Di-basic acid as cationic co-polymer surfactants additives for enhancement the rheological properties of water based mud.
The oil industry has used drilling mud or fluids since the beginning of oil well drilling operation for oil and gas. Well drilling operations are carried out using a variety of drilling fluids, some of which are aqueous, some of which are oil and some of which are oil-water emulsions [1-4]. The fluid must have a proper thickness or viscosity to meet the many different criteria required by the drill owner/ operator. The fluid must provide filtration control, the fluid must suspend and transport solid particles to the surface for screening out and disposal, and the fluid must keep suspended solid particles and weighting agent to increase specific gravity of mud [5-10]. The above functions must be satisfactory provided throughout the time that fluid is in the entire length of the drill hole. Since the drill hole can be as much as tens of thousands of feet longs, varying and extreme temperatures are encountered which temperatures changes affect the fluids physical properties and performance. Finally it should be noted that a drilling fluid must perform its various functions not only when the drilling bit is actively encountering the bottom of the borehole, but also at all times and at all locations in the drill stem. A drilling fluid is typically a thixtrophic system; that is it exhibits low viscosity when sheared, such as an agitation or circulation (as by pumping or otherwise). fluid must became thick relatively readily, reaching a sufficient gel strength before suspended materials fall any significant distance and this behavior must be totally reversible at all temperatures encountered. In additional, even when a free flowing liquid, the fluid must retain a sufficiently high viscosity to carry all unwanted particulate matter from the bottom of the hole to the surface [11-15]. One prominent type of water-based mud is the clay-water mud which uses Na-montmorillonite with water to achieve necessary rheological properties. Water-based drilling fluids are generally considered to be more environmentally acceptable and less expensive than oil based mud [16-20]. Na-Monttnorillonite is used in drilling mud due to its ability to form viscoelastic and thixottopy dispersion. Local raw bentonite exhibit high filtration loss and do not develop sufficient viscosity so, they cannot meet the API (30cp minimum viscosity at 600rpm, 15[cm.sup.3] filtration loses and 22 ml swelling index) standards . By alkali activation or by introducing some polymer additives it is possible to upgrade row bentonite to meet the above standards and thus require appropriate activation formulations. This activation typically employs various additives such as inorganic salts like soda ash, Mgo salt, the inorganic salt improves the swelling or viscosity[22-24]. In the oil drilling fluid, the polymer is usually selected to reduce fluid loss, increase cutting carrying capacity serve as emulsifiers and lubricants, especially as shale inhibition additives in water-based mud. Modification of bentonite with polymers (soluble in water) and similar compounds has been studied by different investigators and outstanding rheological behaviors such as viscosity, thixotroply, etc. have been measured. Mechanisms governing activation can be usually advanced as ion exchange, ion adsorption and particle interaction (hetirocogulation) [25-28]. Organic compounds in particle--particular polymers, generally are more effective additives than inorganic salts. Polymeric materials are generally considered useful as viscosifiers agent and water loss additive when dissolved in appropriate solve system, but when drilling at high temperatures the individual polymer chains begin to overlap in order to overcome the difficulties experienced in conventional polymer viscosifiers and rheological control additives in aqueous media .The modifications of Na- montmorillonite with surfactants increase the adsorption capacity. Cationic surfactants are easy to be inter-calated into the clay interlayer space vacations exchange. It has been providing that interaction of cationic surfactants not only changes the surface properties of the clays from hydrophilic to hydrophobic, but also greatly increase the basel spacing of the clay interlayer [29-30]. A novel family of cationic alkyl monomers ie.Polymerizeable moieties, form a large structure in solution and enables the efficient viscosification of aqueous fluids without a need for a moderate or high molecular weight water soluble polymer[31-33]. These monomers have markedly unique and improved solution properties as compared to the conventional water soluble polymers. The main property of these monomers are being a cationic surfactants, so they a achieve solubility and thickening efficiency which make this system, as well as very sensitive to small change in surfactant and polymer concentration. The cationic monomers viscosities are highly expensive to be used and did not control the water loss. Cationic co-polymer surfactants were prepared from di-basic acid to be used as viscosifiers and rheological controlled for water-based mud. Cationic co-polymer surfactants are of low molecular weight so, at high temptations no chain overlap and they have high viscosity and they are capable of forming viscoelastic fluids with water-based mud and also they are less expensive to be used. The use of co-polymer overcome the difficulties of using convention polymer and is less expensive than cationic monomer viscoelastic surfactants.
All chemicals that were used throughout this investigation are of analytical grade and used as they are without more purification.
Preparation of the Co-Polymer through Esterification Reaction:
In a three necked flask equipped with Dean-Stark apparatus succinic acid (1 mole) with triethanolamine (1mole) and/ or (2mole) were reacted in present of (0.02 mol) sulphric acid as a catalyst, xylene as a solvent. The temperature of the reaction was raised slowly up to 50[degrees]C, nitrogen gas was passed in with continuous stirring. The reaction mixture was heated with continuous stirring until a theoretical amount of water was collected. The product was purified by washing with (5%) sodium bicarbonate solution followed by petroleum ether (b.p. 40-60[degrees]C)The product obtained were Triethanolamine Mono-Succinate Ester ([ST.sub.1]) after collecting 18 ml of water and Triethanolamine Di-Succinate Ester ([ST.sub.2]) after collecting 36 ml of water. Elemental analysis ,Infra-red spectrum of the products were carried out by Fourier transform infrared (FTIR) spectrophotometer ATI Mattsonm infinity series TM, Bench top 961 controlled by win first TM V 2.01 software. (Egyptian Petroleum Research Institute) and [H.sup.1]NMR spectra was measured on a Varian GEMINI 200 (200 MHz) (Micro analytical center, Cairo University) for each product.
Determination of surface tension of prepared co-polymer surfactant was carried out using [KRUSSTYPE Kb] tensiometer equipped with platinum--iridium duNouy ring. Doubly distilled water has a surface tension of 37Nn/m at room temperature was used in preparation of sample. Apparent surface tension values were measured about three times for the sample within2 min interval between each reading .
Tests for water-based mud:
a. Mud formulation:
All sample were prepared according to American pet-oleum institute [API RP 13B-1 1997] and oil companies petroleum institute [OCMA specification No. DFCP-4 1983]. Mud was formulated as following:
1-The base component of water based muds was prepared by adding 6% of API bentonite mixed with 500 ml fresh water.
2-The samples were mixed in Hamiltan mixer for 20 minutes and cured overnight.
3- The samples were stirred for 15 minutes before the rheological properties and filtation were measured before adding the viscosifier.
4-0.7 gm of the newly prepared esters [ST.sub.1] [ST.sub.2] and commercial one (R) were separately added to mud batched and stirred for 20 minutes and cured overnight.
5-Each sample was stirred for 5 minutes before the rheological properties and filtration were measured .So we have three mud batches:
[M.sub.R]: Water -based Mud formulated of 6% API bentonite and commercial viscosifier (R).
[MT.sub.1]: Water-based Mud formulated of 6% API bentonite and the newly prepared ester (ST)).
[MT.sub.2]: Water-based Mud formulated of 6% API bentonite and the newly prepared ester ([ST.sub.2]). Rheological prop
Rheological properties of the water-based mud were measured by using chandler engineering laboratory model (API) viscometer Chan 35 Model (3500). Apparent viscosity (AV), plastic viscosity (PV) and yield point (YP) Unit of: PV in centipoises (CP), AV in centipoises (CP) and YP in 1b/100 [ft.sup.2] . of gel strength and Thixotropy:
The gel strength of the water-based muds a measure of the minimum shearing stress necessary to produce slip-wise movement of fluid. Two readings are generally taken (1) after 10 sec (G10 sec) (2) after the mud in the cup has been rested for 10 min (G10 min). Thixotropy of the mud is the difference between the low reading after 10 sec, and 10 min.
Effect of temperature on the rheological properties:
Viscosity of the water-based mud is a function of temperature more than pressure. It is necessary to measure viscosity at elevated bottom hole temperature. This is done by using the viscosity cup heater which is a thermostat-controlled unit for heating the mud sample directly on a viscometer. Filtration properties:
Using Standard filter press fann model 300 multichamper for filtration at 100 psi after 30 minutes.
Density measurements using fann mud balance model 140 .the Density was measured in pounds per gallon (LB/Gal) or pounds per cubic feet (LBs/cubic feet)
RESULTS AND DISCUSSION
Preparation of the Co-Polymer through Esterification Reaction:
The chemical structures of the prepared co-polymer cationic compounds [ST.sub.1] and [ST.sub.2] were confirmed by:
1. Correct Elementary analysis was measured in Micro Analytical center ,Cairo university
2. FTIR spectroscopy
3. [H.sup.1]NMR spectra
Elementary analysis, FTIR spectroscopy, [H.sup.1]NMR analysis confirm that the products are very pure and have molecular structure as shown in Fig. (1)
Elementary analysis showed good coincidence between the calculated and found values of C, H, O and N (%) as shown in Table (1).
FTIR spectroscopy was used to identify the function groups of the prepared co-polymer cationic surfactants. FTIR for ([ST.sub.1]) and ([ST.sub.2]) showed characteristic bands as show in Table (2) and Fig. (2).
The surface tension values were measured for aqueous solutions of prepared cationic surfactants [ST.sub.1] and [ST.sub.2] with different concentration at room temperatures and the data represented in table (3).
Evaluation of the prepared viscosifier:
Evaluation of the prepared co-polymer cationic surfactants as viscosifier and water--loss control agents for water-based mud. The prepared co-polymer cationic surfactants ST and [ST.sub.2] were evaluated as viscosifier and filter loss additives in water-based mud. The mud formulation contains API bentonite (6%) and 0.7 gm of both the new viscosifiers and imported viscosifier [M.sub.R]. The rheological properties at 60.F were illustrated that:
Fig (4) showed that water-based mud heated with cationic co-polymer [ST.sub.1] and [ST.sub.2] were 27.5 and 30 cp and the apparent viscosity of the reference mud was 19 cp.
for [MT.sub.1] and [MT.sub.2] were 20 and 18 cp. while for [M.sub.R] was 15 cp.
for [MT.sub.1] and [MT.sub.2] were 15 and 24 lb/100 [ft.sup.2], where [M.sub.R] was 8 lb/100 [ft.sup.2].
From the above results we can conclude that water-based muds [MT.sub.1] and [MT.sub.2] exhibited rheological properties better than [M.sub.R].
Fig (5): illustrated the results of gel strength for water-based mud [MT.sub.1], [MT.sub.2] compared to [M.sub.R] at 60.F.
G10sec.for| [MT.sub.1] and [MT.sub.2] were 13 lb/100 [ft.sup.2] and for [M.sub.R] it was 5 lb/100 [ft.sup.2].
G10min. it was 13 lb/100 [ft.sup.2]for both [MT.sub.1] and [MT.sub.2] for [M.sub.R] it was 5 lb/100 [ft.sup.2].,So water-based mud [MT.sub.1] and [MT.sub.2] which treated with the new co-polymer [ST.sub.1] and [ST.sub.2] exhibited gel strength higher than [M.sub.R].
Fig (5): illustrated that for [MT.sub.1] and [MT.sub.2] thixotropy were zero lb/100 [ft.sup.2] which was compatible with thixotropy of [M.sub.R], so [MT.sub.1] and [MT.sub.2] mud were stable and can keep their rheological properties for period of time during the drilling operation without change as well as [M.sub.R] mud.
Effect of Temperature on the Rheological Properties of Water-Based Mud:
In our study, the rheological properties of water-based mud changes with increasing temperature ranging between 60.F and 200.F. For water-based mud heated with imported viscosifier ([M.sub.R]); form the data represented in Fig.(6-8) it showed that the apparent viscosity decreased from 19cp to 10cp while the plastic viscosity decreased from 15cp to 7cp and the yield point also changed from 8 lb/100 [ft.sup.2] to 6 lb/100 [ft.sup.2]. Form water-based mud heated with the new viscosifier: [MT.sub.1]: the apparent viscosity changed from 27.5 cp to 18 cp, plastic viscosity changed form 20 cp to 12cp and yield point decrease from 15 lb/100 [ft.sup.2] to 12 lb/100 [ft.sup.2]. [MT.sub.2]: the apparent viscosity changed from 30 cp to 18 cp, the plastic viscosity changed from 18 cp to 10 cp and yield point changed from24 lb/100 [ft.sup.2] to 7 lb/100 [ft.sup.2].
Results of the rheology-temperature relation indicate that the new additives [ST.sub.1] and [ST.sub.2] satisfy the minimum requirements for API specification compared to imported viscosifier [M.sub.R].
Effect of Temperature on Gel Strength:
Mud treated with imported viscosifier ([M.sub.R]) Fig.(9-10) revealed that the gel strength G10 sec. decreased from 5lb/100[ft.sup.2] to 3lb/100[ft.sup.2] after the temperature raised from 60[degrees]F to 200[degrees]F. Also G10 min. decreased from 5lb/100[ft.sup.2] to 3lb/100[ft.sup.2] after 10 mints. Mud treated with the new viscosifier as the temperature raised from 60[degrees]F to 200[degrees]F:
[MT.sub.1]: the gel strength changed from 13lb/100[ft.sup.2] to 9lb/100[ft.sup.2], after 10 sec. as the temperature raised from 60[degrees]F to 200[degrees]F. Also it decreased from 13lb/100[ft.sup.2] to 9lb/100[ft.sup.2] after 10 mints as the temperature raised from 60[degrees]F to 200[degrees]F.
[MT.sub.2]: the gel strength changed from 13lb/100[ft.sup.2] to 5lb/100[ft.sup.2], after 10 sec. as the temperature raised from 60[degrees]F to 200[degrees]F. Also it decreased from 13lb/100[ft.sup.2] to 5lb/100[ft.sup.2] after 10 mints as the temperature raised from 60[degrees]F to 200[degrees]F.
Relationship Between Shear Stress and Shear Rate of Water-Based Mud:
Mud treated with imported viscosifier [M.sub.R]: At 60[degrees]F the value of shear stress decreased from 38 to 5 1b/[ft.sup.2] as the shear rate decreased from 1020 [sec.sup.-1] to 5.1 [sec.sup.-1]. At 120[degrees]F the value of shear stress decreased from 28 to 4 1b/[ft.sup.2] as the shear rate decreased from 1020 [sec.sup.-1] to 5.1 [sec.sup.-1]. At 180[degrees]F the value of shear stress decreased from 20 to 4 1b/[ft.sup.2] as the shear rate decreased from 1020 [sec.sup.-1] to 5.1 [sec.sup.-1]. [MT.sub.1]: At 60[degrees]F the value of shear stress decreased from 55 to 13 1b/[ft.sup.2] as the shear rate decreased from 1020 [sec.sup.-1] to 5.1 [sec.sup.-1]. At 120[degrees]F the value of shear stress decreased from 51 to 12 1b/[ft.sup.2] as the shear rate decreased from 1020 [sec.sup.-1] to 5.1 [sec.sup.-1]. At 180[degrees]F the value of shear stress decreased from 36 to 9 1b/[ft.sup.2] as the shear rate decreased from 1020 sec-1 to 5.1 sec- 1. [MT.sub.2]: At 60[degrees]F the value of shear stress decreased from 60 to 13 1b/[ft.sup.2] as the shear rate decreased from 1020 [sec.sup.-1] to 5.1 [sec.sup.-1]. At 120[degrees]F the value of shear stress decreased from 50 to 9 1b/[ft.sup.2] as the shear rate decreased from 1020 [sec.sup.-1] to 5.1 [sec.sup.-1]. At 180[degrees]F the value of shear stress decreased from 27 to 5 1b/[ft.sup.2] as the shear rate decreased from 1020 [sec.sup.-1] to 5.1 [sec.sup.-1]. fig.(11) was illustrated that The value of shear stress decreased as shear rate decreased at same Temperature.
Effective viscosity of Water-Based Mud:
Plotting viscosity of mud versus the value of shear rate are illustrated if fig.(12). the testing result showed that : the effective viscosity of the mud decreased with increased shear rate, these results are similar to field mud ([M.sub.R]) formulated with the reference mud. From the fig (12) we conclude that: the values of the effective viscosity verses the shear rate of water-based mud treated with the new prepared co-polymer cationic surfactants [ST.sub.1],[ST.sub.2] are extremely shear thining.
Table (4) illustrated pH measurements for water-based mud treated with the new co-polymers [ST.sub.1] and [ST.sub.2] which have high alkalinity pH than [M.sub.R] mud. The density for both water-based mud treated with co-polymer [TS.sub.1], [TS.sub.2] and the reference mud sample [M.sub.R] were the same 8.6 (1b/gal).
As show in Table (4) the stander filter loss at 100 psi after 30 minutes was measured and the corrected filter loss was determined for [MT.sub.1], [MT.sub.2] compared to [M.sub.R]. The results of filtration show that the less filter loss for both of [MT.sub.1] and [MT.sub.2] mud was less than the reference mud sample [M.sub.R].
From the obtained results we can conclude that:
1-The spectroscopic result (FTIR, [H.sup.1]NNMR, elemental microanalysis and molecular weight) for the new prepared co-polymer have been conformed the chemical structure of the co-polymer
2-The new prepared co-polymer [ST.sub.1] and [ST.sub.2] showed a good surface properties
3-The new prepared co- polymers [TS.sub.1] and [TS.sub.2] showed good results when utilized in the formulation of water--based mud as viscosifiers compared to the commercial viscosifier
4-Rheological, filtration properties of the water--based mud treated with the new prepared viscosifier performed a superior results compared to the commercial viscosifier
5-Water- based mud that treated with the new prepared co-polymer TS' and TS2 has a good mud density compared to the commercial water- based mud [M.sub.R].
Received 5 September 2015
Accepted 18 October 2015
Available online 28 October 2015
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(1) Dardir, M.M., (1) M. I. Abdou, (1) S. Ibrahim, (2) M.H. Helal, (2) E.A. El-mwlla and (2) M. Kamal
(1) Production Department- Drilling Fluids Laboratory, Egyptian Petroleum Research Institute (EPRI) p.o 1727 Cairo, Egypt. (2) Chemistry Department, Faculty of Science Helwan University, P.O 11795 Cairo, Egypt
Corresponding Author: Mohamed kamal Hassan, Chemistry Department, Faculty of Science, Helwan University, P.O 11795 Cairo, Egypt;
Table 1: Elemental analysis and molecular weight of prepared co-polymers [ST.sub.1] and [ST.sub.2]. Cpd. Elemental Analysis C% H% N% Found Cal Found Cal Found Cal [ST.sub.1] 47.8 48.19 8.01 7.68 57 5.62 [ST.sub.2] 47.3 48.13 6.5 6.64 3.9 4.01 Cpd. Molecular Weight Found Cal [ST.sub.1] 236.7 249.28 [ST.sub.2] 331 8 349.37 Table 2: FT-IR spectroscopic analysis of prepared co-polymers [ST.sub.1] and [ST.sub.2]. Functional groups FT-IR Bands ([cm.sup.-1]) [ST.sub.1] [ST.sub.2] v OH stretching 3360.31 3402 v C-O stretching 1291.37 1196.02 v C-H sym and C-[H.sub.asym] 2900-2933 2872.52-2944.09 stretching v C= O (ester) stretching 1732.02 1711.85 v COO- stretching 1291.37 1196.02 Table 3: Surface tension and interfacial tension of prepared cationic surfactants [ST.sub.1] and [ST.sub.2]. Surfactants Surface Tension value (mN/m) Interfacial Tension [ST.sub.1] 37 12 [ST.sub.2] 40 23 Table 4: The density, the pH value and stander fluid-loss for the water-based mud [MT.sub.1], [MT.sub.2] compared to [M.sub.R]. pH Density Fluid-loss Filter cake description Mud value (1b/gal) (ml) 10.8 8.6 15 Filter cake thickness [M.sub.R] (mm) =1.4 11.5 8.6 13.5 Filter cake thickness [MT.sub.1] (mm) = 0.9 11.5 8.6 13 Filter cake thickness [MT.sub.2] (mm) = 0.9
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|Author:||Dardir, M.M.; Abdou, M.I.; Ibrahim, S.; Helal, M.H.; mwlla, E.A. El-; Kamal, M.|
|Publication:||Advances in Environmental Biology|
|Date:||Sep 1, 2015|
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