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Journal of Dispersion Science and Technology, 30:10791090, 2009 Copyright # Taylor & Francis Group, LLC ISSN: 0193-2691

print=1532-2351 online DOI: 10.1080/01932690802598754

Oil Base Mud. Part I: Synthesis of Some Local Surfactants Used as Primary Emulsiers for Oil Base Mud and Evaluation of Their Rheology Properties
A. M. Al-Sabagh, M. R. Noor El-Din, and H. M. Mohamed
Department of Petroleum Applications, Egyptian Petroleum Research Institute (EPRI), Nasr City, Cairo, Egypt

Six oil soluble nonionic surfactants with different HLBs have been prepared. Their HLBs situate between 3.9 and 6.7. Transesterication was carried out for glycerol and triethanol amine with oleic acid at different moles to obtain six emusiliers. They named glycerol momooleate (I), glycerol diooleate (II), glycerol trioleate (III), triethanol amine mono-, di- and tri-oleate (IV), (V,) and (VI). The chemical structure was conrmed using; the elemental analysis, FTIR and 1 HNMR. They were evaluated as a primary emulsiers (PE) for thdrilling uids (oil base mud) comparing with a currently used primary emulsier (Fc). The water in oil base mud (w/o emulsions) was prepared. The concentration of emulsiers and their HLB exhibited interesting rheology properties including shear-thinning behavior, yield value, viscoelastic effects, thixtropy, gel strength, and ltration loss. The rheology properties of such emulsions strongly depended on the average size distribution of the dispersed droplets that could be varied both with the bulk concentration and HLB value of the emulsiers. The interfacial and surface properties of these emulsiers suggest that the droplet size of the dispersed phase and bulk concentration are strongly related to the HLB value of emulsiers. The w/o emulsion (mud formulation) stability is sensitive to the droplet size of the dispersed phase and HLB value of the used emulsier. The results were discussed on the light the chemical structure of the primary emulsiers and the emulsion ingredients. Keywords Drilling uids, drilling mud, ltration loss, gel strength, interfacial properties, oil soluble emulsiers, rheology

INTRODUCTION In many wells drilled with aqueous drilling uids suffer serious decreases in permeability of oil bearing zones as results of water blocking of the pore spaces and swelling of anhydrous clays within the pore spaces. This water contamination difculty can be avoided by the use of oil, such as crude petroleum oil as a drilling uid. This means usually involve adding materials such as blown nally divide solids to the oil to increase the density, viscosity and gel strength, and to give the uid plastering properties to decrease loss of the uid to the permeable formation.[1,2] The success of any well drilling operation depends on many factors; one of the important of which is the drilling uid. The uid performs a variety of functions that inuence the drilling rate and the cost, efciency and safety of the operation. Drilling uids generally are composed of
Received 24 January 2008; accepted 6 February 2008. Address correspondence to A. M. Al-Sabagh, Department of Petroleum Applications, Egyptian Petroleum Research Institute (EPRI), 1 Ahmed El- Zomor St., Nasr City, Cairo 11727, Egypt. E-mail: alsabaghh@gmail.com

uids (water and gas-oil) and suspended erily divided solid of various types. The proportions determine the treatment strategy, the efciency of the mud- handling equipment, and affect the amounts of materials needed to bull up density and viscosity.[46] No additives are used in dry-air-, or gas-drilling operation. Gas based uids are not recalculated and materials are added continuously.[7] The functional properties include water loss, gel strength, viscosity and thixotropy, and resistance to salts and alkaline earth ions.[8,9] One of the most widely used ingredients in water base drilling mud is carboxy methyl cellulose. It is very effective in preventing water loss and in controlling the viscosity.[10,11] Freshwater mud may be operated at pH levels ranging from 7 to 11. When drilling occulent may be added to remove drill solids in large settling with clear, and a small amount of pit in order to maintain a clean uid for fast drilling. Generally, seawater mud is formulated and maintained in the same way that freshwater mud is used. However, because of the presence of salts in seawater, more additives are needed to achieve the desired ow and ltration properties.[12,13] Fresh- or seawater mud may be

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treated with gypsum on lime to alleviate or clay bearing problems that may arise from drilling water-sensitive shale or clay bearing formation.[1418] Fluid with less than (5 to 10 vol% water) is called oil base mud. Most oil mud maintain a xed oil-water ratio depending on the desired properties. Oil mud are employed for high temperature wells, where water-based system may be unstable and a problem may be raised from sensitive shale formations, or where corrosive gases such as hydrogen sulde and carbon dioxide may be encountered. Usually, the cutting removal efciency increase with increasing the viscosity and the density. Viscosity depends on the concentration, quality, and state of dispersion of suspended colloidal solids.[1922] Most concentrated emulsions show shear rate dependent non-Newtonian type shear thinning behavior at low and intermediate shear rate domain, where the shear viscosity (g) decays exponentially as a function of shear rate. On the contrary, at high shear rate domain, these emulsions show Newtonian type shear rate independent shear viscosity. Materials with such mixed ow proles, viscosity shear rate in steady state shear mode are usually known as pseudoplastic materials,[23] and these generally show a combination of shear thinning behavior and yield stress, it means that ow on these materials can only be induced with the application of a certain minimum amount of force=stress which is referred to as yield stress. High value of yield stress is indicative of higher degree of material structuring and good emulsion stability[24] Rheology of most viscoelastic materials, including surfactants solution,[25] and surfactant stabilized emulsions tend to show Maxwell model type uid ow behavior.[26] The rst goal of this work is focusing on the preparation of some primary emulsiers based on glycerol and triethanol amine with oleic acid. The second goal is to make six formulations of oil base mud using the prepared emulsiers to increase the plstic and dynamic viscosity, yield value, thixtropy, gel strength, and ltration loss properties.

emulsiers named; glycerol monooleate (I), glycerol dioleate (II), and glycerol trioleate (III), triethanol amine monooleate (IV), triethanol amine dioleate (V) and triethanol amine trioleate (VI). Emulsion Preparation To 100 ml of gas-oil, 1, 2, and 3% of the prepared primary emulsier (I to VI) was added individually at room temperature with continuous stirring and then 10% of distal water was added gradually with continuous stirring until a milky emulsions were formed. The solids added to form the mud formulation were (3.5% guiletane, 1.4% durtane and 1.4% soda lime, wt=wt) were added and they mixed gradually. Finally, 1.2% of E.Z mud as a second emulsier was added with stirring. The ingredients were mixed well for 10 minutes to form six different formulations (F1 to F6). Surface and Interfacial Tension Measurements The surface tension of surfactants solutions was measured at 25 C against the hydrocarbon system (gas-oil) using a Kru ss made surface tensiometer K12. An oil bath was used in this case to maintain the temperature. The Du Nou y ring method was employed, where the ring is dipped into the solution whose surface tension is to be measured and pulled out afterward. The maximum force needed to pull the ring through the interface is expressed as the surface tension in mN=m. On the other hand, the interfacial tension at the w=o interface was measured at 25 C using Kru ss made Drop Volume Tensiometer DVT 10. Droplet Size Measurements The droplet sizes distribution can be measured with help of optical microscopy. An account of the use the optical microscopy to measure the emulsion droplet size is extensive.[27] In this study, a German made leica DMRXP light polarizing microscopy was used. This system consists of a high voltage beam source, a polarizing unit and a detector unit. The detector unit is interfaced with a camera. Note that the images were focused both under the dark and bright eld mode as well as between the cross polarizer using long working distance objectives with magnication ranging from 20 to 50 to 100. This microscope unit is controlled by computer which is equipped with image analysis software. This software not only helps capture images from the stage of the microscope, but with its help one can process these images as electronic documents including measuring droplet size. High PressureHigh Temperature Filter Press Measurements High pressure-high temperature lter press is especially designed for testing mud at elevated temperature and pressure. It consists of a heating unit with a thermostat,

EXPERIMENTAL Preparation of Emulsiers Based on Glycerol and Triethanol Amine Into three-necked ask, 1.0 mol of glycerol and triethanol amine were added to (1.0, 2.0, 3.0 mol) of oleic acid individually. The reaction was carried out in the presence of 0.1% p-toluenesulfonic acid as a catalyst and xylene as a solvent. The reaction was heated with continuous stirring and the reux of solvent was carried out until the theoretical amount of water was collected. The product was puried by washing it with 5% worm solution sodium carbonate then was dissolved in petroleum ether (4060 C), and the organic layer was separated. The solvent was distilled off. This method was carried out to obtain six

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250 ml lter cell, and the pressure unit. The uid loss value obtained with this apparatus more truly represents the actual uid loss in the well pore. For tests which are to be run above 200 F, the back pressure receiver must be used in place of the graduated cylinder to prevent evaporation of the ltrate. Procedure Into a clean aging cell, 200 ml of the mud formulation was transferred. Be sure that the sealing edge of the cell is clean and put the inner cap in its place. Then use an Allen Wrench to tighten the small center screw in the middle of the screw cap. The cell was placed in a portable aging oven and adjusted to the desired aging temperature. A hot air oven may also be used provided a constant temperature (200 F). A graduated dry cylinder was placed under the ltrate tube. A 500 psi pressure was applied to the cell, and the time of the test was started. At the end of 30 minutes, rst close of the pressure source valve was carried out and then the safety bleeder value was opened to release the pressure from entire the system. The volume of ltrate was collected and expressed on the ltration loss in ml. Rheology Properties Measurements The rheological properties of emulsions were measured using a rotational viscometer with coaxial cylinders (Rheotest 2, Germany). Samples were placed in the temperature-controlled measurement vessel and equilibrated to required temperature for 5 min period to making the measurements. The rheological behavior of the emulsions

was measured 24 hours after preparation. The measurements were only accepted when the emulsion had not shown any coalescence before and after shearing. The shear rate (D.S1) was changed from 3 to 1024 (s1). Determination of Gel Strength and Thixotropy of Mud The gel strength of mud using the rheometer was determined. The mud sample was stirred at high speed (4000 rpm) for 15 seconds. The mud emulsion left to rest about 10 minutes and then the gel strength knob was turned on the hub of the speed change level clockwise slowly and steadily. The maximum deection of the dial before the gel breaks is considered the gel strength in 1 b=100 ft2. The difference between the low readings after 10 seconds and 10 minutes is considered to be the measure of thixotropy of the undertaken mud formulations (F1 to F6 Fc). RESULTS AND DISCUSSION FTIR and 1HNMR Spectroscopes for Chemical Structure Justication The FTIR of glycerol dioleate is shown in Figure 1, The characteristic broad bands are 3498 cm1 assigned to OH group stretching vibration, two bands at 2921 and 2862 cm1 for asymmetric and symmetric aliphatic CH stretching vibration of fatty acid moiety, respectively. A band at 1732 cm1 characteristic for CO stretching of the ester group conrming the ester formation, a band at 1490 cm1 pair for CC stretching absorption. The 1 HNMR spectra in Figure 2 for triethanol amine dioleate

FIG. 1. FTIR spectra of glycerol dioleate (II).

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FIG. 2.

HNMR spectra of triethanolamine dioleate of (V).

shows splitting at chemical shift d 5.345.27 ppm (s, 1H, 1OH), d 4.974.38 (s, 1H, of CHCH of oleic alkyl group, d 2.712.35 (s, 2H, CH2 of oleic alkyl group), d 1.451.40 (s, 2H, CH2 adjacent to oxygen or nitrogen atom in the tri ethanolamine structure, and d 0.990.64 (s, 3H, of CH3 of the alkyl group). The elemental analysis (C, H, and N) for all the prepared emulsiuers was carried out and the data are presented also in Table 1. The all used analysis tools together introduced the evident of the chemical structure as excepted. Interfacial Properties The HLB values of the emulsiers employed in this work is given in Table 2. The HLB value is the balance between the hydrophilic and lipophilic strength of the emulsier. It can be calculated using Grifn approach as:[28] HLB 20 MH MS

Where MH is the molecular weigh of the hydrophilic head group and Ms is the total molecular weight of the emulsier, this relation suggests that the HLB value is closely related to the size and molecular weight of the head group. The hydrophobic effect of an emulsier is better described by its surface and interfacial properties. The surface and interfacial properties of these emulsiers are given in Table 2, which suggests that the critical micelle concentration (CMC) value of these emulsiers is related to their HLB values. With decreasing HLB value, the CMC of glycerol and triethanol amine series of emulsiers shifts to a

higher bulk concentration. Since the alkyl tail hydrophilic head of the emulsier tested here is different, it is evident that the head group polarity and the hydrophopicity of the alkyl chain play a strong role in the micellization and adsorption processes. The lower the CMC of an emulsier enhances its performs as emulsifying agent. From the data obtained in Table 2, it was found that the CMC increased by the degree of estrication with oleic acid in the two groups of emulsiers; glycerol (I and II) or triethanolamine derivatives (IV and VI). In this case the surface tension was measured in gas-oil. From the obtained results, it was found that the decrease in HLB increases the CMC because in the emulsiers IIII, the hydrophobes were mono-, di-, and trioleate groups. The increase of hydrophobe branch leads to increase the solubility of the emulsier in the oil phase, therefore the CMC increased. This behavior has been seemed also for the second series (IVVI). By inspection the data of Table 2, it was found that, the decrease of HLB and increases the Amin as a result of the increase hydrophopic tail. These results reected on the data of Cmax, which decreased by decreasing of HLB. The Cmax and Amin were calculated as:   1 dr Cmax T Rt d ln c Amin 1016 CN

Whereas, R is the gas constant in Joul, d is the surface tension at 25 C, C is the surfactant concentration and N is the Avogadros number. The surface tension decreased from 40 mNm1 (gas-oil) to 31 and 29 mNm1 against the glycerol monooleats (I)

TABLE 1 General characterization of the investigated emulsiers Elemental analysis

Primary emulsier (Ex) HO-CH2-CHOH-CH2CO2-CH17H33 CH17H33CO2CHOHCH2CO2CH17H33 C17H33CO2CH(CH2CO2C17H33)2 [HO-(CH2)2]2N(CH2)2CO2 C17H33 HO-(CH2)2N[(CH2)2 CO2C17H33]2 N[(CH2)2CO2C17H33]3 n.a F1 F2 F3 F4 F5 F6 Fc 356 606 885 328 678 942 n.a. 69.9 74.5 74.8 69 73.8 75.7 n.a. 70.74 75.19 75.69 69.4 74.34 76.45 n.a. 11.2 11.3 11.1 11.52 11.81 11.92 n.a.

Chemical strcuture

C% H% N% Oil mud formulation M. Wt. Found Calc. Found Calc. Found Calc. 11.3 11.6 11.03 11.65 11.74 11.87 n.a. 3.9 1.9 1.2 n.a. 4.2 2.06 1.48 n.a.

Glycerolmonooleate (I) Glyceroldioleate (II) Glyceroltrioleate (III) Triethanolamine monooleate (IV) Triethanolamine dioleate (V) Triethanolamine trioleate (VI) Envermol, commercial sample (PEc)

n.a. not available.

1083 TABLE 2 Surface and thermodynamic properties of primary emulsier HLB 6.7 4.4 3.9 6.3 5.9 4.9 0.016 0.038 0.049 0.011 0.020 0.045 31 29 34 29 26 31 CMC 103, (mol dm3) rcmc, (mNm1) Pcmc (mNm1) 7 9 4 9 12 7 Amin (nm2) 61.5 66.4 79.1 47.4 48.8 53.6 Cmax X 1010 (cm2) 2.7 2.5 2.1 3.5 3.4 3.1 DGad, (Kj mol1) 27.6 25.6 24.8 28.6 27.2 25.0 ceq. int (mNm1) 0.11 0.01 0.55 0.14 0.02 0.78

Emulsier code

I II III IV V VI

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and glycerol dioleate (II), respectively, then it increased again with the glycerol trioleate (III) [34 mNm1]. This behavior also was noticed with triethanol amine mono, di, and trioleate (r 29, 26, and 31 mNm1, respectively). This may be explained as; in emulsiers (I) and (IV) one tail hydrophope and the two hydrophils terminate by two hydroxyl group. In this case the structure is look like surfactant structure (head and tail). In the case of (II) and (V), the surfactant molecule has tow hydrophope tails and one terminal hydrophil OH group. In this case the emulsier molecule is look like to gemmini surfactant molecule (excellent surfactant model), so that these surfactants pronounced a maximum reduction in the surface tension. But in the case of (III) and (VI) the molecule is completely surrounded by three hydrophope and the hydrophil is not terminal but may be concentrate on the carbonyl group in (III) or carbonyl and nitrogen atom in (VI). This structure may be deactivates the molecule to adsorb regularly on the surface to reduce the surface tension. This observation was noticed also for the equilibrium interfacial tension (ceq.int), the Amin increased by increasing of hydrophope branch which increases the molecular weight of the emulsier molecule. As can be seen, the Gibbs free energy of adsorption DGad, also varies strongly with the variation of HLB value of the used emulsiers. The DGad, increased with decreasing of HLB. The increasing of the negative value of DGad with increasing of HLB value in its turn indicates that a higher degree of interface stabilization is achieved with increasing HLB value in the water-in-oil emulsion case. This can be accounted for the fact that owing to enhance the degree of hydrophobic interactions with decreasing HLB value, the adsorption at the given w=o interface decreases with decreasing HLB value. The more negative the DGad the greater the degree of interfacial adsorption. The DGad was calculated by: DGad DGmic 0:6032 Amin pCMC Where; DGmic RT lin CMC pCMC p of solvent (40 mNm1) p surfactant (measured). The greater the degree of interfacial adsorption, the greater the emulsifying effect. The interfacial adsorption Cmax, also referred to as surface excess concentration. The value of Cmax imply that all emulsiers examined here tend to adsorb strongly at the given interface, and that the degree of adsorption enhanced with increasing the HLB value of the emulsiers. The equilibrium interfacial tension, (ceq.int) also varied strongly with HLB value of the surfactant. As shown in Table 2, a higher degree of reduction of (ceq.int) is achieved with decreasing HLB value from 6.7 to 4.4 then the value increased against HLB 3.9 for the different glycerol derivatives (I), (II), and (III) respectively.

FIG. 3. Viscosity shear rate curves for mud formulations obtained


with 2% PE 10:90 water oil ratio at 25 C.

The same behavior had been also seen for the triethanol amine oleate derivatives as cleared in Table 2. This is a further indication that given the hydrophope tail branch is strongly related to adsorb the surfactants molecule on the w=o interface and to reduce the interfacial tension. Rheoloigy Characterization of Oil Base Emulsions The viscosity concepts were rstly announced by Isaac Newton. It is synonymous with internal friction and a measure of the resistance to the ow. The force per unit area, s (donated as a required shear stress). The gradient producing the motion is proportional to the viscosity gradient (denoted as shear rate coefcient dd=dt). The constant of proportionality, g, is called the viscosity coefcient, that is, sg dd dt

FIG. 4. Flow curves of mud formulations prepared with PEs.

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TABLE 3 Viscosity Shear rate and shear stress of mud emulsions with 2% PE and 10:90 water oil ratios at different temperature 25 C Temp.  C Fc F1 F2 F3 F4 F5 F6 gd 75 70 78 90 65 70 85 sB 42.4 39.5 40.3 52.2 39.5 40.1 55.0 gd 74 69 77 85 64 69 82 35 C sB 40.4 39.3 40.2 50.2 36.3 40.1 52.1 gd 73 69 76 87 63 68 80 45 C sB 35.7 38.4 33.9 48.2 35.2 38.1 45.6 gd 72 68 74 86 62 66 79 55 C sB 33.6 30.2 28.8 44.2 35.9 35.2 40 gd 70 67 74 84 63 65 78 65 C sB 30.6 31.3 30.8 35.2 30.6 31.6 35.1 Dg= C 0.13 0.10 0.10 0.17 0.10 0.13 0.18 DsB= C 0.29 0.21 0.24 0.43 0.22 0.21 0.37

A uid is said to be Newtonian, if the viscosity independent on the shear rate. The viscosity decreases with increasing the shear rate, which is called shear thinning or pseudo- plasticity, while the increasing of the viscosity with shear rate is called shear thickening or dilatancy. In this work, the shear stress and the dynamic viscosity against the shear rate were measured at different temperatures (25 C to 65 C), different primary emulsier concentrations (1, 2, and 3%), and different water content (5, 10, 20%). The emulsiers were compared using measurements of the ow properties of the model emulsions (Fc). Figures 3 and 4 show the rheolograms (viscosity and shear stress against shear rate plots) of the emulsion systems at different values of the dispersed phase concentration and HLB of the emulsier used. The shape of the hysteresis loop is characteristic for the viscoelastic uids e.g. concentrated emulsions.[11,12] From the data illustrated in Figures 3 and 4, it was found that the rheological behavior of the oil base mud (w=o) emulsion is the data observed almost Newtonian nearly above 150 D.sec-1 and the non-Newtonian behavior appears before this limit. The increasing tendency toward Newtonian behavior was obtained by increasing the applied temperature for the oil mud. The dynamic viscosities, gd, and Bingham yield values, sB, for the six complete oil base mud emulsions (F1 to F6) and the control sample (Fc) at different temperatures (25 C to 65 C), 2% and 10=90 w=o are listed in Table 3 and illustrated in Figure 3. F1, F2, F4, and F5 exhibited dynamic viscosity closed to that obtained by the control sample (75 mPa.s). But the F3 and F6 exhibited (90 and 85 mPas), respectively at 25 C. By increasing the temperature from 25 C to 65 C, the viscosity temperature coefcient (Dg= C) decreasing for the F1, F2, F4, and F5 was 0.08, 0.10, 0.1, and 0.13 was nearly close to Fc. Meanwhile, the other samples F3 and F6 recorded Dg= C higher than the former samples (0.17 and 0.18). This means that the formulations which used the primary emulsiers I, II, IV, and V are most tolerance to the increase of the temperature program than the others. This is a good property of the oil

base mud. Otherwise, the Dsb= C for the F1, F2, F4, and F5 were 0.21, 0.24, 0.22, and 0.21, respectively. They were also closely with the Dsb obtained by the Fc (0.29). But the other samples F3 and F6 recorded Dsb= C 0.43 and 0.37. This mean that the former formulations are most tolerance to the decrease of yield value of the mud emulsions than the others. The formulations F1, F2, F4, and F5 were selected as the best formulations to investigate the effect of the primary emulsiers concentration on the mud property. The chemical structure of the corresponding primary emulsier was mono- and dioleate of glycerol and monoand dioleate of triethanol amine, respectively. In spite of the trioleate esters gave a late results comparing with the former mono- or dioleate esters. This means that the chemical structure plays a central role to stabilize and enhance the rheological properties of the oil base mud formulations. Thixotropy of the Oil Base Mud Generally, the most drilling uids contain clays that exhibit thixotropic properties. Thixotropic of uid from gels upon in quiescence static condition and region their uidity under dynamic conditions. The shear- or gel-strength of drilling uids in a measurement of the minimum shearing stress necessary to produce slip-wise movement of the uid.

TABLE 4 Thixotropy for mud complete emulsion formulations at 2% PE and (10=90) w=o ratio Temp.  C 25 35 45 55 65 Fc 1 1 0 0 0 F1 0 0 0 0 0 F2 0 0 0 0 0 F3 1 1 1 1 1 F4 0 0 0 0 0 F5 0 0 0 0 0 F6 1 1 1 1 1

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TABLE 5 Gel strength for mud formulation at 2% PE and (10=90) w=o ratio Fc F1 F2 F3 F4 F5 F6

Temp,  C 10 sec 10 min 10 sec 10 min 10 sec 10 min 10 sec 10 min 10 sec 10 min 10 sec 10 min 10 sec 10 min 25 35 45 55 65 8 8 7 7 7 8 8 7 7 6 9 9 8 8 8 9 9 8 8 7 8 8 7 7 6 8 8 6 6 6 12 11 10 10 9 12 11 9 8 7 9 9 6 6 6 9 9 6 6 6 9 9 8 8 7 9 9 8 8 7 14 14 13 12 11 14 13 12 11 10

The data listed in Table 4 clear the thrixotropy of the prepared six oil base mud formulations. From the represented data in Table 4, it was found that F1, F2, F4, and F5 have not thixotropy, while the formulations F3 and F6 exhibited thixothropy along the term of temperature (25 C to 65 C). On the other hand, the control sample (Fc), F3 and F6 exhibited a thixotropy at two temperatures 25 C and 35 C, but they recorded no thixotrpy at higher temperature (45 C to 65 C). This behavior means that there are four emulsiers in the oil base mud (F1, F2, F4, and F5 are time- independent viscosity. It was also found that Fc, F3 and F6 have thixotropy and are timedependant viscosity at low temperatures (25 C and 45 C), then their behavior changed at high temperature (55 C to 65 C), this means that they are time- independent viscosity at high temperature. By analysis the data in Table 4, it was found that the mono and diester of glycerol (F1 and F2) and of triethanol amine (F4 and F5), are time-independent materials especially in the oil base mud formulation (no thixatropy obtained). This means that, these primary emulsiers can be used successfully in the oil base mud at high range of applied temperatures. Meanwhile, the emulsiers (III) glycerol trioleate ester, and (VI) triethanol amine monooleate esters are time dependent at low temperature (25 C and 35 C) but at temperatures (45 C to 65 C) exhibited a non-thixotropy behavior. At the same time, F3 and F6 were nearly closed with the control sample Fc. Regarding to the chemical structure and the thixotropy behavior, the emulsiers can be ranked in the order of the best behavior as, I, II, IV, and V > III, VI corresponding to the oil base mud, F1, F2, F4, and F5 > F3 and F6, respectively. Gel Strength of the Oil Base Mud The data in Table 5 reveal the gel-strength for the complete emulsion formulation (oil base mud) at different temperatures. From the data listed in Table 5, it can be concluded that the six investigated formulations are having gel strength greater than the control sample (Fc). In general, the increasing of the temperature leads to decrease the gel-strength for all the investigated formulations (oil base mud).

Table 6 shows the stability the mud formulations expressed by Gel strength=1=T after 10 seconds and 10 minuets. By inspection the presented data in Table 6, it can be concluded that the maximum stability of the oil base mud may be exhibited emulsiers I, II, IV and V corresponding to the formulations F1, F2, F4, and F5. Otherwise, the F3 and F6 exhibited the lowest stability. On the other hand, this nding may be justied by the emulsion droplet size (mm) as shown in Table 6. The droplet size of the internal phase of emulsion plays an important role in the stability of this emulsion. The low droplet sizes were obtained from F1, F2, F4, F5, and Fc (4.2, 3.1, 4.6, 3.2, and 3.5 mm), respectively. These formulations exhibited the highest stability. The formulations F3 and F6 gave droplet size 6.3 and 8.3 mm, respectively. These formulations pronounced the lowest emulsion stability. The concentration effect of the primary emulsier on the stability and droplet size of mud emulsion is shown in Table 7. From the obtained data, it was found that the stability (expressed by G=t1) increases by increasing of PE concentrations. The stability increased with decreasing the droplet size of emulsion. The 2% PE exhibited maximum stability and minimum droplet size. So that, 2% PE is the most effective concentration on the stability and the emulsions droplet size of mud emulsion. TABLE 6 Stability of mud formulations expressed by GS=(1=T) and the average droplet size during 90 days at 2% PE GS=1=T Formulations F1 F2 F3 F4 F5 F6 Fc 10 sec 2.7 2.5 6 3.5 3.2 8 2.7 10 min 3.1 3.2 7 4 4.5 8.5 3.5 Droplet size (mm) 4.2 3.1 6.3 4.6 3.2 8.3 3.5

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TABLE 7 Relation of G=(1=T) for F5 at different concentrations and the average droplet size during 90 days PE Conc. 1% 2% 3% 10 sec 6.4 3.2 4.3 10 min 10.2 4.5 7 Droplet size (mm) 6.3 3.2 3.4

Filtration Losses of the Base Mud The effect of ltration on oil base mud was shown in Table 8 for the six investigated formulations and the control sample (Fc). The data show that the F1, F2, F4, and F5 exhibited 5 ml ltrate at high pressure and temperature (500 psi and 200 F) and 2% primary emulsier, respectively. Meanwhile, the ltration loss of the control sample was 9 ml. But, the formulations F3 and F6 exhibited ltration loss 10 and 11 ml at 2% emulsier concentration and 10% water in oil emulsion. This means that the formulations (F1, F2, F4, and F5) are greater than the formulations (F3 and F6). This is the obvious evident that the derived emulsiers from the locally materials can be used as good primary emulsiers in the formulation of oil base mud. This means also that there are a direct proportion relationship between the stability of the oil base mud formulations and their ltration loss. The effect of PE concentration on the ltration loss is clearly from the same Table 8. From the obtained data, it was found that the ltration loss increased at 1 and 3% PE. But the optimum loss was exhibited at 2% PE. This means that at 2% PE, the maximum stability of the emulsion was exhibited so that, at which may be the droplet size of the emulsion particles are nearly the same size. The ordered adsorption of the PE molecules around the droplet makes it more regular size and further the stability increases. Therefore, the distance between the pores decreases leading to decrease the ltration loss. The low or high concentration of the PE may enhance the coalescence properties of the emulsion particles and the destabilization may be obtained quickly, therefore the ltration losses increased. On increasing the dispersed phase concentration of emulsion, the viscosity was found to increase in all the TABLE 8 Filtration loss, [ml] for the mud formulations at different PE concentrations and 10:90 water oil ratio PE conc. 1% 2% 3% FC 9 6 6 F1 5.5 5 5.5 F2 5.5 5 5.5 F3 10 8 9 F4 7 5 5.5 F5 5 5 5.5 F6 11 9 10

FIG. 5. Viscosity shear rate curves for F5, Fc at 2% PE and different water: oil ratios.

FIG. 6. Pesidoplatic behavior of (a) Fc, F2, F5, and (b) F3 and F6 at
2% PE concentration and 10:90 water oil ratio.

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TABLE 9 Filtration loss, [ml] for the mud formulations at different water content Water content, % 5 10 20 Filtration loss, [ml] FC 8 6 7 F1 6 5 5.5 F2 6.5 5 5.5 F3 9 8 9.5 F4 7.5 5 6.5 F5 6.5 5 7 F6 10 9 10.5

emulsion systems studied as shown in Figure 5. When log viscosity is plotted against log shear rate, the resulting curve has a shape similar to that for pseudoplastic ow and shear thinning as shown in Figure 6b for the mud emulsions F6 and F3. But the plots in Figure 6a show pesudoplastic ow without shear thinning. For the control sample (Fc) and the tested mud emulsions (F2 and F5). The effect of water content on the ltration loss for F1, F2, F4, and F5 was remarked also in Table 9. From the data presented in this table, the increasing of water content (5% to 20% water) leads to increase the ltration loss. This may be due to decrease the internal distance between the droplets, which leads to increase of the water coalescence which followed by deformation of the emulsion. Some investigators (ref) found that as the water content in the emulsion increases, the distance between the water droplets decreases. This leads to adjust themselves to regular shape of pores, followed by decrease in the ltration loss. In this study at 10% water, the best results was obtained, but when the concentration of water in the oil mud increased to 20% the distance between the droplets

FIG. 8. The relationship between viscosity of mud emulsions and HLB of PE; at 25 C, (a) HLB-g at shear rate 64 s1 and (b) HLB-sB.

FIG. 7.

Effect of temperature on viscosity for F5 evaluated for different shear rates (D.s1) 2% PE and 10:90 water oil ratio.

FIG. 9. Effect of PE concentratin on (a) gd and (b) sB for F5.

OIL BASE MUD. PART I

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decrease and adjusting themselves to the irregular shape of the pores, which leads to increase the ltration loss. Effect of Temperature on the Property of Oil Base Mud The relation between viscosity and shear rates at different temperatures is shown in Figure 7. From the shown plots, it can be concluded that the increase of shear rate and temperature decrease the viscosity. The obtained relation is following Arrhenius-type relationship. The relationship between viscosity and shear rate versus HLB properties of the synthesized emulsiers is shown in Figures 8a and 8b at shear rate was 64 s1. A decrease of emulsion viscosity with increase of HLB is shown in Figure 8a. But the same decrease was seen against the shear stress in Figure 8b for HLBs (3.9, 4.4, and 4.9) and the curve became steady with HLBs (5.9, 6.3, and 6.7). Figure 9a shows the effect of temperature on the viscosity of the emulsion and Figure 9b shows the effect of temperature on the shear stress for F5 at different concentrations of PE with water content. An increase in temperature

evidently decreases the viscosity signicantly. The viscosity and shear stress versus the temperature data followed on Arrhenius- type relationship. The increase of PE concentration increases the viscosity and shear stress. The effect of temperature after 10 seconds and 10 minutes for the prepared emulsions on gel strength is shown in Figures 10a and 10b. The effect of temperature on the concentration is shown in Figures 11a and b. the plots in Figures 10 and 11 are following also Arrhenius-type relationship. By inspection of Figures 10a and 10b, it was found that the F1, F2, F4, and F5 have a better results than of Fc. Emulsion Stability The mud emulsion stability was expressed by gel strength against HLB, ceq.int, Amin and DGad by inspection the plots in Figures 12a through 12d. It was found that, the maximum stability of mud emulsions was obtained at HLB 5.9 and 6.7 (F5 and F1). The same results were exhibited on plots of mud stability against Amin, DGad, and ceq.int. This nding may be used to evaluate and classify the stability of mud emulsions formulations. Also, it can be concluded that the stability of mud emulsion is strongly related to the surface active properties of the used primary emulsier (PE).

FIG. 10. Gel strength 1=T relationship; (a) after 10 seconds and (b) after 10 minutes.

FIG. 11.

Effect of PE concentration on gel strength for F5 (a) after 10 seionds and (b) after 10 mmutes.

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FIG. 12. REFERENCES

Mud stability [gel strength=(1=T)] against (a) HLB; (b) Amin; (c) DGad and (d) ceq.

int.

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[15] Goddard, E.D. (1985) J. Colloid Surf., 13: 87103. [16] Besra, L., Roy, S.K., and Ay, P. (2002) Int. J. Miner. Process, 66: 203232. [17] Sjoblom, J., Aske, N., Brandal, O., Johnsen, T.E., and Kallevik, H. (2003) Colloid Interf. Sci., 100: 399473. [18] Angle, C.W. (2001) In Encyclopedic Handbook of Emulsion Technology, edited by J. Sjoblom; New York: Marcel Dekker, chap. 24. [19] Ezzat, A.M. and Al-Buraik, K.A. (1973) Society of Petroleum Engineers (SPE) R. Chardsan; TX, USA, pp. 353361. [20] Hoffman, H. (1994) Viscoelastic Surfactant Solution; Washington, DC: American Chemical Society. [21] Barry, B.V. (1974) Rheology of Pharmaceutical and Cosmetics Semisolids; London: Academic Press. [22] Steven, C.C. (1957) J. Am. Oil Chem. Soc., 34: 181185. [23] Mounts, T.L., Worner, K., and Heating, A. J. (1978) J. Am. Oil Chem. Soc., 55(1): 277. [24] Markley, K.S. (1961) Fatty Acids, Part 2; New York: Wiley Interscience, p. 757. [25] Hoffman, H. and Ulbricht, W. (1997) Viscoelastic Surfactant Solutions; New York: Dekker. [26] Tadros, T.F. (1993) In Fundamental Principles of Emulsion Rheology and their Application, First World Congress on Emulsion; New York: Marcel Dekker; vol. 4, pp. 237265. [27] Pal, R. (1997) Chem. Eng., 67: 3744. [28] Grifn, W.C. and Drummond, J. (1949) J. Soc. Cosmet, Chem., 311326. [29] Kamogawa, K., Akatsuka, H., Matsumoto, M., Yokoyama, S., Sakai, T., Sakai, H., and Abe, M. (2001) Colloids and Surf. A, 180: 4153.

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