Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
  • C10L1/328—Oil emulsions containing water or any other hydrophilic phase
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
  • B01F23/40—Mixing liquids with liquids; Emulsifying
  • B01F23/41—Emulsifying
  • B01F23/4105—Methods of emulsifying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
  • B01F33/80—Mixing plants; Combinations of mixers
  • B01F33/82—Combinations of dissimilar mixers
  • B01F33/821—Combinations of dissimilar mixers with consecutive receptacles
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
  • F17D1/00—Pipe-line systems
  • F17D1/08—Pipe-line systems for liquids or viscous products
  • F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
  • F17D1/17—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by mixing with another liquid, i.e. diluting

Definitions

• the present invention relates to a emulsions formed from precursor emulsions having any particle modal distributions with the result being a unimodal emulsion with maximized desired chemical and physical characteristics .
• Simple two phase emulsions are generally classified by the concentration of the dispersed phase, the size distribution of the dispersed droplets, and the rheological properties of the emulsion.
• Emulsions with 0-30% by volume of dispersed phase are known as low internal phase ratio emulsions (LIPR)
• MIPR medium internal phase emulsions
• MIPR medium internal phase emulsions
• HIPR high internal phase emulsions
• the rheological behavior of an emulsion can be Newtonian or non-Newtonian. The extent of this behavior would depend upon the properties and concentrations of the two liquids used to make the emulsion.
• LIPR emulsions generally show Newtonian behavior. As the dispersed oil phase concentration increases, behavior becomes progressively more non-Newtonian.
• 0/W emulsions can be considered Newtonian up to a dispersed phase volume of 0.4 (i.e. 40% dispersed phase). This was achieved by manufacturing 0/W emulsions at different dispersed phase concentrations and measuring the shear stress ( ⁇ ) at different shear rates (Y) . All the emulsions contained droplets of the same mean diameter and were performed at a constant temperature.
• the viscosity of an emulsion is defined as the ratio of shear stress ( ⁇ ) to shear rate ( 3 ⁇ ). This is given by the equation:
• the viscosity of the dispersed phase can sometimes play a part in determining the emulsion viscosity. This is especially true when internal circulation of the droplets occurs, which reduces the distortion of the flow field, resulting in a reduced viscosity of the emulsion. In such a system, an increase in the viscosity of the dispersed phase will result in decreased internal circulation and consequently increases the effective emulsion viscosity. When an emulsifying agent is present, internal circulation is greatly inhibited, and the dispersed phase droplets behave more like solid particles according to R. Pal et al .
• ⁇ > is the relative viscosity of the emulsion and ⁇ is the volume fraction of dispersed phase. This equation is accurate but highly limited in its applicability. The suspension must be extremely dilute
• K is a constant reflecting droplet packing
• the Krieger-Dougherty equation appears to adequately fit most collected data for emulsions with a total volume fraction up to the critical deformation volume fraction ( ⁇ d ) . This is the point at which high levels of droplet deformation can occur under shear stress.
• the critical deformation volume fraction is variable for different emulsions and depends on both the properties of the dispersed phase and the emulsifying agent used. As the total volume fraction increases, emulsion rheology becomes less Newtonian.
• Viscosity predicting equations such as the Krieger-Dougherty equation and the Mooney equation are not exact, but are based upon experimental data and various assumptions. They show accuracy at lower volume fractions but their limitations are shown at higher volume fractions where deviations also occur in experimental data.
• the optimum packing structure (hexagonal lattice formation) would result in a maximum packing concentration of 0.74.
• the maximum packing concentration, and consequently the viscosity will depend upon the relative contribution (by volume) of the different sized particles being mixed together. It would also depend on the shape of the particles and their size distribution.
• the maximum packing concentration can also be reduced if aggregation occurs within the system as this can trap fluid between solid particles.
• TaJbIe 1. Optimum composition of small and large particles to achieve specific concentrations (from Farris [Trans. Soc . Rheol . - 12.281(1968)] .
• This system results in greatly improved packing efficiency and a consequent increase in system fluidity according to Tsenoglou and Yang [Polymer Engineering and Science, Mid-Nov 1990, VoI 30, No 21, Fluidity and optimum packing in suspensions of mixed dissimilar particles] .
• the industrial relevance of this could be to create a bimodal suspension (or emulsion) containing an increased dispersed volume fraction with the same viscosity as a mono-modal system.
• the technology could be used to create a bimodal system with the same dispersed volume fraction > but with a significantly reduced viscosity compared to a mono-modal system.
• the minimum viscosity achieved was measured to be almost 200 times smaller than that of the pure fine fraction.
• the layer of dispersant that surrounds the particles becomes much more significant when the particles are small. In this case, the minimum viscosity is occurring at 25% small particles by volume, but the effective volume fraction calculates as 31.6% when the dispersant layer is taken into account .
• Solid spheres can pack in many different ways, but
• Fig. 2 shows the viscosities at 25% small particles by volume [Greenwood et al. [J. Colloid Interface Sci, 191, 11-21 (1997), The effect diameter ratio and volume ratio on the viscosity of bimodal suspensions of polymer lattices] ] .
• Fig. 3 shows the results at a diameter ratio of 6.37 where the viscosity minimum can be observed at 25% small particles as expected.
• a diameter ratio of 1.08 does exhibit a minimum in viscosity at 75% small particles that is lower than that of the large particles alone. Although it is only a minor reduction, it does occur at all concentrations tested. There do not seem to be any detailed explanations behind these results in the original paper, although due to it being observed at numerous concentrations it may be an area that requires some attention in the future.
• the long term stability of the emulsion have also been considered, with regard to dehydration and desalting as this is an important property considering transportation of the emulsion. It is claimed in these patents that the primary controlling factor of the viscosity is the proportion of small and large droplets.
• An ethoxylated alkylphenol emulsifying agent was used at a concentration of 3000mg/l of oil to produce the coarse emulsion and a concentration of 5000mg/l of oil for the fine emulsion. Diameter ratios of 14 , 7 and 6 were tested and all produced viscosities well below the two constituent emulsions. The lowest viscosities achieved were at diameter ratios greater than 10.
• the viscosity of dispersions is affected by several factors, with the volume fraction of the dispersed phase and the average particle size and distribution being of particular interest.
• the viscosity is known to increase as the volume fraction of the dispersed phase increases, and also as the average particle/droplet size decreases. This can be extremely limiting in industry when trying to disperse a high volume fraction of a highly viscous liquid or a solid, as it is necessary to reduce viscosity to manageable levels for purposes of transport and handling.
• the composite dispersion also allows for a greatly increased maximum packing fraction, reduced shear-thinning or shear-thickening behavior and reduced storage/loss moduli.
• Three main variables have shown to affect the viscosity reduction in a composite dispersion.
• the addition of fine particles to a dispersion of larger particles increases the volume fraction of the dispersed phase, by filling the voids created by the large particles they increase the maximum packing fraction, increase the fluidity and reduce viscosity.
• the mixing ratio of these fine and coarse particles is important, and maximum fluidity has been found to be achieved at 20-30% small particles by volume.
• the particle diameter ratio is correct to achieve improved fluidity in the dispersion.
• the fine particle diameter must be 6.49 times smaller than the large particle diameter to be able to fit into any of the voids created by the lattice of large particles.
• Experimental evidence suggests that maximum viscosity ' reductions are likely to be achieved at diameter ratios greater than 6.49, as in reality it is very unlikely that all particles will be hard spherical objects.
• Emulsion droplets for example will, at high dispersed phase concentrations, be deformed and as a result the voids between droplets will be reduced in size from the model used and an increased diameter ratio will be required for fine droplets to fill these voids.
• emulsified hydrocarbon fuels have become increasingly important as a useful fuel for steam generation in power plant and other steam raising facilities to replace coal and petroleum coke, has environmental drawbacks, and natural gas which is relatively more expensive.
• the high cost of natural gas has particular ramifications in the petroleum processing art and specifically in the steam assisted gravity drainage technique (SAGD) as related to the production of heavy oils and natural bitumens.
• SAGD steam assisted gravity drainage technique
• the SAGD and congener techniques require the use of steam generators for injecting steam into a subterranean formation to mobilize highly viscous hydrocarbon material.
• natural gas has been used to fire the steam generators, however, this is unattractive from a financial point of view and has other inherent drawbacks.
• With the advent of emulsified hydrocarbons, especially those manufactured from hydrocarbons or their products from indigenous hydrocarbon production it has been found that the heat content is adequate to burn in a steam generation environment.
• MSARTM Multi-Phase Superfine Atomized Residue
• Quadrise Ltd. emulsified fuels
• MSARTM is an oil-in- water emulsion fuel where the oil is a hydrocarbon with an API gravity between 15 and -10. Typical oil-water ratios lie in the range 65% to 74%. Because of the presence of oil droplets in water, MSARTM is essentially a pre-atomized fuel.
• the burner atomizer does not do mechanical work to produce oil droplets, as in conventional fuel oil combustion, but that it is the emulsion manufacturing equipment that produces the oil droplets.
• Pre-atomization literally means 'before the atomizer' and so the MSARTM manufacturing equipment is essentially the atomizer of this process.
• Typical mean droplet size characteristics of MSARTM are around 5 microns, whereas typical mean droplet size characteristics produced during fuel oil atomization in a burner atomizer are between 150 and 200 microns. Therefore, the enormous increase in surface area brought about by producing much smaller droplets in the MSARTM production process, compared with a conventional burner atomizer, leads to much more rapid and complete combustion, despite the fact that there are significant quantities of water present.
• MSARTM passes through a conventional atomizer, as it must do in order to be combusted, 150 - 200 micron water droplets containing the 5 micron oil droplets are formed. Water therefore finds itself located in the interstitial zones between each assembly of oil droplets. This interstitial water, between the oil droplets, spontaneously vaporizes and this leads to further break-up of the already small (5 micron) droplets. This process is known as secondary atomization. Because of this secondary atomization and the earlier described pre-atomization, MSARTM has been found to be a particularly effective fuel, with a carbon burnout rate of 99.9%.
• Carbon burnout is obviously an important aspect of any combustion process and the fact that MSARTM carbon burnout is so high, substantially reduces the amount of carbon coated ash that collects in the burner and/or furnace. As is known, if the carbon burnout is low, then carbon will deposit with ash and on boiler surfaces and will effectively lead to the production of coke; this leads to inefficiencies and/or inoperability in the overall process. By providing a 99.9% carbon burnout rate, these problems are obviated.
• bimodal emulsions i.e. emulsions which have two distinct droplet size peaks in their droplet size profile.
• ⁇ oil-in-water emulsion viscosity (cs)
• ⁇ o viscosity of the water continuous phase (cs)
• ⁇ volume fraction of the dispersed oil phase
• cpp maximum packing fraction for the emulsion oil droplet size distribution
• the equation illustrates that the viscosity of an oil- in-water emulsion may be reduced if the oil droplet size distribution results in a larger maximum packing fraction. This reduction may be accomplished by forming the oil-in- water emulsion such that a wide range of oil droplet sizes results, or by the formation of a bimodal oil droplet size distribution.
• a bimodal oil-in-water emulsion with an oil droplet size ratio of 5 to 1 theoretically has a viscosity reduced by a factor of about 10, assuming spherical and non-interacting oil particles. The larger this maximum packing factor, the lower the viscosity.
• a single emulsion with a wide particle size distribution will have a lower viscosity.
• bimodal emulsions have a lower viscosity and that not all mixtures of emulsions will lead to a reduction in viscosity.
• the reference does not specify how to eliminate the "guesswork" from selecting which particle size results in maximum polydispersity in a unimodal emulsion.
• a bimodal or multimodal oil-in-aqueous phase emulsion (s) may be formed with any of the emulsifying agent (s) of the present invention by varying the residence times and/or the shear rate of the mixture of emulsifying composition (s) and produced hydrocarbon crude in any suitable dynamic shearer and mixer (e.g. a rotor stator mixer, etc.), and collecting the effluent oil-in- aqueous phase emulsion (s) emanating from the dynamic shearer and mixer at various residence times and/or shear rates in any suitable tank or container, such as emulsion tank 122.
• a suitable dynamic shearer and mixer e.g. a rotor stator mixer, etc.
• the collected effluent oil-in-aqueous phase emulsion (s) produced from various residence times and/or shear rates in any suitable dynamic shearer and mixer combine in the emulsion tank 122 to form bimodal or multimodal oil -in-aqueous phase emulsion (s) having a lower viscosity of oil-in-aqueous phase emulsion (s) produced from one dynamic shearer and mixer having a fixed shear rate and/or residence time of the emulsifying composition (s) and the produced hydrocarbon crude in the dynamic shearer and mixer; or from the static shearing and mixing device 108 with one flow (and shear) rate.
• the viscosity of a bimodal oil-in-aqueous phase emulsion (s) produced by positioning for 4 sees. a mixture of emulsifying composition (s) and produced hydrocarbon crude in a dynamic shearer and mixer having a shear field intensity of 500 sec. "1 , and combining the resulting oil-in-aqueous phase emulsion (s) with the oil-in-aqueous phase emulsion (s) formulated from subsequently positioning for 4 sees, the same mixture in the same dynamic shearer and mixer having a shear field intensity of 6,000 sec.
• the fact that mixing emulsions (two or more) gives a reduction in viscosity is acknowledged.
• the final emulsion can be either multimodal or bimodal.
• the Example is presented to prove that bimodal oil-in-water emulsion (s) has an improved viscosity.
• the crude was Manatokan.
• the aqueous phase was water.
• the surfactant was a mixture of 714.3 ppm NP40 (714.3 ppm of NP40 by weight of Manatokan) and 714.3 ppm NPlOO (714.3 ppm of NPlOO by weight of Manatokan) .
• the emulsifying composition was prepared by mixing water with the surfactant.
• Two oil-in-water emulsions were prepared by mixing a known amount of the emulsifying composition (s) with a known amount of the Manatokan and agitating with a rotor-stator mixer having a mixer energy of 3000 rpm for 40 sees.
• the first oil-in-water emulsion (s) had a mean oil droplet size ( ⁇ ) of 69.9, a dispersity of 3.27, and a viscosity (cp) of 221.
• the second emulsion with less Manatokan had a mean oil droplet size of 54.9, a dispersity of about 3.56, and a viscosity (cp) of about 198.
• bimodal emulsion have a lower viscosity than any of its emulsion constituents.
• the present invention has now collated the most desirable properties for a fuel emulsion where the final emulsion is effectively a composite emulsion of at least two precursory emulsions and which composite emulsion provides for a unimodal distribution, i.e. a single peak, emulsion as opposed to bimodal distribution which is exemplified in the prior art.
• Unimodal refers to a majority peak with the potential for shoulders, but absent discrete peaks. This may also be defined as having a unique volumetric mode where the volumetric probability of finding particles on each side of the mode is monotonically decreasing and there are no other local maxima .
• the present invention has successfully unified unrelated technologies to result in a particularly efficient composite fuel emulsion and methodology for synthesizing fuels regardless of the characteristic of the precursor emulsions, while fully controlling polydispersity .
• the present technology has industrial applicability in the emulsion synthesis field.
• One aspect of the present invention is to provide a substantially improved atomized fuel emulsion, which emulsion is a composite fuel emulsion having very desirable burn properties, calorific value and which can be custom designed for burning in any furnace or burning arrangement which is vastly different from the prior art.
• an emulsified hydrocarbon fuel comprising a composite of a plurality of hydrocarbon- in-water emulsions, the composite emulsion having a unimodal hydrocarbon particle distribution, the hydrocarbon being present in an amount of between 64% and 90% by volume.
• a significant advancement with the present technology is the formulation of a way to formulate composite emulsions where the polydispersity can be controlled much better than if we were looking at a single precursor emulsion.
• the instant technology teaches a way to make a composite emulsion from whatever precursor emulsion is used. This is in marked contrast to the reference discussed above, where there is taught a way to make a composite emulsion from two very specific precursor emulsions .
• Second portion 62 is mixed with hydrocarbon 70 in a mixer of module 54 so as to form a second emulsion 72 which has a small average droplet size.
• Emulsions 68 and 72 are then combined in module 56 to form the desired end emulsion.
• additional water 74 may advantageously be added to the system, for example by adding to small droplet diameter emulsion 72, so as to provide a final bimodal emulsion having a desired water content, for example of greater than or equal to about 29%, and/or further water can be added downstream of the emulsion mixing process as well...
• bimodal emulsions can advantageously be formed by first making a plurality of monomodal emulsions, and then mixing the emulsions in accordance with the process described above.
• FIG.11 shows two different monomodal emulsions in terms of droplet size distributions, and also shows the droplet size distribution for a bimodal or final emulsion product prepared from the two monomodal emulsions. This final product is stable and has desired properties.
• the precursor emulsions may contain the same hydrocarbon material or different hydrocarbon materials depending upon the specific use of the emulsion.
• the particle size distributions and droplet size may be the same or different.
• the hydrocarbon material will be different in the discrete emulsions.
• the composite emulsion may be a composite emulsion combined with a hydrocarbon in water emulsion. Similar to that noted above, the composite emulsion and hydrocarbon in water may comprise the same or different hydrocarbon material, same or different droplet size and/or the same or different particle size distribution.
• a method of formulating a composite emulsion made from different hydrocarbon materials which possess widely differing viscosities and therefore widely differing emulsion preparation temperatures Consequently, the precursor emulsion which is made at the lower temperature can be used as a cooling agent when mixed with the precursor emulsion which is made at the higher temperature. This obviates or reduces the need to use heat exchangers to reduce the temperature of emulsions which are made above 100 deg C to below 100 deg C prior to storage.
• a method of formulating a composite emulsion having unimodal particle distribution with reduced viscosity relative to precursor emulsions used to form said composite emulsion : providing a system having an n-modal particle distribution; forming a precursor emulsion for each n-modal distribution present in the system, each precursor emulsion having a characteristic viscosity; and mixing precursor emulsions to form the composite emulsion with a unimodal size distribution and reduced viscosity relative to each precursor emulsion.
• a still further aspect of one embodiment of the present invention is to provide a method for transporting viscous hydrocarbon material comprising: providing a source of hydrocarbon material; generating a plurality of emulsions of the hydrocarbon material, each emulsion having a characteristic viscosity, each emulsion having a different particle size distribution; mixing the plurality of emulsions in a predetermined ratio to form a composite emulsion having a lower viscosity relative to the plurality of emulsions; and mobilizing the composite emulsion.
• a still further aspect of one embodiment of the present invention is a method of maximizing viscous hydrocarbon content in an aqueous system for storage or transport, comprising: providing a hydrocarbon emulsion having a hydrocarbon internal phase volume sufficiently high such that the droplets in the emulsion are aspherical; converting the emulsion at least to a bimodal emulsion system; forming at least two precursor emulsions from the system; mixing the precursor emulsions in a predetermined ratio to effect reduced viscosity; and synthesizing a composite emulsion from the precursor emulsions having the reduced viscosity.
• a still further aspect of one embodiment of the present invention is a method of formulating a composite emulsion having unimodal particle distribution with reduced viscosity relative to precursor emulsions: providing a system having an n-modal particle distribution; forming a precursor emulsion for each modal distribution present in the system; each the precursor emulsion having a characteristic viscosity; forming a plurality of composite emulsions each having a unimodal size distribution and reduced viscosity relative to each the precursor emulsions; and mixing the composite emulsions to form an amalgamated composite emulsion having a unimodal particle distribution and reduced viscosity relative to the viscosity of the composite emulsions.
• the HIPR (High Internal Phase Ratio) emulsions with extremely high hydrocarbon content could also be transported efficiently.
• these emulsions can be converted to at least a bimodal or n-modal emulsion system depending upon the number of particle size distributions within the HIPR emulsion and then these individual bimodal emulsions could be formed into precursor emulsions and mixed to form a composite emulsion in accordance with the methodology previously discussed herein.
• aspherical or substantially non- spherical oil in water particles can be reconfigured or converted into discreet modes for individual emulsion synthesis with subsequent mixing for composition of a more favorably transportable composite emulsion.
• This has particular utility in permitting mobilization of high hydrocarbon content material without expensive unit operations conventionally attributed to processes in the prior art such as pre-heating, the addition of diluents or other viscosity reducing agents.
• the material can simply be converted, to a composite emulsion and once so converted, inherently has the same transportation advantages of the composite emulsions discussed herein previously.
• a method of modifying at least one of the combustion, storage and transportation characteristics of an emulsion during at least one of pre-formation, at formation and post formation comprising: providing an emulsion; treating the emulsion to a unit selected from the groups consisting of additive addition, mechanical processing, chemical processing, physical processing and combinations thereof; and modifying at least one characteristic of the characteristics of the emulsion from treatment.
• the present invention in many of its aspects makes what, under present technology is extremely complex, very straight-forward with infinite range of design possibilities.
• any given polydispersed system there are a number of different particle sizes. Each one of these particle sizes could theoretically be mixed in any ratio to result in an infinite number of composite emulsions with varying polydispersity, droplet size and dynamic stability. It has been stated herein previously that prior art has attempted to teach methodology for preparation of a specific emulsion.
• dynamic stability of any emulsion can be improved, i.e., an existing composite emulsion.
• the process allows for reconfiguration of an existing composite emulsion to improve or otherwise alter the physical and chemical properties. This is a marked advantage; it allows for essentially rendering a potentially ineffective emulsion effective for subsequent use. As will be appreciated, this is very beneficial for in situ or on-site fuel modification and obviates the need for power generation stations, etc. to have at their avail a number of different types of fuels. Once one set of parameters for a given fuel is achieved, the parameters can be altered to suit the burning requirements in a different environment.
• off-specification materials such as fuels, precursor materials for pharmaceutical and food production, etc. can be corrected to be acceptable or on the specification for subsequent use. This obviously presents sizable cost savings for material that would otherwise be discarded for lack of utility.
• Figure 1 shows the results obtained in Greenwood et al . , and is a plot of viscosity measurements at varied small particle volume and total volume (from ref. Greenwood et al . , [Colloids and Surfaces A: Physiochem. Eng. Aspects, 144 (1998) 139-147, Minimising the viscosity of concentrated dispersions by using bimodal particle size distributions] ) .
• Figure 2 is a plot of the effect of diameter ratio on suspension viscosity (Greenwood et al . [J. Colloid Interface Sci, 191, 11-21 (1997), The effect diameter ratio and volume ratio on the viscosity of bimodal suspensions of polymer lattices] ) .
• Figures 3, 4 and 5 each indicate concentration and mixing ratio effects on suspension viscosity at diameter ratios of 6.37, 2.81 and 1.08.
• Figure 6 plots the composition (small particles by- volume) on the relative viscosity of the bimodal suspension at a diameter ratio of 6.37. Total volume fractions are indicated to be 0.40, 0.45, 0.50, 0.55 and 0.60.
• Figure 7 plots the effect of the composition (small particles by volume) on the relative viscosity of the bimodal suspension at a diameter ratio of 2.81. Total volume fractions indicated are 0.40, 0.45, 0.50, 0.55 and 0.60.
• Figure 8 plots the composition (small particles by volume) on the relative viscosity of the bimodal suspension at a diameter ratio of 1.08. Total volume fractions indicated are 0.40, 0.45, 0.50, 0.55 and 0.60.
• Figure 9 plots viscosity as a function of total oil volume fractions.
• Figure 10 is a schematic illustration of the overall synthesis mechanism of the instant technology
• Figure 1OA is a schematic illustration of a variation in the overall synthesis mechanism of the instant technology
• Figure 11 is a graphical illustration of particle size as a function of shear,-
• Figure 12A and 12B are graphical illustrations of viscosity as a function of droplet size ratio
• Figure 13 is graphical illustration of percentage of oil in the emulsion as a function of further length
• Figure 14 is a graphical illustration of two precursors and a composite emulsion of a surfactant in 70% NE Alberta bitumen for a median particle size of 5 ⁇ m and 24 ⁇ m;
• Figure 15 is a graphical illustration of the composite emulsion viscosity for varying percentages of the same median particle size
• Figure 16 is a graphical illustration of a two modal distribution for North Eastern Alberta bitumen particles with two particle sizes (5 microns and 10 microns) ;
• Figure 17 is a graphical illustration of viscosity as a function of the percentage of 5 micron MSARTM used in the precursory emulsion and percentage of 10 micron MSARTM used in the second precursory emulsion;
• Figures 18A through 18C illustrate particle distributions for composite emulsions formed from the 5 and
• Figure 19 illustrates the individual distributions for a 6 micron 12 micron mode where both precursory emulsions are formed using a surfactant and a 70% content of refinery residue;
• Figure 20 illustrates a viscosity as a function of the MSARTM mixture composed of 5 microns in the first emulsion and 12 microns in the second emulsion;
• Figures 2OA through 2OC illustrate the result of the particle distribution in the composite emulsions for the 6 and 12 micron particles in the following percentages: 20% and 80%, 50% and 50% and 80% and 20%, respectively;
• Figure 21 is a graphical illustration of the precursors where emulsion number 1 comprises 6 micron median particle size distribution and emulsion to a 16 micron median particle size distribution;
• Figure 22 is a graphical representation of the viscosities of the MSARTM mixtures composed of 6 micron and 16 micron 80/100 Asphalt MSARTM;
• Figures 22A through 22C illustrate varying percentages of 6 micron and 16 micron particles, namely 20% and 80%, 80% and 20%, and 50% and 50%, respectively;
• Figure 23 is front view of a burner where the illustration is of a North Eastern Alberta bitumen MSARTM fuel number 1 being combusted;
• Figure 24 is a side view of the flame illustrated in Figure 23;
• Figure 25 is an illustration of the coke deposits on the nozzle subsequent to the combustion of the fuel being burned in Figures 23 and 24;
• Figure 26 is a view similar to Figure 28 after a second burning run of MSARTM fuel 1 ;
• Figure 27 is a view of the combustion from the burner of the North Eastern Alberta bitumen MSARTM fuel 2;
• Figure 28 is a photograph of the nozzle after combustion of the MSARTM fuel 2 illustrating the coke deposit ;
• Figure 29 is a figure depicting the flame generated from the burning of the North Eastern Alberta bitumen MSARTM composite fuel between the MSARTM fuel 1 and MSARTM fuel 2 ;
• Figure 30 is a side view of the flame of Figure 29.
• Figure 31 is an illustration of the burner nozzle illustrating the minimum deposition of coke on the nozzle.
• the synthesis mechanism includes two broad steps denoted by numerals 12 and 14.
• step 12 a hydrocarbon material 16 is mixed with water 20 containing a surfactant 18 and the material, as a mixture, is mixed in a mixing device 22.
• the hydrocarbon material may comprise any hydrocarbon material fuel, non limiting examples of which include natural gas, bitumen, fuel oil, heavy oil, residuum, emulsified fuel, multiphase superfine atomized residue (MSARTM), asphaltenes, petcoke, coal, and combinations thereof. It is desirable to employ hydrocarbon material of less than 18 API.
• emulsion stabilizer a chemical composition which presents premature phase separation of the emulsion
• the surfactants are useful for this as well as a host of other members in the class of stabilizers.
• the surfactants may be non-ionic, zwitterionic, cationic or anionic or mixtures thereof. Further, they may be in a liquid, solid or gaseous state. It is well within the purview of the scope of this invention to use combinations of materials to achieve a properly dispersed system normally attributable to emulsions.
• the mixer may comprise any suitable mixer known to those skilled in the art. Suitable amounts for the emulsion stabilizer or surfactant comprise between 0.01% by weight to 5.0% by weight of the emulsion with the hydrocarbon comprising any amount up to 90% by weight.
• a mixer such as a colloidal mill, is used. Once the materials are subjected to the colloidal mill a first precursor emulsion 24 is generated. Similar steps are effected to result in the second precursory emulsion 24', with common steps from the preparation of emulsion one being denoted by similar numerals with prime designations.
• a mixing device 26 which may comprise a similar shear apparatus as the colloidal mill or more likely a further selected device such as an in-line static mixer.
• the composite emulsion 28 which is a polydispersed fuel emulsion.
• the predetermined ratio is determined by making use of a particle packing algorithm such as that which has been set forth in the discussion of the prior art.
• the final properties desired in the composite dictate the initial mix-in ratio.
• any emulsion can be formulated or designed with any composition of precursor emulsions.
• the composite emulsion has a viscosity that is less than the viscosity of the precursor emulsions by a factor of between 3 and 5 times the viscosity of the precursor emulsion containing the small droplets.
• a further advantage that flows from this unification of unrelated technologies is the requirement for lower preheat temperatures in the composite emulsion as opposed to those preheat temperatures required for the previous or precursor emulsions.
• the composite emulsion also has been found to have much improved dynamic and static stability and handling (anything in-between manufacture and burner tip, e.g. storage, valves, pipes, tanks, etc.) characteristics and therefore easier storage and transportation possibilities.
• burn testing the composite emulsions provided greater than 99.9% carbon burnout, despite the fact that the emulsion contained a high percentage of the hydrocarbon material in water.
• Figure 1OA shown is a variation of the overall arrangement shown in Figure 10.
• the process may be modified at various stages to effect the transportation storage and/or combustion of the individual components within the emulsions or the composite emulsion itself.
• Figure 1OA provides for modification of at least one of the above noted aspects by modification at the pre-synthesis mixing point prior to the surfactant and water entering the mill 22 as denoted by numeral 30 or as a further option by modifying the hydrocarbon prior to introduction to the mill, this step being indicated by numeral 32.
• the emulsion may be modified at the point of fabrication, denoted by numeral 34 or subsequent to formation at 36.
• first emulsion 24 and second emulsion 24' may modified at mixer 26 denoted by numeral 38 or subsequently modified once the composite emulsion 28 has been formed. This step is denoted by numeral 40.
• the emulsion may be modified in terms of combustion, storage and/or transportation characteristics during at least one of pre-formation, at formation and post formation where the modification involves a unit operation selected from at least additive addition, mechanical processing, chemical processing and physical processing, as well as combinations thereof.
• the additive addition will be discussed herein after.
• FIG 11 shown is a schematic graphical illustration of particle size as a function of the amount of shear. This permits the selection of different particle size distributions for the emulsions by changing the amount of shear used to make particles for the emulsion. It is known that the amount of shear is related to the average particle size and width of distribution as shown in Figure 11. The lowest droplet size is related to the parameters used to formulate the emulsion. The shear amount is increased by increasing the residence time in the mixing device, or increasing the speed at which the rotatable mixing device rotates.
• FIGS 12A and 12B shown are schematic graphical illustrations of viscosity as a function of a ratio of small droplets versus big droplets with the larger droplets being represented on the left hand side of the graphs.
• FIG. 14 shown is pre-mix particle distributions for a bimodal system where numeral 1 represents an emulsion containing surfactant with 70% North Eastern Alberta bitumen with the balance comprising water.
• the first distribution was formulated using a high shear mixer at a high revolution.
• the median particle size in this distribution was 5 microns whereas in distribution number 2, the median particle size was 24 microns.
• the premix it is evident that each emulsion possesses a distinctly different mean and median droplet size.
• Figure 15 plots the composition (small particles by volume) on the relative viscosity of the bimodal suspension at a diameter ratio of 6.37. Total volume fractions indicated are 0.40, 0.45, 0.50, 0.55 and 0.60.
• Figure 15 is a graphical representation of viscosity as a function of percentage of 5 micron MSARTM emulsion and 24 micron MSARTM used in the mixture.
• Inset Figure 15A is a distribution representation for a 20% 5 micron and 80% 24 micron mixture having a characteristic viscosity indicated by the arrow in the graph of Figure 15, whereas Figure 15B is an inset where the mixture or composite emulsion contained 80% 5 micron particle size and 20% 24 micron particle size with the arrow pointing in Figure 15 to the characteristic viscosity.
• inset Figure 15C depicts a 50/50 blend of 24 micron and 5 micron particles ⁇ with the characteristic of viscosity being indicated by the arrow. From a review of Figures 15A through 15C, it is evident that the particle distribution representations are effectively unimodal despite containing two individual emulsions which independently possess distinctly different mean and median droplet sizes.
• FIG. 15D shown is a ternary diagram for a three-fraction system of 1 micron particles, 5 micron particles and 10 micron particles. As is generally known, these plots are effective to display packing fractions. The data can be interpreted to determine what combinations of the particles would yield the best possible packing fraction. In the ternary diagram illustrated, the data is representative of 67 different particle mix combinations. The varying shading illustrates different packing fractions with the range comprising .62 through .76. As is evident from the Figure, in order to determine the best possible packing fraction, the use of an algorithm in this scenario is critical to avoid the guesswork involved in determining the best packing fraction. It will be appreciated by those skilled in the art that it would be next to impossible to try to predict what is depicted in Figure 6D.
• Figure 16 provides a North Eastern Alberta bitumen particle distribution where there is a greater degree of overlap between the two modal distributions in view of the median particle size.
• similar materials were used with respect to the previous discussion with the 5 micron median particle distribution being represented by numeral 1 which occurred at a relatively high speed, whereas peak 2 comprises medial particle distribution of 10 microns which was created at a lower speed.
• mixing can occur in a low and high intensity mixer with the rpm selected based on final requirements.
• Figure 17 illustrates a viscosity as a function of the percentage of 5 micron MSARTM used in the precursory emulsion and percentage of 10 micron MSARTM used in the second precursory emulsion.
• Insets 18A, 18B, and 18C illustrate particle distributions for composite emulsion formed from the 5 and 10 micron individual emulsions for 5 and 10 micron percentages of 20% and 80%, 50% and 50%, and 80% and 20%, respectively.
• Individual arrows from each of insets 18A through 18C are representative of the viscosity of the individual final composite mixtures of insets 18A, 18B and 18C.
• FIG. 19 illustrates the individual distributions for a 6 micron and 12 micron mode where both precursor emulsions were formed using a suitable surfactant and a 70% content of refinery tank 9 with a balance of water.
• the contents of the refinery residue are approximately 10% gas oil and 90% viscous hydrocarbon material .
• the 6 micron distribution was generated at a relatively high speed, whereas the 12 micron was generated at a lower speed.
• Figure 20 illustrates the viscosity as a function of the MSARTM mixture composed of 5 microns in the first emulsion and 12 microns in the second emulsion.
• Figures 2OA through 2OC illustrate the results of the particle distribution in the composite emulsion for the 6 and 12 micron particles in the following percentages: 20% and 80%, 50% and 50% and 80% and 20%, respectively.
• each has a characteristic viscosity indicated on the graphical representation of Figure 20.
• the composite emulsion in all cases is effectively unimodal and accordingly provides a broad particle size distribution.
• Figure 21 tabulates the characteristics of pre-cursor emulsion where emulsion number 1 comprises 6 micron median particle size distribution and emulsion 2 a 16 micron median particle size distribution.
• the surfactant was employed as the surfactant with the hydrocarbon material comprising 70% 80/100 Asphalt with the balance being water.
• the 6 micron distribution was formulated using the mill at a relatively high speed where the 16 micron was synthesized at a lower speed.
• Figure 22 Similar data to the examples presented previously are presented in Figure 22 where the viscosity is represented.
• Figures 22A through 22C represent specific composite emulsion formulations of 6 and 16 micron distributions in the following amounts: 20% and 80%, 80% and 20%, and 50% and 50%, respectively.
• the composite emulsion demonstrates a unimodal particle distribution with characteristic viscosities for each of the insets 22A through 22C.
• a host of very useful features flow from the use of this methodology not only to make an improved emulsified fuel with higher carbon burnout than the individual emulsions in the composite, but also the lower water requirement for transportation.
• HIPR emulsions which are characteristically composed of aspherical particles which are generally polyhedral which can be converted into individual emulsions and then subsequently combined to form a composite mixture having the advantages that flow from the instant technology.
• the HIPR emulsions can be converted to provide the desirable properties of a composite emulsion in terms of having a wider particle distribution with reduced viscosity and improved combustion. It is a well known fact that HIPR emulsions have exceptionally high viscosities, and are very shear thinning.
• the emulsion technology set forth herein allows the emulsion to be designed for the furnace or burning arrangement individually as opposed to having to design a furnace to specifically burn the emulsion.
• the cost savings on this point are extremely substantial; the modification of the emulsion is obviously a much less involved exercise than having to design and fabricate a new piece of expensive equipment .
• the precursor emulsions are not limited in number and are well within the scope of the instant technology to provide an n-modal system.
• the individual emulsions would have to be formulated and then subsequently mixed together to form the composite emulsion as an attendant feature to this aspect of the invention, individual groups of emulsions may be mixed to form composite emulsions and the so formed composite emulsions then further mixed to form an amalgamated emulsion of individual composite emulsions.
• the composite may be reintroduced into a shear or mixing device to form a processed composite emulsion.
• the initial temperature for the MSARTM fuel 1 was a fuel temperature of 85 0 C and was slowly increased to 100 °C, based on the flame characteristics observed.
• Fuel is the input to the furnace (mass rate, temperature and pressure are the same for each of the three cases, i.e., 22 microns, 5 microns and composite)
• Atomizing air is the air that is used for the primary atomization of the liquid droplet. Typically, primary atomization usually produces a liquid droplet of 50 to 200 microns.
• Combustion air is the major source of oxygen for the combustion.
• Flue gas the emissions are normalized to 3.5% oxygen content in the flue gas. For this reason, two columns are employed; one for fuel, which is measured, and one which is normalized.
• Carbon monoxide emissions the amount of carbon monoxide is an indication of incomplete combustion.
• Particulates the amount of carbon on the particulates is an indication of incomplete combustion. The more carbon on the particulates, the greater the degree of incomplete combustion.
• Thermal transfer rate this is a measure of the key transfer rate measured radially to the flame. All of the emulsions show higher radial heat transfer rate than natural gas. The heat transfer rate of all three emulsions are somewhat the same in each instance.
• Table 3 provides flue gas emission data which again provides evidence that the NO x and SO 2 emissions are very appealing from an environmental point of view in the blend. It is particularly note worthy that the MSARTM blend composite has a lower carbon content in the particulates and a lower CO concentration in the flue gas than the precursor emulsions, indicating a much better carbon burnout for the composite emulsion.
• FIG. 22 shown is a photograph of a burner where the North Eastern Alberta bitumen MSARTM fuel 1 is being combusted.
• the flame shape is illustrated in the Figure .
• Figure 23 illustrates a side view of the flame from the burner of the fuel being burned in Figure 22.
• Figures 24 and 25 illustrate the coke deposit on the nozzle of the burner after the first run of burn, while Figure 25 illustrates the coke deposit on the nozzle of the burner after a second run; the difference being fairly significant .
• Figure 26 provides a view of the burner during the burn of the North Eastern Alberta bitumen MSARTM fuel 2.
• Figure 27 illustrates the coke deposit on the nozzle of the burner subsequent to the combustion of the MSARTM fuel 2.
• Figure 28 the burning of the composite emulsion is indicated in the photograph. It is interesting to note that the flame shape is much more consolidated than the flame shape of the individual precursor emulsions when burned. This is further corroborated by Figure 29, which shows a fairly significant flame length and intensity when taken from a side view of the burner. As discussed herein previously with respect to the burn characteristics and other features of the composite emulsion, Figure 30 illustrates the cleanliness of the flame; the coke deposit on the nozzle subsequent to burning is virtually nonexistent when one compares this illustration with the coke deposits from Figure 25 relating to the combustion of MSARTM fuel 1.
• the composite emulsion has many significant benefits over the burning of the precursor emulsions and in many cases approximates the beneficial features of burning natural gas.
• the combustion of the composite emulsion provides a more desirable energy output from a lower monoxide emission, lower coke deposits at the burner nozzle, lower sulfur dioxide emissions among other very desirable properties.
• the composite emulsion flame characteristics provide for a much brighter and more stable flame with less brownish discolouration, lower carbon monoxide emission among other features .

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