Proc. Indian natn. Sci. Acad, 58, A, No. 3, 1992, pp. 181-194. © Printed in India ULTRASONICATION FOR BREAKING WATER- IN-OIL EMULSIONS BP SINGH* AND B P PANDEY Enhanced Oil Recovery Laboratory, Department of Petroleum Engineering, Indian School of Mines, Dhanbad 826 004, India (Received 7 December 1990; Revised 25 April 1991; Accepted 19 June 1991} Studies have been made on the effectiveness of ultrasound in resolving water-in- oil emulsions with and without chemical demulsifiers. Separation of water from emulsion by conventional chemical methods and ultrasonication are compared, In some cases, ultrasound gives faster separation than that obtained by chemical process. The present paper deals with the results of demulsification of Sanand Oilfield emulsion, It has been shown that ultrasound is able to cause the separation of 90—100% of water from the emulsion when used with demulsifiets. Even without a demubsifer, separation is more than 75% at room temperature. It is observed that even for relatively stable emulsions, which do not respond to chemical treat- ment, separation of water is appreciable by ultrasonication. A mechanism for de- mulsification is proposed which is consistent with the experimental observations. Key Words : Uitrasonication; Demulsification; Emulsion; Interfacial Tension (IFT); Coalescence; Emulsifying Agent; Flocculation: Interface; Disjoining Pressure Introduction One-third or more of the crude oil being produced in the world, comes to the sur- face associated with appreciable proportions of water in emulsified form even where the percentage of emulsion in total production is very low, storage tanks tend, eventually, to accumulate significant volumes of emulsion'. Emulsion resolu- tion is, therefore, an important element in the handling of crude oil, from the time it is produced until it enters the refining process. Since India does not have large accumulation of oil, it is necessary to develop recovery methods in the most ra- tional and efficient way to recover maximum oil at minimum cost. One of the earli- est investigations concerning the resolution of crude-oil emulsion was reported by Levchenko et al2, by ultrasonication. They extensively studied the use of ultra- sound in the emulsification of crude oil emulsions and achieved partial success. Recent work by Grang et al, describes the use of microwaved radiation. The la- boratory and field tests showed that microwave radiation can break oil-water solid emulsions and recover oil from oily sudge and bottoms sediment and water. Tests samples included crude oil-water emulsions and separation of oil from water by gravity-settling, conventional heating, and microwave radiation were compared. ‘or correspondence. Scientist’, MB Division, Regional Research Laboratory, Bhubaneswar 751 013.182 BP SINGH AND BP PANDEY ‘They found that in some cases, microwave radiation gives faster separation than that obtained by the other two methods. In our work, we have attempted to resolve the emulsion at room temperature by applying ultrasound, For this purpose the effect of emulsifiers, alongwith ultra- sound on separation of water was studied. It was concluded that relatively stable emulsions experience poor coalescence rates and hence poor oil recovery in chemical processes. In such cases however, the separation of water from the emul- sion was appreciable by ultrasonication. Experimental Samples : The crude oil emulsion samples used in this study were obtained from Sanand (Gujarat), Oilfield of India. The water content was determined by Dean and Stark method and was found to be 34%. The nature of the crude oil was naph- thenic. The containers were thoroughly shaken before taking a sample for labora- tory experiments to ensure a representative sample. Demulsifier : The demulsifiers used in this study were commercially available materials supplied either by oil industry or chemical dealers. The chemical com- positions in most casés were not known but the demulsifiers are known to consist of more than one surface active compounds. The chemicals were selected on the basis of preliminary tests in the laboratory called ‘bottle tests’, Selection of the op- timum chemical to use usually starts with bottle tests*. A representative sample of fluid is taken and transferred into several test bottles. Several demulsifying chemi- cals are added to the test bottles in various amounts to determine which chemical will best break the emulsion. Additional tests are made to determine the optimum ratio of chemical to fluid. Several series of tests may be necessary at various ratios and temperatures before a selection can be made. After the bottle tests are made, the best two or three chemicals are selected, The optimum chemical is one that will provide the clearest, cleanest separation of water from oil at the lowest tempera- ture in the shortest time at the lowest cost per barrel treated and that which will not interfere with subsequent deoiling of the water. Equipment and Procedure The equipment comprises of an electronic generator delivering 120 or 250 watts of average ultrasonic energy, a suitable stainless steel tool normally termed as -ve- locity horn’ and a pedestal unit. The horn is attached to a pair of lead-zirconate ti- tanate transducer elements which convert the electrical oscillation fed from the generator to corresponding mechanical vibrations. These vibrations are minute, of the order of a few microns, in amplitude. These are amplified by the velocity horn or Transformer’. A schematic representation of the working principle of the ultra- sonic processor is shown in Fig.1. This amplified vibrating energy is available at the tool tip and is used for processing applications. The tool tip must be dipped in the sample to be treated. Alll the experiments were carried out in a 250ml graduatd beaker specially de- signed for this purpose, so that hot water if needed, can be circulated through the annulars, without disturbing the sample. A measured volume of emulsion sample was taken into beaker and kept on the platform which can be adjusted at anyULTRASONICATION FOR BREAKING WATER-IN-OIL EMULSIONS 183 Electronic | Etectricat Generator 120-220 Toot tip Fig 1 The schematic representation of working principle of ultrasonic processor 80} 70) 60) 50] 40] 30| ° WATER SEPARATION, PERCENT 20 10 ol 20 30 “0 50 60 70 80 90 100 TIME — (MINUTES) Fig 2. Effect of ultrasonic energy on the separation of water without demulsifier height. Then the ultrasound was passed through the sample. The reading of the separated water was taken at different time intervals. Results Effect of Ultrasound on Emulsion Stability without Dernulsifiers Fig. 2 shows water separation per cent (which is the ratio of water separated/ total water X 100) vs. time. Initially separation of water is very fast and it becomes constant after sometime. There are two reasons for constant separation after184 BPSINGH AND BP PANDEY sometime. Firstly, residence time has very profound effect on the stability of emul- sion, Demulsifiers should not be present in the emulsion during excessively pro- longed agitation because the beneficial effect of the demulsifier may be spent or counteracted by the agitation and re-emulsification may occur. The role played by interfacial shear viscosity in the stabilization of emulsions is very vital and it in- creased with the lapse of time’. In certain cases, however, complex formation be- tween the surfactant and other species can increase interfacial viscosity and emul- sion stability with timeS, Secondly, polydispersity of the particles diameters can ef- fect emulsion viscosity and hence emulsion stability”, which is also time depend- ent. The maximum water separation by ultrasonication was 75.3% at room tem- perature (28 °C) and time taken was 80 minutes. During the operation tempera- ture of the systems rose from 28 to 68 °C. Separation of water by only thermal process was found to be 12.5, 38.8 and 47.2% at temperatures of 40,70 and 80 °C respectively and time taken was pretty large i.c., 2 hours. The sepatation trends by ultrasonication at room temperature (28 °C) and thermal processes are shown in Fig.3 @ Uitrason: © Thermal WATER SEPARATION, PERCENT 0 20 » 40 80 TEMPERATURE (°C) 6070 60 90 Fig 3 Separation trend : ultrasonic vis-a-vis thermalULTRASONICATION FOR BREAKING WATER-IN-OIL EMULSIONS 185, 5p 80} 50] 30 WATER SEPARATION, PERCENT ol 10 20re=ss 90 20 70 8030100 30-60 TIME (MINUTES) Fig. 4 Effect of ultrasonic energy on the separation of water with demulsifier Triton x ~ 100 Effect of Ultrasound on Emulsion Stability with Demulsifiers Chemical surfactants (Demulsifiers) employed in this study were Triton X-100, DE-205, SOT-320, JM-485, DE-2350 (all non-ionic) and cetyltrimethyl ammoniumbromide (CTAB) (cationic). Only the nature of the surfactants (cation- ic, anionic or non-ionic) were known. Structure was not completely known. Fig’s 4-9 show the water separation per cent vs. time, for the demulsifiers mentioned above accordingly. Water separation percent shows a plateau period during which separation is constant in all the cases. The starting time of plateau period is im- portant, because separation was maximum here and after that the separation was morse or less constant. It is interesting to note that the time observed in different cases, for the plateau to be reached is significant and it should be minimum and se- paration must be maximum. The most striking feature of Figs 8 & 9 is the efficiency of the demulsifiers and its separatibility. In both the cases separation was found to be 100% approximately and IFT reduction was maximum. It is commonly as- sumed that the separation efficiency can be improved by the addition of the effec- tive demulsifiers doses during conditioning and selective ultrasound frequency. The most obvious experimental parameters associated with ultrasonication and186 BPSINGH AND BP PANDEY 90r sor 70r 60r PERCENT 8 30r 250 PPM 4 1000 — 1500 WATER SEPARATION 20F ——1 30 40 50 60 70 80 30 100 110 TIME (MINUTES) Fig 5 Effect of ultrasonic energy on the separation of water with demulsifier DE-205 thermal process are frequency of ultrasound, residence time, temperature, demul- sifier dose and nature. These are summarized in Tables I & I. Surface Chemistry of Water-in-oil System The investigation involved a look at the surface chemistry of water-in-oil sys- tems to determine which properties at the interface or in the bulk phases were re- sponsible for emulsion stability. A great deal of misconception exists about the rel- atives importance of IFT to emulsion stability and surfactant performance in gener- al. Several investigators’-!? have shown that lowering IFT is conducive to emul- sion stability. They have also shown, however, that if the IFT becomes too low, the emulsion becomes unstable and in some cases an emulsion cannot form at all. Ros- ano et al? state that “a sufficiently low positive value of ris always better for emul- sion formation. Nevertheless, below a certain value of phase separation, will beULTRASONICATION FOR BREAKING WATER-1D 901 sor 70 60} PERCENT so} 30] WATER SEPARTION & 20 “0 50 60 70 TIME OIL EMULSIONS 30 (MINUTES) Fig 6. Effect of ultrasonic energy on the separation of water with demulsifier CTAB == 1000 + 1500 100 o-© 250PPM 187 ola gg 0 Table 1 Effect of ultrasonication : summary of separations achieved Demulsifier Water separation per cent Time taken Temperature at different concentration for maximum cc) (ppm) separation (minutes) 250 S00 -1000—1S00 Triton x —100 73S 80 894 60.0 50 28 DE 205 R80 86S RS 83.6 90 - Cetylerimethyl 88.2 85 820 81S 100 ammonium bromide (CTAB) SOT-320 50 80) 80.0) = 278.0) 100 JM-485 80 83 93.0 (900 130 DE-2350 79 100980970 120 .188 BPSINGH AND B P PANDEY WATER SEPARATION, PERCENT 40 50 60 70 80 30 100 or) 120 TiME (MINUTES) Fig 7 Effect of ultrasonic energy on the separation of water with demulsifier SOT—320 Table IL Effect of thermal process: suramary of separations achieved Demulsifiers Water separation per cent Time taken Maximum at different concentration for maximum temperature (ppm) separation ec) —~ (minutes) 250 S00 10001800 Triton x—100 39 62 64.7 62 95 80° DE-205 355 32 310 306 100 : CTAB 265 26 230 200 100 z SOT-320 610 60 580 58.0 100 7 JIM—485 71282 895 90.0 130 : DE-2350 860 88.788 88.0 140 yULTRASONICATION FOR BREAKING WATER-IN-OIL EMULSIONS 189 PERCENT WATER SEPARATION Le Ce LL) TIME (MINUTES) Fig 8 Effect of ultrasonic energy on the separation of water with demulsifier JM—485 produced but not emulsification. Moreover, emulsion stability is, in turn, not de- pendent on the value of the interfacial tension but solely on the structure of the in- terfacial film surrounding the individual droplet. Interfacial tension measurements were carried out before and after treatment in ultrasonic field and it was found that lowering of an IFT with effective as well as ineffective demulsifiers were more or less same. It clearly implies that an IFT lowering is not indicative of demulsifica- tion performance in itself. A low IFT may imply rapid migration to the oil/water interface, but what the surfactant does once it is at the interface is determined by its structure. It has been shown that the rate at which surfactants orient themselves at interfaces is an important factor in determining their effectiveness. Answers to the question as to why superimposition of ultrasound improves the performance of a particular demulsifier will be of great theoretical as well as practical interest and there is need to carry out investigations in this direction. Discussion It was observed that increase in temperature alone was not sufficient to produce a desirable effect on emulsion stability. Increased temperature appears, primarily, to reduce viscosity of the continuous phase (oil) and hence induce separation of190 BP SINGH AND BP PANDEY 550PPM 100 80) WATER SEPARATION, Percent ® 5 70 30 10 wi TIME (min) Fig 9 Effect of ultrasonic energy on the separation of water with demulsifier DE~2350 10 30 50 water droplets. Higher temperature might increase the solubility of emulsifiers, from interface, into oil phase, resulting in weaker film and greater degree of water droplet coalescence and separation‘. It was also observed that the separation of emulsified water first increased then decreased with an increase in demulsifier con- centration in most of the experiments. This may be due to the fact that with an in- crease in demulsifier concentration, remulsification is started, Remulsification may produce water droplets of various sizes resulting in emulsions with smaller particles diameters which have higher viscosities. In addition, the poly-dispersity of particle diameters can effect emulsion viscosity and hence emulsion stability” ‘The stability of the emulsion is controtled by the type and amount of indigen- ous surface active agents and/or finely divided solids, which commonly act as emulsifying agents or emulsifiers. These emulsifying agents form interfacial films around the droplets of the dispersed phase and create a barrier that slows down or prevent coalescence of the droplets. From the infrared spectroscopic results, it was. found that the film forming material consisted of a multicomponent mixture of hy- drocarbons comprising of carboxylic acid, ketones, aldehydes, ethers, ester, ter tiary amides, with the possible existence of quinoline, amides and imido com- pounds. Pyridine derivatives and naphthalene derivatives, to a minor extent, arc also indicated. The molecules of these compounds are believed to get adsorbed at crude oil/water interface causing decrease in interfacial tension of the system and thus act as emulsion promoter as well'. Knowing the nature of the emulsifyingULTRASONICATION FOR BREAKING WATER-IN-OIL EMULSIONS 191 agents present in a particular system one can possibly suggest the appropriate demulsifiers but often emulsifiers are not a single compound so itis difficult to sug- gest a particular kind of demulsifier. The common practice is to employ a mixture of demulsifiers. Demulsification process involves coalescence of smaller water droplets into larger ones. During this process, the oil in the liquid film between the droplets drains out, thereby thinning the film and finally rupturing it. The faster the film thins, the greater is the demulsification effectiveness. The chemical counteracts the emulsifying agents, allowing the dispersed droplets of the emulsion to. coalesce into larger drop and settle out of the matrix. For demulsifiers to work, they must (1) be injected into the emulsion, (2) intimately mix with the emulsion and migrate to all of the protective films surrounding all of the dispersed droplets and (3) dis- place or nullify the effect of the emulsifying agent at the interface. A period of continued moderate agitation of the treated emulsion to produce contact between and coalescence of the dispersed droplets followed by a quiet settling period must exist to allow separation of the oil and water. Four actions are required of a chemical demulsifier : Strong Auraction 10 the Oil/Water Interface : The demulsifier must have ability to migrate rapidly through the oil phase to reach the droplet interface where it must counteract the emulsifying agent. Flocculation: The demulsifier must have an attraction for water droplets with a si- milar charge and bring them together. In this way, large clusters of water droplets gather, which look like bunches of fish eggs under a microscope. Coalescence : After flocculation, the emulsifier film is still continuous. If the emul- sifieris weak, the flocculation force may be enough to cause coalescence but this is not truc in most cases, and the demulsifier must therefore neutralize the emulsifier and promote rupture of the droplet interface film. This allows coalescence to occur. With the emulsion irra flocculated condition, the film rupture results in growth of water drop size. Solid Wetting: Iron sulphides, clays, and drilling muds can be made water-wet, causing them to leave the interface and be diffused into the water droplets. Paraf- fin and asphaltenes can be dissolved or altered by the demulsifier to make their films less viscous, or they can be made oil-wet so that they will be dispersed in oil. Coalescence rate enhancement by the addition of demulsifier was further con- firmed microscopically. On the whole, we can say, demulsifier molecules when injected into the crude oil emulsion orient themselves at the oil-water interface and render the protective film formed by indigenous surfactants ineffective by dis- placing, recapturing and dissolving the same. Furthermore, the thinning of the in- terfacial films depend on the magnitude of the disjoining pressure (which is de- fined as the derivative of free energy to film thickness with negative sign, ~(6G/6h), where G = free energy and h = film thickness}. If it is negative, the film is urtstable and rupture. If it is positive, the film is stable enough and may not rupture's, Demulsifiers should be able to make the disjoining pressure nega- tive which is not possible emulsifiers. That is the reason emulsifiers are replaced by demulsifiers.aa BPSINGH AND BP PANDEY Mechanism of Demulsification by Ultrasonication Following is the most probable mechanism of demulsification by ultrasound : Ultrasound wave of high intensity 4 Cavitation + Rapid alteration of pressure 1 Formation of large masses of minutes, vacuuous bubbles 4 Bubble growth & pulsation till critical size iy Implosion of Bubbles 1 Generation of intense shockwave, High temperature & Microstreaming of the liquid 1 Production of high shear gradient t Emulsion breaking Limitations A sinusoidal sound wave propagated through a liquid is an elastic wave and is accompanied by periodic changes in pressure. The frequency of such waves can vary between a few hertz and several gigahertz (1 GHz = 10° Hz), Frequencies upto about 15 KHz lie within the audible range while those between 15 KHz and about 800 MHz are said to be in the ultrasonic range; frequencies above 10° Hz lie in the so-called hypersonic range. The most obvious experimental limitation was that we could not vary the fre- quency of ultrasonic waves since energy at only one frequency 125 KHz could be used in our experiments. As there is wide variation in the properties and composi- tions of both crude oil and brine water, emulsions of varying characteristics are formed in oil field, Also there is need to investigate its effectiveness in flow pro- cesses. Ultrasonication experiments were carried out with synthetic emulsions prepared in laboratory and oil field emulsions. It was comparatively easy to break synthetic emulsions than oil field emulsions. From the comparison of results of synthetic and oilfield emulsions, it is evident that for oilfield emulsions, demulsifi- er doses required arc little higher, due to the difference in stability of the two emul- sions. There are more differences in synthetic and field emulsion. In synthetic emulsion fresh water is used as dispersed phase whereas in field emulsion brine is the dispersed medium. Another important factor which is responsible for contri- buting greater stability is ageing. Synthetic emulsion was investigated within 36 hours of formation in most cases whereas sometimes even a few months elapsedULTRASONICATION FOR BREAKING WATER-IN-OIL EMULSIONS 193 before the field emulsions could be investigated. The results of experiments con- ducted on synthetic emulsions have not been reported in this paper. Conclusions Ultrasonic waves have long been used for emulsification, homogenization, scrub, and to wash machinery and delicate jewellery. In the last decade, attention has been focussed on extending the application of ultrasound to various engineering disciplines, particularly to Chemical Engineering, in areas like mass transfer, heat" transfer, mechanical operations, and polymerization. There is a wide scope for study of the application of ultrasonics specially in petroleum engineering (in me- chanical operations). In this study, ultrasonication is imposed on chemical demul- sification and appears to be a useful technique to destabilize water-in-oil emul- sions. There is a need to study the commercial viability of this technique for dem- ulsification in Petroleum Engineering where use of ultrasound is still in the initial stages of development. The following conclusions were drawn:- (1) The use of ultrasound seems to display promise in demulsification of water-in- oil emulsion; upto 75.5% water separation was observed without demulsifier. (2) The use of M-485 (Nonionic) & CTAB (cationic) appear to have best demul- sification properties at 1000 ppm and 500 ppm respectively, leading to 100% separation of emulsified water. (3) The results at the study suggest that demulsifiers at lower concentration were more effective than at much higher concentration. At higher concentrations, separation decreased due to re-emulsification. Demulsifiers should not be present in the emulsion during excessively prolonged agitation because the beneficial effect of the demulsifier may be spent or counteracted by the agita-~ tion and re-emiulsification may occur. (4) A comparative study of ultrasonic and chemical demulsification clearly re- veals that the ultrasonic method of separation is more effective. Acknowledgement The authors wish to thank Professor D K Sinha, Director, Indian School of Mines, Dhanbad for his kind encouragement. The authors are also very thankful to Insti- tute of Oil and Gas Production Technology (Oil and Natural Gas Commission), for sponsoring the project and financial support. References 1 LT Monson, Chemical resolution of petroleum emulsions In: Surface Operation in Petroleum Production (Eds. G V Chilinger and M Beeson) American Elsevier Publishing Company Inc. New York (1969) 2 DN Levchenko, A $ Ermilov, G A Teplykh and N K Volobue Primenenie Ultraakustilssed Ves- cchesta 14 (1961) 337; CA. 7, 1179C. 3. CS Frang, K L Change Bruce, M C Lai, Peter and WJ Klaila Chem Engng Commun 73 (1988) 9 (Engng). Chem Abstr Tract 110 (1989) 306pp ‘Studies on Crude Oil Emulsions and Parameters Affecting Demulsification, Ph.D. Thesis, ISM, Dhanbad (1991)194 B PSINGH AND B P PANDEY 5 PHElworth J Colloid Sci3S (1971) 34 6 DJ Jeffrey and A Acrivos AICHE J22(1976)417 7 TH Pleque. 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