Synthesis of Environmentally Friendly Composite-Metal (Calcium and

Dec 23, 2010 - ... the Chinese Academy of Sciences, Beijing 100049, People's Republic of China ... Graduate University of the Chinese Academy of Scien...
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Synthesis of Environmentally Friendly Composite-Metal (Calcium and Magnesium) Oleate Detergent Yonglei Wang,†,‡ Wumanjiang Eli,*,† Letao Zhang,†,‡ and Guoxing Cai† Xinjiang Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Urumqi Xinjiang 830011, People’s Republic of China, and Graduate UniVersity of the Chinese Academy of Sciences, Beijing 100049, People’s Republic of China

This article presents a method for synthesizing an environmentally friendly composite-metal (calcium and magnesium) oleate detergent, using oleic acid and composite alkaline salts (Ca(OH)2 and active-60 MgO) with high activity and reactivity as raw materials. Reaction conditions, including the molar ratio of composite alkaline salts (Ca(OH)2 and active-60 MgO) to oleic acid, the molar ratio of xylene to composite alkaline salts (Ca(OH)2 and active-60 MgO), the molar ratio of methanol to composite alkaline salts (Ca(OH)2 and active-60 MgO), the molar ratio of ammonia to composite alkaline salts (Ca(OH)2 and active-60 MgO), the molar ratio of injected CO2 to composite alkaline salts (Ca(OH)2 and active-60 MgO), and CO2 rate, were optimized. Using the optimized conditions, a high-alkali composite-metal (calcium and magnesium) oleate solution with a total base number (TBN) of 316 mg KOH/g and an overbased composite-metal (calcium and magnesium) oleate solution with a value of TBN ) 412 mg KOH/g could be obtained. In addition, the relationship between the TBN of the product and the metal content (calcium and magnesium) also was discussed. 1. Introduction Metal-type lubricant detergent has been used for many years as a main lubricant additive. In addition, its metals1-5 mainly have included calcium, magnesium, and barium. However, increasing attention to environmental protection has been a driving force for the elimination of metal barium salt detergent, because of its toxicity. Currently, the calcium metal salt detergent is most commonly used, because of its low cost and high alkalinity, and the use of the magnesium metal salt detergent also has developed rapidly, because of its low ash content, which can meet the requirements of low-ash oil better. With the development of the machinery industry, the demands on the lubricating oil have become more and more rigorous. To meet the demands of high-grade lubricating oil better, some different single-metal-type (calcium or magnesium) detergents were mixed, to improve their comprehensive performance; however, this also resulted in some problems in their mixture process, such as poor compatibility of different metal detergents and high manpower consumption. Compared to a single-metal detergent, a composite-metal (calcium and magnesium) detergent would have much better comprehensive performance. Compared to a simple mixture of the two single-metal detergents, the stability and compatibility of colloidal carbonate of the compositemetal (calcium and magnesium) detergent were better and manpower consumption was low. Until now, few studies have been conducted on the synthesis of composite-metal (calcium and magnesium) detergents, so the synthesis of a compositemetal (calcium and magnesium) detergent has been proposed. A major concern in environmental issues today promoted the environmentally friendliness6-9 of the lubricating oil and its additives to increase gradually. In our previous studies, the environmentally friendly calcium oleate detergent10,11 and magnesium oleate detergent,12,13 using biodegradable oleic acid * To whom correspondence should be addressed. Tel.: (086)09913662347. Fax: (086) 0991-3835229. E-mail: [email protected]. † Xinjiang Technical Institute of Physics and Chemistry. ‡ Graduate University of the Chinese Academy of Sciences.

as material, were studied and satisfactory products were acquired. To meet the requirements of high-grade lubricant oil better, the environmentally friendly composite-metal (calcium and magnesium) oleate detergent was synthesized to improve the comprehensive performance of lubricant detergent further. 2. Experimental Section 2.1. Materials. Oleic acid (with a purity of 85 wt %) and diluent oil (light lubricating oil) were technical grade and provided by Xinjiang Fine Chemical Engineering Center. Methanol (analytical pure, Luoyang Chemical Co., Ltd.), ammonia (analytical pure, Urumqi Tianyue Reagent Co., Ltd.), and active-60 magnesium oxide (MgO) (technical grade, Shanghai Dunhuang Chemical Plant) were used. Xylene and calcium hydroxide (Ca(OH)2) were analytical pure and were provided from Tianjin Zhiyuan Chemical Co., Ltd. Carbon dioxide (CO2) was technical grade and was received from Urumqi Industrial Air Company. All other materials were obtained from commercial sources. 2.2. Analytical Methods. The total base number (abbreviated as TBN and expressed in units of mg KOH/g) and viscosity (given in units of cSt, at 100 °C) were determined according to standard test methods ASTM D2896 and ASTM D445, respectively. The calcium and magnesium contents were measured using a VISTA-PRO-type inductively coupled plasma spectrometer (U.S. Varian, Inc.). 2.3. Synthesis of Environmentally Friendly CompositeMetal (Calcium and Magnesium) Oleate Detergent. Measured quantities of oleic acid and diluent oil were dissolved in xylene and methanol solution. The mixtures of Ca(OH)2 and active-60 MgO then were added for a neutralization reaction and stirring was initiated. When the neutralization reaction was completed, the ammonia was added to the mixture and gaseous CO2 was then introduced into the reactor via the gas flowmeter for a carbonation reaction. Finally, the environmentally friendly composite-metal (calcium and magnesium) oleate detergent was obtained via filtration and evaporation, to remove residue and

10.1021/ie101835v  2011 American Chemical Society Published on Web 12/23/2010

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Scheme 1. Synthesis Mechanism of Composite-Metal (Calcium and Magnesium) Oleate Detergent

the solvent (xylene, methanol, water, etc.). The synthesis mechanism of environmentally friendly composite-metal (calcium and magnesium) oleate detergent is shown in Scheme 1. The feed for the synthesis of high-alkali composite-metal (calcium and magnesium) oleate solution had the following composition: 8.3 g (0.025 mol) of oleic acid (85 wt % purity) + 10 g of diluent oil + 5.5 g (0.075 mol) of Ca(OH)2 + 3.02 g (0.075 mol) of active-60 MgO + 5.8 g (0.18 mol) of methanol + 2.62 g (0.075 mol) of ammonia + 5.3 g (0.12 mol) of CO2 + 80 g (0.75 mol) of xylene. The final product of this synthesis had the following properties: TBN ) 316 mg KOH/g, viscosity ) 64 cSt. The feed for the synthesis of overbased composite-metal (calcium and magnesium) oleate solution had the following composition: 8.3 g (0.025 mol) of oleic acid (85 wt % purity) + 10 g of diluent oil + 9.3 g (0.125 mol) of Ca(OH)2 + 5.04 g (0.125 mol) of active-60 MgO + 9.6 g (0.3 mol) of methanol + 4.38 g (0.125 mol) of ammonia + 8.8 g (0.20 mol) of CO2 + 132.5 g (1.25 mol) of xylene. The final product of this synthesis had the following properties: TBN ) 412 mg KOH/ g, viscosity ) 136 cSt.

3. Results and Discussion 3.1. Molar Ratio of Composite Alkaline Salts (Ca(OH)2 and Active-60 MgO) to Oleic Acid. Generally, as the amount of alkaline salts was increased, the TBN of the product also increased. However, excessive alkaline salts often induced the product to be too viscous to be readily used and the utilization ratio of alkaline salts was low, so they were considered to be waste material. An appropriate molar ratio of alkaline salts (Ca(OH)2 and active-60 MgO) to oleic acid is essential to produce a satisfactory product. The effects of the molar ratio of composite alkaline salts (Ca(OH)2 and active-60 MgO) to oleic acid on both the TBN and viscosity of the compositemetal (calcium and magnesium) oleate detergent are shown in Figure 1. It can be observed that, as the molar ratio of composite alkaline salts (Ca(OH)2 and active-60 MgO) to oleic acid was increased, the TBN and the viscosity of the product each increased gradually. Initially, the TBN of the product increased rapidly as the molar ratio of composite alkaline salts (Ca(OH)2 and active-60 MgO) to oleic acid increased. However, when the molar ratio of composite alkaline salts (Ca(OH)2 and active60 MgO) to oleic acid was>10, the TBN of the product did not

Figure 1. Effects of the molar ratio of composite alkaline salts (Ca(OH)2 and active-60 MgO) to oleic acid on both the total base number (TBN) and viscosity of the composite-metal (calcium and magnesium) oleate detergent. Reaction conditions: molar ratio of Ca(OH)2 to active-60 MgO, 1:1; molar ratio of xylene to composite alkaline salts (Ca(OH)2 and active-60 MgO), 5:1; molar ratio of methanol to composite alkaline salts (Ca(OH)2 and active-60 MgO), 1.2:1; molar ratio of ammonia to composite alkaline salts (Ca(OH)2 and active-60 MgO), 0.5:1; molar ratio of injected CO2 to composite alkaline salts (Ca(OH)2 and active-60 MgO), 0.8:1; and CO2 rate, 60 mL/min.

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Table 1. Relationship between the Molar Ratio of Xylene to Composite Alkaline Salts (Ca(OH)2 and Active-60 MgO) and the Filtration Effecta amount of alkaline salt (mol)

molar ratio of xylene to alkaline salts

filterability

0.15 0.15 0.15 0.2 0.2 0.2 0.25 0.25 0.25 0.3 0.3 0.3

3:1 4:1 5:1 3:1 4:1 5:1 3:1 4:1 5:1 3:1 4:1 5:1

unfilterable poor good unfilterable poor good unfilterable poor good unfilterable poor good

a Reaction conditions: molar ratio of Ca(OH)2 to active-60 MgO, 1:1; molar ratio of methanol to composite alkaline salts (Ca(OH)2 and active-60 MgO), 1.2:1; molar ratio of ammonia to composite alkaline salts (Ca(OH)2 and active-60 MgO), 0.5:1; molar ratio of injected CO2 to composite alkaline salts (Ca(OH)2 and active-60 MgO), 0.8:1; and CO2 rate, 60 mL/min.

increase significantly, but the viscosity of the product increased rapidly so that the product was difficult to be handled. To improve the utilization ratio of alkaline salts and obtain a satisfactory product, a molar ratio of composite alkaline salts (Ca(OH)2 and active-60 MgO) to oleic acid of 6-10 was feasible. 3.2. Molar Ratio of Xylene to Composite Alkaline Salts (Ca(OH)2 and Active-60 MgO). In the synthesis of compositemetal (calcium and magnesium) oleate detergent, the viscosity of the reaction mixture consequently increased rapidly in the carbonation process, which often induced the reaction mixture to become too viscous to be filtered. This phenomenon was different from that of synthesizing calcium oleate detergent and magnesium oleate detergent.10,12,13 This is probably because the micelles of different oleate salts dispersed different colloidal carbonates (namely, the calcium oleate micelle dispersed

colloidal calcium carbonate and colloidal magnesium carbonate; the magnesium oleate micelle dispersed colloidal magnesium carbonate and colloidal calcium carbonate), and the sizes of the different colloidal carbonate particles in the same micelle was different, because of their different physicochemical properties (thus, larger micelle sizes induced increases in the viscosity of the reaction mixture). The problem was solved by correspondingly increasing the amount of xylene, according to the amount of composite alkaline salts (Ca(OH)2 and active-60 MgO). The relationship between the molar ratio of xylene to composite alkaline salts (Ca(OH)2 and active-60 MgO) and the filtration effect is shown in Table 1. It can be seen that, as the molar ratio of xylene to composite alkaline salts (Ca(OH)2 and active60 MgO) was increased, the filtration effect gradually changed for the better. When the molar ratio of xylene to alkaline salts (Ca(OH)2 and active-60 MgO) was 3:1, the reaction mixture with high viscosity was unfilterable. When the molar ratio of xylene to alkaline salts (Ca(OH)2 and active-60 MgO) was 4:1, the reaction mixture with poor filterability also was unsatisfactory. The reaction mixture with good filterability was satisfactory at a 5:1 molar ratio of xylene to alkaline salts (Ca(OH)2 and active-60 MgO). Therefore, the optimal molar ratio of xylene to composite alkaline salts (Ca(OH)2 and active-60 MgO) was chosen to be 5:1. 3.3. Molar Ratio of Methanol to Composite Alkaline Salts (Ca(OH)2 and Active-60 MgO). Methanol14,15 was used as a promoter (to promote the multiphase reaction), and the effects of the molar ratio of methanol to composite alkaline salts (Ca(OH)2 and active-60 MgO) on both the TBN and viscosity of the composite-metal (calcium and magnesium) oleate detergent are shown in Figure 2. It can be seen that the TBN and viscosity of the product initially increased and then decreased as the molar ratio of methanol to composite alkaline salts (Ca(OH)2 and active-60 MgO) was increased. This is probably due to the following factors: on the one hand, the diffusivity of alkaline salts in organic solution increased and make the formation of calcium oleate and magnesium oleate become

Figure 2. Effects of the molar ratio of methanol to composite alkaline salts (Ca(OH)2 and active-60 MgO) on both the TBN and viscosity of the compositemetal (calcium and magnesium) oleate detergent. Reaction conditions: molar ratio of Ca(OH)2 to active-60 MgO, 1:1; molar ratio of composite alkaline salts (Ca(OH)2 and active-60 MgO) to oleic acid, 6:1; molar ratio of xylene to composite alkaline salts (Ca(OH)2 and active-60 MgO), 5:1; molar ratio of ammonia to composite alkaline salts (Ca(OH)2 and active-60 MgO), 0.5:1; molar ratio of injected CO2 to composite alkaline salts (Ca(OH)2 and active-60 MgO), 0.8:1; and CO2 rate, 60 mL/min.

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Figure 3. Effects of the molar ratio of ammonia to composite alkaline salts (Ca(OH)2 and active-60 MgO) on both the TBN and viscosity of the compositemetal (calcium and magnesium) oleate detergent. Reaction conditions: molar ratio of Ca(OH)2 to active-60 MgO, 1:1; molar ratio of composite alkaline salts (Ca(OH)2 and active-60 MgO) to oleic acid, 6:1; molar ratio of xylene to composite alkaline salts (Ca(OH)2 and active-60 MgO), 5:1; molar ratio of methanol to composite alkaline salts (Ca(OH)2 and active-60 MgO), 1.2:1; molar ratio of injected CO2 to composite alkaline salts (Ca(OH)2 and active-60 MgO), 0.8:1; and CO2 rate, 60 mL/min.

easier as the amount of methanol increases, which induced an increase in the TBN of the product; on the other hand, excessive methanol may affect the quality of the micelles and increase the solubility of colloidal carbonate extremely, which induced a decrease in the TBN of the product and the filtration became difficult. Experimental results demonstrated that the molar ratio of methanol to composite alkaline salts (Ca(OH)2 and active60 MgO) should be within certain limits. Therefore, it was feasible that the molar ratio of methanol to composite alkaline salts (Ca(OH)2 and active-60 MgO) be within a range of 0.9-1.2. 3.4. Molar Ratio of Ammonia to Composite Alkaline Salts (Ca(OH)2 and Active-60 MgO). In general, ammonia2,16 often was used as a promoter aid, to synthesize high-TBN product. In the synthesis of calcium oleate detergent, we used water instead of ammonia as a promoter aid, because of the strong metallicity of calcium salts. The effect of ammonia on the TBN of the magnesium oleate detergent was more obvious than that of calcium oleate detergent. This is probably because the metallicity of magnesium salts is weaker than that of calcium salts. In the synthesis of the composite-metal (Ca and Mg) oleate detergent, the effects of molar ratio of ammonia to composite alkaline salts (Ca(OH)2 and active-60 MgO) on both the TBN and viscosity of the composite-metal (calcium and magnesium) oleate detergent are shown in Figure 3. It can be seen that, as the molar ratio of ammonia to composite alkaline salts (Ca(OH)2 and active-60 MgO) was increased, the TBN and viscosity of the product each initially increased and then decreased, but their trends all were less significant than that of synthesizing magnesium oleate detergent.13 This is probably due to the following factors: on the one hand, the metallicity of the metal composite (calcium and magnesium) was stronger than that of magnesium and the induced effect of ammonia on the TBN was not significant; on the other hand, during carbonation, the reaction Ca(OH)2 + CO2 f CaCO3 + H2O produced water, and then the water participated in the reaction MgO + H2O f Mg(OH)2, so, thus, the need for water in the reaction can be

Table 2. Effects of the Molar Ratio of Injected CO2 to Composite Alkaline Salts (Ca(OH)2 and Active-60 MgO) on Both the Total Base Number (TBN) and Viscosity of the Composite-Metal (Calcium and Magnesium) Oleate Detergenta molar ratio of CO2 to alkaline salts

total base number, TBN

viscosity (cSt)

0.2:1 0.4:1 0.6:1 0.8:1 1:1 1.2:1 1.4:1

145 192 294 316 310 306 297

82 64 60 62 58

a Reaction conditions: molar ratio of Ca(OH)2 to active-60 MgO, 1:1; molar ratio of composite alkaline salts (Ca(OH)2 and active-60 MgO) to oleic acid, 6:1; molar ratio of xylene to composite alkaline salts (Ca(OH)2 and active-60 MgO), 5:1; molar ratio of methanol to composite alkaline salts (Ca(OH)2 and active-60 MgO), 1.2:1; molar ratio of ammonia to composite alkaline salts (Ca(OH)2 and active-60 MgO), 0.5:1; and CO2 rate, 60 mL/min.

solved (which was also a reason for the weak effect of ammonia on the TBN of the composite-metal (calcium and magnesium) oleate detergent). The TBN of the product attained its highest value for a molar ratio of ammonia to composite alkaline salts (Ca(OH)2 and active-60 MgO) of 0.5. Therefore, to increase the utilization ratio of ammonia and obtain a product with a satisfactory TBN, the optimal molar ratio of ammonia to alkaline salts (Ca(OH)2 and active-60 MgO) was 0.5. 3.5. Molar Ratio of Injected CO2 to Alkaline Salts (Ca(OH)2 and Active-60 MgO). The appropriate amount of injected CO2 should be in accordance with the amount of composite alkaline salts (Ca(OH)2 and active-60 MgO) to obtain a product with a satisfactory TBN. The effects of the molar ratio of injected CO2 to composite alkaline salts (Ca(OH)2 and active-60 MgO) on both the TBN and viscosity of the composite-metal (calcium and magnesium) oleate detergent are shown in Table 2. It can be observed that, as the molar ratio of injected CO2 to alkaline salts (Ca(OH)2 and active-60 MgO)

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was increased, the TBN of composite-metal (calcium and magnesium) oleate detergent initially increased and then decreased slightly, whereas the viscosity of the product decreased gradually. When the molar ratio of injected CO2 to composite alkaline salts (Ca(OH)2 and active-60 MgO) was 210 mL/min, all products obtained were crystalline material with no fluidity, which was different from that obserevd for the synthesis of calcium oleate detergent and magnesium oleate detergent.10,12,13 The composite-metal (calcium and magnesium) oleate detergent attained the highest TBN value at CO2 rate of 60 mL/min. Therefore, the optimal CO2 rate was chosen to be 60 mL/min. 3.7. Relationship between the TBN of the CompositeMetal (Calcium and Magnesium) Oleate Detergent and Metal Content (Calcium and Magnesium). The TBN of the product and the calcium content, the magnesium content, and sum of the calcium and magnesium contents have some relationship; generally, as the TBN of the product is increased, the total content of metal (the sum of the calcium and magnesium contents) also should increase. The relationship between the TBN of the composite-metal (calcium and magnesium) oleate detergent and metal content (calcium and magnesium) is shown in Table 4. It can be seen that, as the TBN of the product was increased, the calcium content and the sum of the calcium and magnesium contents increased, which was consistent with the theory, whereas the content of magnesium appeared to exhibit a downward trend, which was inconsistent with the theory. This is probably because the poor reaction stability due to multiphase reaction induced the magnesium content to exhibit a downward trend; thereby, the TBN of the product and the magnesium content do not have a stable linear relationship in the experiments, but the sum of the calcium and magnesium contents would increase as the TBN of the product increases. In addition, in composite alkaline salts, the molar ratio of Ca(OH)2 to active-60 MgO always is 1:1; therefore, if their capacity of reactivity was the same and the reaction was stable, the molar ratio of calcium to magnesium in final product also should be close to 1:1. However, because of multiphase reaction and their different physicochemical properties (Ca(OH)2, active-60 MgO), the molar ratio of calcium to magnesium fluctuated dramatically; therefore, the molar ratio

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of Ca(OH)2 to active-60 MgO in composite alkaline salts does not have a corresponding relationship with the molar ratio of calcium content to magnesium content in the final product. 4. Conclusions A high-alkali composite-metal (calcium and magnesium) oleate detergent and an overbased composite-metal (calcium and magnesium) oleate detergent were synthesized using biodegradable oleic acid and composite alkaline salts (Ca(OH)2 and active60 MgO) as raw materials. Compared to a single-metal salt lubricant detergent, the composite-metal (calcium and magnesium) oleate detergent, as an environmentally friendly lubricant additive with more comprehensive performance, can meet the demands of high-grade lubricating oil better. Using the optimized conditions and the feed for the synthesis of high-alkali composite-metal (calcium and magnesium) oleate solution, a high-alkali composite-metal (calcium and magnesium) oleate detergent with a total base number (TBN) of 316 mg KOH/g was obtained. When a product with a higher TBN was required, an overbased composite-metal (calcium and magnesium) oleate detergent with a TBN of 412 mg KOH/g can be obtained, using the feed for the synthesis of an overbased composite-metal (calcium and magnesium) oleate solution. Experiments also showed the changing trend of the TBN of the product and the sum of the calcium and magnesium contents was consistent. Acknowledgment The authors thank H. Liu, Z. He, and F. Zhang for their fruitful discussion; the authors also appreciate the technical and instrument support provided by the Analysis Center of Xinjiang Technical Institute of Physics and Chemistry. Literature Cited (1) Besu¨ergil, B.; Akın, A.; Celik, S. Determination of Synthesis Conditions of Medium, High, and Overbased Alkali Calcium Sulfonate. Ind. Eng. Chem. Res. 2007, 46, 1867. (2) Kocsis, J. A.; Baumann, A. F.; Karn, J. L. Process for Preparing an Overbased Detergent. U.S. Patent 7,238,651, 2007.

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(3) Dickey, C. R.; Williamson, P. M. Overbased Magnesium Sulfonate Process. U.S. Patent 4,192,758, 1980. (4) Swami, K. K.; Gupta, A. A.; Parkash, S.; Mohan Rai, M.; Bhatnagar, A. K. Method for Producing Magnesium Borate Overbased Metallic Detergent and to a Hydrocarbon Composition Containing Said Detergent. U.S. Patent 5,854,182, 1998. (5) Valcho, J. J.; Slama, F. J.; Strukl, J. S.; Park, C. M. Lubricant overbased detergent-dispersants with improved solubility. U.S. Patent 4,614,602, 1986. (6) Haigh, S. D. Fate and Effect of Synthetic Lubricants in Soil: Biodegradation and Effect on Crops in Field Studies. Sci. Total EnViron. 1995, 168, 71. (7) Erhan, S. Z.; Asadauskas, S. Lubricant Basestocks from Vegetable Oils. Ind. Crop. Prod. 2000, 11, 277. (8) Wagner, H.; Luther, R.; Mang, T. Lubricant Base Fluids Based on Renewable Raw Materials: Their Catalytic Manufacture and Modification. Appl. Catal., A 2001, 221, 429. (9) Cermak, S. C.; Isbell, T. A. Physical Properties of Saturated Estolides and Their 2-Ethylhexyl Esters. Ind. Crop Prod. 2002, 16, 119. (10) Wang, Y.; Eli, W.; Liu, Y.; Long, L. Synthesis of Environmentally Friendly Calcium Oleate Detergent. Ind. Eng. Chem. Res. 2008, 47, 8561. (11) Wang, Y.; Eli, W.; Nueraimaiti, A.; Liu, Y. Synthesis and Characterization of Polyol Poly-12-Hydroxy Stearic Acid: Applications in Preparing Environmentally Friendly Overbased Calcium Oleate Detergent. Ind. Eng. Chem. Res. 2009, 48, 3749. (12) Wang, Y.; Eli, W. Synthesis of Biodegradable High-Alkali Magnesium Oleate Detergent. Ind. Eng. Chem. Res. 2010, 49, 2589. (13) Wang, Y.; Eli, W. Synthesis of Environmentally Friendly Overbased Magnesium Oleate Detergent and High Alkaline Dispersant/Magnesium Oleate Mixed Substrate Detergent. Ind. Eng. Chem. Res. 2010, 49, 8902. (14) Galsworthy, J.; Hammond, S.; Hone, D. Oil-soluble Colloidal Additives. Curr. Opin. Colloid Interface Sci. 2000, 5, 274. (15) Hudson, L. K.; Eastoe, J.; Dowding, P. J. Nanotechnology in Action: Overbased Nanodetergents as Lubricant Oil Additives. AdV. Colloid Interface Sci. 2006, 123, 425. (16) Park, C. M.; Richardson, E. E. Preparation of Highly Based Magnesium Sulfonate. U.S. Patent 4,474,710, 1984. (17) Cunningham, I. D.; Courtois, J. P.; Danks, T. N.; Heyes, D. M.; et al. Evidence for a fragmentation mechanism during the formation of calcium carbonate organo-nano-particles. Colloids Surf., A 2007, 301, 184.

ReceiVed for reView September 1, 2010 ReVised manuscript receiVed November 16, 2010 Accepted November 19, 2010 IE101835V