water mixtures. Four alkanes were used - pentane, hexane, heptane, and octane - and fuel rich emulsions (in which water was the continuous phase) were employed. The ability of the aqueous phase of the emulsion to inhibit the release of fuel into the vapor phase plays an important role in the observed behavior. That is, the rate at which fuel can diffuse through both the emulsion and the thin liquid layers that reside on it, is an essential kinetic aspect of the phenomena which determine the flame propagation rate across gelled alkane-in-water emulsions.     

Dynamic modelling of oil boom failure using computational fluid dynamics

The common response to an oil spill on water is to contain the oil with booms and recover it with skimming devices. In some situations, however, the booms cannot hold the oil and the oil will escape underneath the boom due to hydrodynamic forces. Computational fluid dynamics (CFD) is a powerful modelling tool combining fluid dynamics and computer technology. We have utilized a commercial CFD program, Fluent, to simulate the oil-water flow around a boom. The studies accurately model channel experiments conducted in recent years. The studies show that the flow patterns around booms are modified by the presence of oil and, therefore, suggest that towing and wave-conformity tests of booms will not be meaningful unless they are undertaken with the presence of oil.     

The technology windows-of-opportunity for marine oil spill response as related to oil weathering and operations

This paper identifies and estimates time periods as ‘windows-of-opportunity’ where specific response methods, technologies, equipment, or products are more effective in clean-up operations for several oils. These windows have been estimated utilizing oil weathering and technology performance data as tools to optimize effectiveness in marine oil spill response decision-making. The windows will also provide data for action or no-action alternatives. Crude oils and oil products differ greatly in physical and chemical properties, and these properties tend to change significantly during and after a spill with oil aging (weathering). Such properties have a direct bearing on oil recovery operations, influencing the selection of response methods and technologies applicable for clean up, including their effectiveness and capacity, which can influence the time and cost of operations and the effects on natural resources.The changes and variations in physical and chemical properties over time can be modeled using data from weathering studies of specific oils. When combined with performance data for various equipment and materials, tested over a range of weathering stages of oils, windows-of-opportunity can be estimated for spill response decision-making. Under experimental conditions discussed in this paper, windows-of-opportunity have been identified and estimated for four oils (for which data are available) under a given set of representative environmental conditions. These ‘generic’ windows have been delineated for the general categories of spill response namely: (1) dispersants, (2) in situ burning, (3) booms, (4) skimmers, (5) sorbents, and (6) oil-water separators. To estimate windows-of-opportunity for the above technologies (except booms), the IKU Oil Weathering Model was utilized to predict relationships—with 5 m s⁻¹ wind speed and seawater temperatures of 15°C.The window-of-opportunity for the dispersant (Corexit 9527^®) with Alaska North Slope (ANS) oil was estimated from laboratory data to be the first 26 h. A period of ‘reduced’ dispersibility, was estimated to last from 26–120 h. The oil was considered to be no longer dispersible if treated for the first time after 120 h. The most effective time window for dispersing Bonnic Light was 0–2 h, the time period of reduced dispersibility was 2–4 h, and after 4 h the oil was estimated to be no longer dispersible. These windows-of-opportunity are based on the most effective use of a dispersant estimated from laboratory dispersant effectiveness studies using fresh and weathered oils. Laboratory dispersant effectiveness data cannot be directly utilized to predict dispersant performance during spill response, however, laboratory results are of value for estimating viscosity and pour point limitations and for guiding the selection of an appropriate product during contingency planning and response. In addition, the window of opportunity for a dispersant may be lengthened if the dispersant contains an emulsion breaking agent or multiple applications of dispersant are utilized. Therefore, a long-term emulsion breaking effect may increase the effectiveness of a dispersant and lengthen the window-of-opportunity.The window-of-opportunity of in situ burning (based upon time required for an oil to form an emulsion with 50% water content) was estimated to be approximately 0–36 h for ANS oil and 0–1 h for Bonnie Light oil after being spilled. The estimation of windows-of-opportunity for offshore booms is constrained by the fact that many booms available on the market undergo submergence at speeds of less than 2 knots. The data suggest that booms with buoyancy to weight ratios less than 8:1 may submerge at speeds within the envelope in which they could be expected to operate. This submergence is an indication of poor wave conformance, caused by reduction of freeboard and reserve net buoyancy within the range of operation. The windows-of-opportunity for two selected skimming principles (disk and brush), were estimated using modeled oil viscosity data for BCF 17 and BCF 24 in combination with experimental performance data developed as a function of viscosity. These windows were estimated to be within 3–10 h (disk skimmer) and after 10 h (brush skimmer) for BCF 17. Whereas for BCF 24, it is within 2–3 d (disk skimmer) and after 3 d (brush skimmer).For sorbents, an upper viscosity limit for an effective and practical use has in studies been found to be approximately 15,000 cP, which is the viscosity range of some Bunker C oils. Using viscosity data for the relative heavy oils, BCF 17 and BCF 24 (API gravity 17 and 24), the time windows for a sorbent (polyamine flakes) was estimated to be 0–4 and 0–10 d, respectively. With BCF 24, the effectiveness of polyamine flakes, was reduced to 50% after 36 h, although it continued to adsorb for up to 10 d. For BCF 17, the effectiveness of polyamine flakes was reduced to 50% after 12 h, although it continued to adsorb for up to 4 d. The windows-of-opportunity for several centrifuged separators based upon the time period to close the density gap between weathered oils and seawater to less than 0.025 g ml⁻¹ (which is expected to be an end-point for effective use of centrifugal separation technology), were estimated to be 0–18 (ANS) and 0–24 h (Bonnie Light) after the spill. Utilizing the windows-of-opportunity concept, the combined information from a dynamic oil weathering model and a performance technology data base can become a decision-making tool; identifying and defining the windows of effectiveness of different response methods and equipment under given environmental conditions. Specific research and development needs are identified as related to further delineation of windows-of-opportunity.     

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.     

Boom failure mechanisms: Comparison of channel experiments with computer modelling results

A large outdoor flowing water channel has been used to obtain experimental data on boom failure mechanisms. Oil containment and failure around a simple barrier has been observed for oil viscosities from 10 to 5600 cSt at relatively low flow velocities from 0.10 to 0.20 m/s. The centre line profiles of stable contained slicks have been measured and underwater videos of escaping oil have been made when the barrier failed. These experiments have been duplicated with a computational fluid dynamics model of the channel and barrier, and satisfactory agreement between the simulated and the experimental measurements has been obtained. The study indicates that computer simulations of these complex processes can be used to obtain data about failure mechanisms that would be difficult to measure experimentally.     

LAND TREATMENT OF PRODUCED OILY SAND: FIELD RESULTS

Land treatment techniques successfully treated oily waste generated during the production of crude oil. Over 13 years of safe operations have demonstrated the environmental acceptability of the method. Natural biodegradation processes removed nearly 80% of the applied waste oil. The oily fraction of the waste had an average half-life in the soil of approximately 3 years, with significant variability between years. There was a slight increase in the proportion of heavy hydrocarbons (resins and asphaltenes) in the soil, suggesting the preferential degradation of the lighter constituents. Metals of environmental concern did not accumulate in, or migrate from, the plowzone of the soil.     

Storage stability of biocrude oils from fast pyrolysis of poultry litter

The unstable nature of biocrude oils produced from conventional pyrolysis of biomass is one of the properties that limits its application. In the disposal of poultry litter via pyrolysis technology, the biocrude oil produced as a value-added product can be used for on farm applications. In this study, we investigated the influence of bedding material (wood shavings) on the storage stability of biocrude oils produced from the fast pyrolysis of poultry litter. The biocrude oils produced from manure, wood (pine and oak), and mixtures of manure and wood in proportions (75:25 50:50, and 25:75 w/w%) were stored under ambient conditions in sealed glass vials for a period of 6 months and their stability were monitored by measuring the changes in viscosity over time. The manure oil had the lowest rate of viscosity change and thus was relatively the most stable and the oils from the 50:50 w/w% litter mixtures were the least stable. The rate of viscosity change of the manure biocrude oil was 1.33 cP/day and that of the 50/50 litter mixture was 7.6 cP/day for pine and 4.17 cP/day for oak.The spectrometric analyses of the biocrude oils showed that the presence of highly reactive oxygenated functionalities in the oil were responsible for the instability characteristic of the litter biocrude oils. The poor stability of the biocrude oil from the 50:50 w/w% litter mixtures was attributed to reactions between nitrogenous compounds (amides) from protein degradation and oxygenated compounds from the decomposition of polysaccharides and lignin. The addition of 10% methanol and 10% ethanol to the oil from 50% manure and 50% pine reduced the initial viscosity of the oil and was also beneficial in slowing down the rate of viscosity change during storage.     

Estimating Time Windows for Burning Oil at Sea: Processes and Factors

This paper discusses processes and factors for estimating time period windows of in situ burning of spilled oil at sea. Time-periods of in situ burning of Alaska North Slope (ANS) crude oil are estimated using available data. Three crucial steps are identified. The First Step is to determine the time it takes for the evaporative loss to reach the known or established limitation for evaporation and compare this time-period with estimated time of ignition at the ambient wind and sea temperatures. The Second Step is to determine the water up-take of the spilled oil and compare it with the known or established limitation for water-in-oil content. The Third Step is to determine the necessary heat load from the igniter to bring the surface temperature of the spilled oil to its flash point temperature so that it will burn at the estimated time period for ignition of the slick.     

阳离子乳液型清水剂的制备及其在油田污水处理中的应用

以二甲基二烯丙基氯化铵(DMDAAC)为阳离子单体,苯乙烯、丙烯酸丁酯为疏水单体,十六烷基三甲基溴化铵和聚氧乙烯辛基苯酚醚-10(OP-10)为乳化剂,过硫酸铵为引发剂,采用乳液聚合法制备乳液型清水剂。优化了制备清水剂的工艺条件,考察了清水剂对油田污水的处理效果。实验结果表明:在x(DMDAAC)小于20%、n(苯乙烯)∶n(丙烯酸丁酯)为2∶1、乳化剂占单体质量分数为5%、引发剂占单体质量分数为0.5%的优化条件下可制备形成稳定的阳离子乳液清水剂;分子量越大、x(DMDAAC)越大,清水剂的除油效果越好;在x(DMDAAC)为20%、其他最优条件不变的情况下制备的Q20清水剂使用浓度为30 mg/L时可使油田污水含油量从295 mg/L降至13 mg/L。自制清水剂的除油效果好于市售清水剂。