West Indian Jounal of Engineering Vol 25, No 1, ly 2002) Techical Paper (Moos & Dawe) 25-41 Oily Wastewater Cleanup By Gas Flotation R. Moosal” & R.A. Dawer* Produced wastewater from hydrocarbon reservoirs always contains some oll. The free oil is often in an emulsified form with the median stroplet diameter usually inthe range of 3.20,um . Gas flotation of oly wastewater isa process in which fine gas bubbles are injected into a water phase. Oil droplets and oilcoated solids, which are suspended in the water become attached to these bubbles, rise othe surface, are ‘rapped in the resulting foam and removed when the foam is skimmed from the surface. The effcveness of flotation depends on the traditional ‘gravity separation paramelers of density difference, oil droplet size, ‘and temperature but also critical are the gas bubble sie distribution ‘and an even dispersion of the bubbles. Gas flotation is particularly valuable for removing oll droplets when the ol density is close to that of water (i.e, heavy oil), such asin Trinidad. Ths paper discusses the ‘operation ofthe gas flotation process for oll wastewater including the ‘mechanisms behind the process, particularly the gas attachent oil droplets. Aclearer understanding of oilbubble contact and the influence ‘of surfactants in aiding this contact could mate flotation applications ‘more widely considered for Trinidad’ oily wastewater treatment. $$ 1. Introduction 1.1. Olly Wastewater Produced water is the water that comes with oil and ‘ms during hydrocarbon production. Ialways contains ‘some ol, The treatment of this produced oily water to an environmentally accepted level before disposal has ‘become mandatory in most countries. In Trinidad and Tobago, government environmental pressure to Improve the quality of oil-water separation i the oilfields is increasing with 40 pats per million (40 img per lire) being the quoted legislated standard, Elsewhere in environmentally sensitive counties, g, Norway, lower figures are mentioned, even zero ‘This implies that dissolved and non-dissolved ‘components will have to be removed from wastewater before disposal “The non-dissolved oi in wastewater isin toe forms as 1. Drops >150 jam in diameter, which an be separated by conventional methods, except fr heavy oll discussed in 1 below; 2. As free droplets 15-150 jum; 3. Asa stabilised (often with indigenous anionic surfactants) oil-in-water ‘emulsion, with the median droplet diameter usually inthe ange of| 3-20 pm BI ‘Such oil-in-water emulsions are generate by shearing in pamps and by twrbulet Mow in pipes as well as from steam injection EOR methods. These crade-in- water emulsions ao often stabilised by the variety of surfactants indigenous to the erade oil olor elu pei Ua, Dermot Chae Lagcena Te anny he Wot Iden St Ani, Tia‘ot aia Jounal of Eagincring Ve. 25, No 1, ily 2002) Techical Paper (Moots & Dawe) 25-41 “The formation of an emulsiow involves the -reation of enormous areas of interface, typically ~ Im? perce of oil ifthe droplets ae of 10 pum in diameter “The dissolved form has to be removed through jon exchange or bioremediation [1,2]; these processes will ot be discussed further here "The separated water must be de-oiled before disposal, otherwise it could become an (expensive) fevirosimental embarrassment if cil polltes potable rater sourees or rivers. Large volumes of oily trastewatcr are being produced. Additionally, the water Fs saline, with conceatrations of salts as high as 25% by weight, but fortunately is usally les (remembering, that seawater is 3.5%) and itself could be an caviroamental jazad "The oily wastewater treating facilities curently teing used by many companies in Trinidad use oaly ‘gravity induced separators and puard basins however, ‘ischarg effluent often have oil concentrations thet ‘exceed 50 pats per million Thete area wide variety ‘f separator designs and configurations, some with father exotic proprietary internal devices. ‘The equipment chosen for any wastewater treatment facilisy must e according to the characteristics ofthe wate to be treated and to its ultimate disposal. The ‘Nandard ol water gravity separators well discussed elsewhere [4-7 1.2 The Problems of Heavy Oil Heavy il has density close to that of water. Much of ‘Trnidad's is heavy s0 that Jacto this sal density ferential, these oly wastewaters cannot be separated {nto oil and water by gravity separators, Additionally, these heavy crade oils tend to form stable emulsions ‘because of the waxes, asphaltines particles and other impurities preveat, which, in combination with ‘properties stich as high viseositis and densities and Foaming characteristics, make these wastewaters difficult to teat by traditional treatment systems For heavy oil, the industry typically uses large separators, long reteation times and heat plus dosing the system with quantities of demulsifir chemicals, ‘Sach facilities are expensive and increase the cost of 8 product whose value is curently Jower than that of Tightcrude. Additionally tbe product may still not meet specifications. "The small density difference betwoen the heavy cil and water make the separation by bydocyelone of centiuge ineffective [8]. Further problems are eeated by the emulsions formed between theo andthe water being extremely strong However, ga ltation is able tocope. 2. Gas Flotation flotation is a process in which numerous microscopic gas bubbesare injected into water phase ‘containing immiscible liquid (oil) o solid particles so thatthe bubbles attach themselves tothe particles and Good flotation, fllowed by > Elficient skimming of the ol that bas floated tothe surface with‘West indian Journal of Engineering Vo. 25,No 1, lly 2002) Techical Paper (Moos Dawe) 25-41 > Aneffective chemical programme (ninimum quantities and maximum oil removal) Flotation units have developed over the years, initially for mineral processing. The water travels through the flotation chamber and by suitable placement of baflles and weirs moves downwards ‘towards an exit, and the oily drops with attached gas tends to move upwards. Good flotation for oily wastewater is brought about by the itroduction of lotof fine bubbles. The smaller the bubbles, the beter, since the small bubbles ean capture the small oil droplets: However, once bubbles are released, they can collide and coalesce into larger bubbles but large ‘bubbles are ineffective for flotation They rise rapidly creating unfavourable turbuleace and break-up of bubble-droplet agglomerates. How the bubbles are Inirodvced into the water systom is also important “Thus, critical desig factors are the aeasinthe flotation ‘chamber where the bubbles ae created and where il and gas attachment occurs, Bubbles can be erested in a number of ways, but in fold practic, there are wo common methods ‘of introducing the gas bubbles - those of induced gas flotation (sometimes termed dispersed gas flotation), IGF and dissolved ga flotation, DGF The siguificant Aiferences between the two flotation processes ate the average bubble size, the mixing conditions snd the hydraulic loading rating, with induced flotation having ‘the higher valuc, There are other more sophisticated (and expensive) methods such as electrolytic gas bubble genration creating stable bubbles of ~10 jun diameter and gas sparging, where gas is pumped ‘through porous tubes to creat the gus bubbles but these are not discussed further here [11]. 3.1. Induced, or Dispersed Gas Flotation (IGF) IGF mechanically introduces the gas as bubbles. Initially, the gus is drawn into the ming area, where (osualy) 2 propeller mochanically gittes the oily water and shears the gas into ~100-1000 um diameter bubbles (Figure ). The gas is draw into the water and mixed with, unlike DOF (discussed below) where 28s disolved in the wate and comes out of solution by depressurisation. The retention time in the wastewater treatment unit may be as low as four minutes. Sludge is gradually formed from the input 29 Water and if this i disturbed by the propellers and moved to the alachment zones, it can destroy the Aetation process ‘The IGFs units ae usually multi-el indesign {in order to improve their performance. The inlet gas ‘nozes, rotors oreductors essentially vacuum pumps) and baffles are patented designs. IGF units ean be ‘operated at much higher hydraulic loading (higher flow thronghput for equivalent surface areas) than DGF. Hence, the capital costs for teatment equipment are Tower than DGF but because ofthe large gas bubble and smal oil droplet sizes andthe quiescent conditions needed for agglomerate formation [OF is wot now the preferred option for oily wastewater cleanup, 3.2. Dissolved Gas Flotation (DGF) GF introduces the gas bubbles in a different way. ‘Waters saturated with gas under pressure (upto four atmospheres), so that gas is dissolved in the water and is released from solution by pressure drop to atmospheric pressure inthe flotation chamber The gas evolves from solution as small bubbles, 10-100 07 diameter (Figure 2) often deseribed as making the water go ‘milky white” (11, 13]. DOF units are so designed that the gas bubbles form inthe environment ofthe oil droplets. Retention time in the flotation chamber is usully about 15-30 mins. and isa fairly gentle process, Suspended solids and minor entrance turbulence acts acl for bubble formation. Cleaty, ‘the amouat of gas available for flotation is dependes ‘onthe operating pressure forthe gas-satuating sytem. ‘The loading rates are smaller than IGF but the bubbles are smaller hence have longer retention times in the flotation units, and slower particle rise rates. ‘Mali cell units are used in practice - often a set of five lotation cells Turbulenceislow ia well-designed and properly operated systems. Chemicals, as discussed [ater in 4.4, are added to neutralise the negative charges on the bubbles and drops in order to floceulate the ol, break the emulsion drops to form lange flocs, so that bubbles have even greater cil-floc area in which to attach, Gas bubbles are formed in and around the suspended solids and emulsified oil droplets. However, the flocs can become a continuous oily sludge, ‘There are # number of ways of designing the ‘as pressursation systems including (11)‘West nda Journal of Engineering Vl.25,No = Total pressrisaion ofall he water Jeedwater, Here, more gasihr is needed ‘which should lead to higher separation ‘elfcieney. Any solids in the influent ‘must be pumped through the pressuristion chamber tothe flotation ‘chamber which ean destroy floating ‘agglomerates by collision Aditionally ‘the ol inthe wastewater can be further emulsified within the pumps by shear Higher power requirements are ‘needed to un the pamping systems. = Pressurisation of only part ofthe inlet water Cleatly, lower power is required compared tothe fll stream prescurisation and less gash ‘Some influent solids and emulsification ‘aust be pamped. = Recycle presurisation (Figure 2). Here, some of the outlet waters ‘pressurised with gas, upto about 60 psig and passed back into the flotation ‘chambers. In the chamber, the pressure release generates the bubbles from the now supersaturated water, provided suitable nucleation sites ae available. These are often cavitation turbulence. As the pressurised waters ‘lean, no influent solids and emulsions fre pumped through the gas solution chamber with this process, The recycle Inti of pressurised water canbe varied from 2e0 to 100%, but typically 10-50%, Homever, larger flotation eels than ‘the other methods are needed (creating higher initial plant costs), butts now the preferred method. 3.3. DGF Designs ‘There are many different designs of flotation unit with 3 and <100 om, Fis shown to be proportional to the diameter of the oil drop squared (the trajectory ofthe drop must be within its diameter of the bubble surface - the collision region), and is not greatly affected by bubble size but Significantly by bubble mumber density. This is because, as Reay and Ratcliff found, E, is lager for more (., smaller) bubbles fora given gas flow rae. ‘Thus, they found itis better to have oil drops as lange as possible and gas bubble size as small as possible longer residence times). Reay and Ratcliff also ‘examined F for patcles <1 pm, when the motion is [Brownian diffusion. They showed that collection was sill posible but the mass of cil collected would be small, and their advice is to grow the drops by ‘coalescence 10 about 20m [25], Eis the faction of particles that collides with ‘the bubbles that actually ‘stick’ and this clearly depends ‘on the surface interfacial forces to attain il thining and spreading. The interfacial science controlling gas flotation of oil droplets by gas in oily wastewater isa combination of a number of processes as discussed later‘West indian Joumal of Hnginering Vl, 25, No.1, uly 2002) Technical Paper (Moos & Dawe) 25-4 Jef fL ot dep being approached in | stds missed by goo ie 4 | cian movi soy up bit collided ol drop now spreading +" oll drop outside collision, Zoe Sas gos bubble FIGURE: The Collin Zone o © “©| (es) Sy es) const (w=) | ie Sak approach ssachment tise FIGURE & The Gar Flotaion Process‘West Indian Journal of Engineering Vl. 25, No.1, uly 2002) Technical Pape (Mossi & Dame) 25-1 ‘rupture JIGURES: The Ascent Peas 4.3 Coalesconce These processes are affected by: CCoalesceace of oil drops and attackmeat of oil drop! gs bubble usually occur simultaneously, however the > Plowrate, «il drop gas bubble attachment is essential for flotation. The flotation process between gas bubbles and > Gas-input rate and volume of gas cil droplets canbe broadly classified into the following released per unit volume of liquid; (Figures 4 and 5): ae Bubble size distribution and degree > emulsification via coalescence of of disperion oil drops: > Temperature; > Approach of gas bubble and fal droplet, > pi (best pH at 7 2 units) so the ‘wastewater pH may need to be > Collision between the oil drop adjusted wo this range; surface and he bubble; > Chemical content ofthe wastewater > ilbubble attachment via film and the ol, drainage and rupture; > Comeet dosage of chemicals > Spreading of oil om the gas, > Rise to surface‘West indian Jounal of Enginetng Vl. 25, No. 1, uly 2002) Technical Paper (Mooi & Dawe) 25-41 44 Chemical Additives - Surfactants and Polyelectrolytes ‘The oil in wastewater is usually inthe form of oi in water emulsion with most droplet diameters being ess than 20m witha median often around Sym. These tiny drops are prevented from coalescing by aegative charges on the surface ofthe oil droplets and gts bubbles duc to electrostatic forces created by the clectric double layers. These create a repulsive force ‘between the drops or bubbles which keep them apart and thus have a low probability of coalescing. ‘Separation by gravity hy letting the wastewater stand (Ge, Stokes Law) can be dismissed asa demulsifying force for industrial purposes, hecause the smal size of the oll drops make ths process extremely slow, © ‘estimates [14] for a density difference of 0.1gm‘ce predict that a 10mm rise in an aqueous mediam will take around 50 sec fora 70jum diameter ol drop, 600 sec for 20jum and 3040 see for 10. . Thus, before flotation can be effective industrially, the emulsion rust be destabilsed and the oil droplets coalesced To break the emulsion, the accumulated electrical charge on the bubbles and drops must be neutralised by introducing an opposite charge. This is achieved by demulsfiers. In terms of physical interactions, the emulsifier serves > To modify the charge of the oil droplet > To.cause flocculation by anchorage and bridging mechanisms ‘Surfactants, or surface active agents, are molecules ‘which ae abe tomodify the properties of an interface, 8, liquid ar or liquid liquid by lowering the surface for interfacial tension. A surfactant possesses the fundamental characteristic of having two essential portions, one being water repellent, usually called hydrophobic (or oleophilic, the other being water tractive, usualy called hydrophilic (or cleophobic) ‘The hyophobic portion comprises a collection of hydrocarbon groups, some at least of which form a linear chain which may o¢ may aot be substituted to varying extents. The hydropbilic portion comprises a solublising group such as sulphate, sulphonate or ehoxylate ‘The number andarangement ofthe hydrocarbon ‘groups together with the ature and position of the lbydrophilic groups combine to determine the surface active properties of the molecule. Ifthe hydrophilic Potton shigh molecular weight itistermed.a polymer Surfactant, Surfactants fall into four categories ‘depending on the distribution of electrical charge on the molecule viz > Anionic in which the bydrophobic portion ofthe molecule caries « residual negative charge, RCOO™ ©, sodium dodecy sulphate: CH,CH/CH),CH, 080,” Na* > Cationic in which the hydrophobic portion carries a residual positive charge, RX" eg, cetyltrimethyl ‘ammonium core: CHYCH),CHNCH)," Cr > Nonionic i which there is 0 residual electial charge, eg odecylaleabol ethoxslte: CHC, CH(OCH,CH), OH > Amphotericin which both postive land negative centres are to be found inthe molecule, eg, alkyldimethylbetaine: (CH).(CH)-R-N’-CH,COO™ ‘These surfactant molecules orient themselves at the co-water interface. A flocculat, whichis bigh weight ‘ationic or anionic polymer, is added after to create smacroflos. Faster flctaton resus cconding i Stokes "and 8 more efficent separation. An emulsion is typically a high charged, low molecular ‘weight, cationic polymer. They have along chain and {naddtion to charge neusalistion enables mechanical ‘bridging of oil drops to create flocs. An anionic polymer, hich has a high molecular weight, can then ‘be used to promote growth ofthe floe through further rechanical bridging. An even larger rising velocity will occur according to Stokes Law when the radi ‘ofthe ‘oil drop increases through suck oe formation ‘This will i tur increas the frequency of ts collision with similar molecules of ol and ths form even larger foes. I will also increase the collision rate with the ‘gus bubbles in the wastewater flotation tak, further‘West nian Jura of Engineering Vl. 25, No.1, uly 2002) Tecaicl Paper (Monnai & Dawe) 25-4 increasing the chances of oilfbubble attachment ‘Organic emulsion breakers, in addition to producing beter effluent quality often reqite less dosage and produce a smaller Volume of sludge, than if an inorgani programme was employed Curreatly, in oily wastewater industrial practice, ‘cationic and anionic surfactant and polymers are used ‘tailor the floc size, loating characteristics and shear strength. In practice, the chemicals used to give ‘optimum results typically would be a primary ‘coagulant (emulsion breaker) being a low molecular Weight, cationic (i, positively charged) polymer Which is able to neutralise the ncgative charge on the oil droplet as it adsorbs atthe negatively charged surface of the oil droplet. This is followed by a high molecular weight (~2000) anionic polymer, often derived from ethylene, propylene, vinyl, vinylidene oF vinylactate, which ca then be wsedto promote growth ‘ofthe lo through mechanical bridging ‘The preferred sie ofthe polymer molecule i such that several oil _lobales can become attached to one polymer, whi ‘causes them to coalesce into larger particles by a ‘bridging mechanism 45 Jar-Testing ‘The maximum amount of surfactant that shoud be used isthat which ceats the Critical Micelle Concontation, ‘me, a the salinity and temperature ofthe wastewater {251 The cmc is the point when a surface is covered by a monolayer of the surfactant. At this point, aggregates of surfactant molecules (micelles) begin form inthe bulk phase, Above this conceutation, the surfactant concentration is “overshot” and causes the ‘droplets to gain increased charge and repel each other so thatthe separation process lose its efficiency, Tt ‘can cause the formation of foam between the surfactant ‘and gas bubble. This foam cannot efficiently trap oil ‘drops and the entire purpose of surfactant usage will be defeated. If too litle surfactant is used, flotation will be less efficient since the conditions are not ‘optimum (perhaps 20% les effective). Hence, before chemicals are added, ther opximum concentration must ‘be determined. This value will vary according tothe field conditions including diurnal temperature ‘variations, conceotration of wastewater, ol properties, and the salinity of water. Unfortunately information on flocculation and surfactant composition used commercially isnot often Aivulged in product iterature, much othe disadvantage 35 ‘of those wishing t minimise their costs or select the ‘optimum floculants- To select and screen demulsifiers, the effect of various factors that affect wil wat ‘separation need tobe quantified. These include shear, asphaltene content, water cut, demulsifier dosage and ‘mixing different crudes and temperature. Increasing the temperature decreases the viscosity’ of the oil and emulsion, increases the frequency of the drop coalescence greatly. Experiments must be caried out to identify suitable chemicals (surfactants) and their concentrations. The inlet wastewater steam must be ‘monitored closely, especially if surges concentration ‘occur frequently. Bote jar-testng or some ater test is essential, Such tests can identify some chemicals, and eliminate others, which might be effective under the field conditions. Bottle tests involve the mixing of the various chemicals with samples cf the contaminated water, shaking and observing the results. It isthe normal procedure used in determining the optimum concentration of polymers needed forthe flotation unit's treatment fluid at any point in time. It is a relatively quick method for selecting the chemscaltype, ‘dosages and treatment conditions. It needs a small volume of material, relatively shor testing time and is olatvely inexpensive. During full scale operation jartestng can be used (0 check chemical feed rates Which may lead toa substantial decrease in the amount ‘of chemicals used, the quantity of sludge produced, a8 well as. heter quality effluent. However, a problem ‘can sometimes occur when sealingup the laboratory {est results for application to field operations, because 4 surfactants effectiveness is highly dependent pautcully onthe cme, which i affected by the current Field water characterises, The Feld conditions canbe ‘ery variable duet changes in production ates, steam salt concentrations, rainwater additions and temperature changes caused by weather or simply day and night variations. Any deviations from the field conditions of evena well planaod laboratory jar-testing programme can be ruined by deviations of the field conditions forthe laboratory tests, which then have ‘detrimental effects om the flotation efficiency. 4.6 Approach of Oil Droplet ‘and Gas Bubble As two drops (ola orl gas bubble) approach each ‘ther ina medium, there is deformation ofthe drops,Wes Indian Journal of Engineering Vl. 25,No 1, uly 2002) Technical Paper (Moossi & Dawe) 25-41 4.6 Approach of Oil Droplet land Gas Bubble Astwodrops (ill orci gas bubble) approach each other in a medium, there isa deformation ofthe drops, which results inthe formation ofa dimple Figure Se) This gradually disappears, giving way to a thin inorsitial water film between the two oil droplets ‘which must drain before it can rupture. 47 Drainage ‘The inesttial film drain under the combined ation ‘of capillary suction and osmotic pressure, balanced by disjoining pressure [26-32]. Disjoining pressure consists of van der Waals dispersion forces and clectrostatic forces. The capillary pressure is the pressure difference between the inside of the drops ‘being greater than the pressure outside. Gravity Forces play only «minor role in the drainage proces; they slightly disturb the shape of the film, although the characteristic dimple is partly caused by the effects of _ravity. The dimple induces a pressure distribution in the film, and hence fluid flow. The lifetime ofthe film isdetermined bythe rate at which drainage takes place; it isthe rate-Limitng step ofthe coslesceace process. The stability of this film is a crucial factor in The amount o ol, which is still ‘within the water after separation by normal skimmer, is not low enough tomect the new environmental adds » The al droplet size is often ess than ‘204m caused by shear when passing ‘through low lines and production equipment > Itis the only possible method for heavy oils i, where the density of cil is close to that ofthe water phase, ‘and for emulsions where the median “rople size is ofthe order of 220)un. Flotation works well with drops 20 Good flatation > Ansppropriate chemical programmeWiest indian Jura of Fnginerng Vt. 25, No.1, ly 2002) Technical Paper (Moca & Dawe) 25-41 ficient skimming of the ol that is fated tothe surface 4 There are many physical factors that influence the flotation of oily wastewater. These include ialt concentration of i, density of oil, salinity and visosity of the aqucoas phase, droplet and bubble sizes and chemical interventions The attachment efficiency is alfected by ‘many parameters and requires further study. Currently interreltionships between cll design and feed parameters determine the separation efficiency. Thus, the flotation sit has to be optimised locally om site. 5. ‘Theeffeetive operation of the gas flotation process requires an understanding ofthe mechanisms behind the process, particularly the gas atachment ool droplets. The physics to aid in the finding ‘of the optimum parameters ofthe Motation process covers oilbubble contact, the interactions of surfactants in aiding this contac, and the spreading ofthe oil around the gas bubble. ‘6 Parther study must be carried out onthe ‘denification of suitable surfactants, their ‘concentrations and effectiveness under the ‘atable field condition so that the chemical ‘costs can be reduced and efficiency increased im the tation proces. ‘Acknowledgement ‘We are grateful to The Campus Research and Publication Fund Commitee, The University of the ‘West Indies (UWI, for financial assistance, We thank Dx. CA. Graltoni of Imperial College, London, UK and R. Gayoso, Tramsep SA, Argeatina for helpful advice References 1. Hansen, BR. and Davies, SRI. (1994), Review of Potential Technologies for the Removal of Dissolved Components from Produced Woter. 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