RESEARCH NOTE pubs.acs.org/IECR
A Novel Method of Quantitative Carbon Dioxide for Synthesizing Magnesium Oleate (Linoleate, Isostearate, and Sulfonate) Detergents Yonglei Wang,†,‡ Xamxikamar Mamat,‡ Zhenhong He,‡ and Wumanjiang Eli*,‡ † ‡
Changzhou Institute of Chemistry, Changzhou 213164, People’s Republic of China Xinjiang Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Urumqi 830011, People’s Republic of China ABSTRACT: In order to improve the utilization efficiency of carbon dioxide and calculate the amount of carbon dioxide better, a series of magnesium salt detergents (including magnesium oleate, magnesium linoleate, magnesium isostearate and magnesium sulfonate) was synthesized using a novel method of quantitative carbon dioxide, and this method has the potential for synthesizing more organic acid magnesium salt detergents.
ubricating oils1 3 are often used to protect mechanical surface and to prevent mechanical corrosion, so they should have these properties, including lubrication, cleaning and suspension, etc. However, in the course of operation, oxidative degradation of the hydrocarbon base oil would produce acidic degradation products4 6 that corrode engine parts and reduce the lubricating effect. Therefore, in order to neutralize these acidic products, adding basic lubricant detergent to base oil is necessary. In our previous studies, a series of environmentally friendly oleate detergents7 10 were synthesized by means of traditional synthesis processes. Generally, the traditional synthesis processes11,12 of these lubricant detergents were as follows. First of all, the organic acid reacted with alkaline compounds for neutralization in the mixing state, then the carbonation reaction occurred under the action of some promoters, and the results was these colloidal carbonates were dispersed in diluted oil by surfactant micelle to provide the total base number (TBN) for final lubricant detergent. However, because the synthesis process of lubricant detergent is always a multiphase reaction, it has some disadvantages. First, because entire reactions (including the neutralization reaction and carbonation reaction) are multiphase reactions, there are still some problems of mass transfer, although some promoters (methanol and ammonia, etc.) were added. In particular, the carbonation reaction system is gas, liquid, and solid three-phase reaction, which frequently results in the poor stability of mass transfer, because of many unstable factors (including flow rate of carbon dioxide, amount of carbon dioxide and reaction efficiency of carbon dioxide, etc). Second, because most processes use nonsealed exposure devices during the carbonation reaction, some carbon dioxide that had no time to react were discharged into the air, which induced any carbon dioxide was wasted and the quantitative calculation of carbon dioxide became difficult. In order to overcome these disadvantages of the traditional synthesis process of lubricant detergent, this letter explores a novel method of quantitative carbon dioxide for synthesis of calcium (magnesium) oleate (linoleate, isostearate, and sulfonate) detergents. This method used a sealed autoclave device with exact scale to quantitatively introduce the amount of carbon dioxide required for the carbonation reaction,
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which can reduce the waste of carbon dioxide and improve the utilization efficiency of carbon dioxide. Moreover, this method reduced the unstable factors (such as flow rate of carbon dioxide and amount of carbon dioxide discharged into the air) in carbonation reaction, so it can improve the mass-transfer stability to some extent. Our experimental method was as follows. Measured quantities of organic acid (oleic acid with a purity of 85 wt % and linoleic acid with a purity of 95 wt % were technical grade and all were provided by Xinjiang Fine Chemical Engineering Center; isostearic acid was technical grade and provided by Shanghai Shengyu Chemical Co., Ltd.; alkylbenzene sulfonic acid was technical grade and provided by Dushanzi Petrochemical Co., Ltd.), dilute oil, xylene, methanol, aid-promoter water or ammonia and alkaline compounds (Ca(OH)2 or active-60 MgO) were added to a 100-mL stainless-steel autoclave fitted with a magnetic stirrer. The autoclave then was sealed and the mixing was initiated. The mixture was held at 50 °C for 1 h and then heated to 60 65 °C. An appropriate amount of carbon dioxide was pressured into the autoclave reactor for the carbonation reaction via a DB-80 single-cylinder pump. Finally, the waste residue was removed by centrifugation and filtration, and the solvent (such as xylene, methanol, and water, etc.) was evaporated to obtain the lubricant detergent product. All materials were obtained from commercial sources. The TBN and viscosity of the product then were tested. The TBN is defined as the amount of potassium hydroxide that would be equivalent to 1 g of the material and is expressed in units of miligrams of KOH per gram. It can reflect the capability of the product to neutralize acid and was determined according to ASTM Standard D2896. The viscosity (cSt, 100 °C) of the product determines whether the product is easy to handle and is measured using ASTM Standard D445. Finally, the lubricant detergent product was characterized via Fourier transform infrared spectrometry (BIO-RAD FTS165).
Received: March 7, 2011 Accepted: May 27, 2011 Revised: May 25, 2011 Published: May 27, 2011 8376
dx.doi.org/10.1021/ie200455z | Ind. Eng. Chem. Res. 2011, 50, 8376–8378
Industrial & Engineering Chemistry Research
RESEARCH NOTE
Table 1. Synthesis Results of Calcium Salt Detergent Using a Novel Method of Quantitative Carbon Dioxidea total base number, TBN organic acid
(mg KOH/g)
viscosity (cSt)
8 5
16 10
isostearic acid
12
12
alkylbenzene sulfonic acid
34
18
oleic acid linoleic acid
a
Reaction conditions: organic acid (oleic acid, linoleic acid, isostearic acid, alkylbenzene sulfonic acid), 3.5 g; Ca(OH)2, 4.5 g; xylene, 50 mL; methanol, 3 mL; ammonia, 1.5 mL; pressure of CO2, 3 MPa; and carbonation time, 1 h.
Table 2. Synthesis Results of Medium-Alkaline and High-Alkaline Magnesium Salt Detergents Using a Novel Method of Quantitative Carbon Dioxide alkylbenzene organic acid
oleic acid linoleic acid isostearic acid sulfonic acid
Figure 1. Typical infrared (IR) spectra of magnesium salt lubricant detergents using a novel method of quantitative carbon dioxide: (a) magnesium oleate, (b) magnesium linoleate, (c) magnesium isostearate, and (d) magnesium sulfonate.
Medium-Alkaline Magnesium Salt Detergenta TBN (mg KOH/g) viscosity (cSt)
273
286
292
283
92
88
94
66
High-Alkaline Magnesium Salt Detergentb TBN (mg KOH/g)
358
360
345
339
viscosity (cSt)
102
126
114
92
a
Reaction conditions: organic acid, 3.5 g; active-60 MgO, 2.5 g; xylene, 50 mL; methanol, 3 mL; ammonia, 1.5 mL; CO2 pressure, 3 MPa; carbonation time, 1 h. b Reaction conditions: organic acid, 3.5 g; active60 MgO, 3.5 g; xylene, 50 mL; methanol, 3 mL; ammonia, 1.5 mL; CO2 pressure, 3 MPa; carbonation time, 1 h.
Table 1 shows the synthesis results of calcium salt detergents (calcium oleate detergent, calcium linoleate detergent, calcium isostearate detergent, and calcium sulfonate detergent) using a novel method of quantitative carbon dioxide. It can be observed that the TBN of products all were low, which demonstrated that this method was not suitable for synthesizing calcium salt detergent. Table 2 shows the synthesis results of medium-alkaline and high-alkaline magnesium salt detergents (magnesium oleate detergent, magnesium linoleate detergent, magnesium isostearate detergent, and magnesium sulfonate detergent), using a novel method of quantitative carbon dioxide. It can be observed that the TBN of medium alkaline products all were above 200 mg KOH/g and the TBN of high-alkaline products all were satisfactory (>300 mg KOH/g), which demonstrated that this method was suitable for synthesizing magnesium salt detergents. Figure 1 is the typical infrared spectra of magnesium salt lubricant detergents using a novel method of quantitative carbon dioxide. It can be seen that Figure 1a (magnesium oleate detergent), Figure 1b (magnesium linoleate detergent), Figure 1c (magnesium isostearate detergent), and Figure 1d (magnesium sulfonate detergent) all have the strong absorption bands at 850 860 cm 1 that are the characteristic absorption bands of magnesium carbonate particles, which showed these lubricant detergents all contained amorphous magnesium carbonate, and this is almost the same as that of magnesium salt lubricant detergent using the traditional synthesis method.
In conclusions, this method of quantitative carbon dioxide for the synthesis of magnesium oleate (linoleate, isostearate, and sulfonate) detergents can calculate the amount of carbon dioxide better (by pressure and volume, etc) and improve the utilization efficiency of carbon dioxide. Experimental results demonstrated that this method was not suitable for synthesizing calcium salt detergents (calcium oleate detergent, calcium linoleate detergent, calcium isostearate detergent, and calcium sulfonate detergent), but it was feasible for synthesizing magnesium salt detergents (magnesium oleate detergent, magnesium linoleate detergent, magnesium isostearate detergent, and magnesium sulfonate detergent). For the synthesis of magnesium salt detergent, experiments showed this method was applicable for different organic acid (oleic acid, linoleic acid, isostearic acid, and alkylbenzene sulfonic acid). Based on these results, this method of quantitative carbon dioxide has the potential to become a general method for synthesizing more kinds of organic acid magnesium salt detergents.
’ AUTHOR INFORMATION Corresponding Author
*Tel.: (086) 0991-3836643. Fax: (086) 0991-3835229. E-mail:
[email protected].
’ ACKNOWLEDGMENT The authors would like to thank Prof. Z. S. Hou for fruitful discussions and also acknowledge the Testing Center of Xinjiang Technical Institute of Physics and Chemistry for their technical and instrument support. ’ REFERENCES (1) 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. (2) Erhan, S. Z.; Asadauskas, S. Lubricant Basestocks from Vegetable Oils. Ind. Crop. Prod. 2000, 11, 277. 8377
dx.doi.org/10.1021/ie200455z |Ind. Eng. Chem. Res. 2011, 50, 8376–8378
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