1264
Ind. Eng. Chem. R e s . 1989,28, 1264-1266
J . Am. Oil Chem. SOC. 1971a,48, 21. Dejarlais, W. J.; G a t , L. E. (11)Conjugation of Polyunsaturated Fats: Activity of Some Group VI11 Metal Compounds. J. Am. Oil Chem. SOC.1971b,48, 157. Deshpande, V. M.; Gadkari, R. G.; Narasimhan, C. S.; Mukesh, D. Studies on Kinetics of Catalytic Isomerization of Methyl Lino1985,62, 734. leate. J. Am. Oil Chem. SOC. Koritala, S.; Scholfield, C. R. Selective Hydrogenation with Copper Catalysts: (I) Isolation and Identification of Isomers formed during Hydrogenation of Linoleate. J.Am. Oil Chem. SOC.1970a, 47, 262. Koritala, S.; Butterfield, R. 0.; Dutton, H. I. Selective Hydrogenation with Copper Catalysts: (11) Kinetics. J. Am. Oil Chem. SOC. 1970b,47, 266. Mukesh, D.; Narasimhan, C. S.; Gadkari, R. G.; Deshpande, V. M. Kinetics and Mathematical Modeling of Isomerization of Methyl Linoleate on Ruthenium Catalyst. 1. Conjugation and Hydrogenation. Ind. Eng. Chem. Prod. Res. Dev. 1985,24, 318. Mukesh, D.; Narasimhan, C. S.; Deshpande, V. M.; Ramnarayan, K. Isomerization of Methyl Linoleate on Supported RutheniumNickel Catalyst, Ind. Eng. Chem. Res. 1988,27, 409. Narasimhan, C. S.; Mukesh, D.; Deshpande, V. M.; Gadkari, R. G. A Novel Process for the Production of Conjugated Compounds from Vegetable Oils. IEL Ltd., Indian Patent Appln. 417/ CALl85, 1985.
Narashimhan, S.; Mukesh, D.; Gadkari, R.; Deshpande, V. M. Kinetics and Mathematical Modeling of Isomerization of Methyl Linoleate on Ruthenium Catalyst. 2. Conjugation and Polymerization. Ind. Eng. Chem. Prod. Res. Deu. 1985b,24, 324. Ucciani, E.; Cecchi, G. Process for Catalytic Conjugation of Double Bonds of Polyunsaturated Fatty Compounds. Institute des Corps Grass, Paris, European Patent 81.430013.3, 1981. Vanderplank, P.; Vanoosten, H. J.; Van Dijk, L. Nonmetallic Pd on Resin: A Very Active & Selective Catalyst for Hydrogenation of 1979,56, Diunsaturated Fatty Acid Esters. J. Am. Oil Chem. SOC. 45, 50, 54. Zwicky, J. J.; Gut, G. Kinetic Poisoning and Mass Transfer Effects in Liquid Phase Hydrogenations of Phenolic Compounds over Pd Catalyst. Chem. Eng. Sci. 1978,33(10), 1363.
* To whom all correspondence
should be addressed.
Doble Mukesh, Chakravarthula S. Narasimhan' Krishnan Ramnarayan, Vinayak M. Deshpande Alchemie Research Centre
P.O. Box 155, Belapur Road Thane 400601, Maharashtra, India Received f o r review July 25, 1988 Accepted April 4,1989
Characteristic Properties of Cutting Fluid Additives Derived from Undecanoic Acid Several derivatives of undecanoic acid were prepared from w-bromoundecanoic acid and w-aminoundecanoic acid, and their characteristic properties as cutting fluid additives were examined. We have found that triethanolamine salts of undecanoic acid having an ethearic substituent in the w-Dosition demonstrated effective rust-inhibiting and antiwear properties in water-based cutting fliids.
A variety of cutting fluids are used for machine operations. Recently, the use of water-based cutting fluids has been of particular interest (Holmes, 1971). The relationship between the properties of water-soluble cutting fluids and the functional groups of various organic additives has not bee reported in detail. The authors have previously shown that epoxides of unsaturated fatty acids have excellent properties as antirust additives for water-soluble cutting fluids (Watanabe et al., 1988). In this work, we examined the antirust properties and lubricity characteristics of various derivatives of undecanoic acid. This communicationwill describe our recent evaluation of these new additives for use in water-soluble cutting fluids.
Experimental Section Preparation of Various Derivatives of Undecanoic Acid. All derivatives were prepared from w-bromoundecanoic acid and w-aminoundecanoic acid by using popular chemical reactions (Fieser and Fieser, 1967). w-Bromoundecanoic acid and w-aminoundecanoic acid used in this work were commercially available from Atochem Co. Ltd. (France). Test Methods. Aqueous solutions of water (100.0 g), triethanolamine (2.0 g), and a carboxylic acid (1.0g) listed in Table I were used. City water in Japan (Chiba and Osaka) was used for all tests. The same results were obtained in the corrosion and lubricity tests as with distilled water. Corrosion tests with cast iron chips were carried out as follows. Two grams of cast iron chips (JIS G 5501, FC-20) which had been washed with benzene was immersed in a sample solution (5 mL) of cutting fluids in a watch glass. The container was covered. After 10 min, the solution was removed by tilting the watch glass. The rust-preventive
effect (the amount of rust on the cast iron chips) was observed after 24 h. A rating of 10 points corresponded to no appearance of rust. Eight points indicated a little appearance of rust. The coefficients of friction were measured a t 25 "C by a pendulum-type oiliness and friction tester (Shinko Engineering Co., Ltd., Tokyo). The special features are as follows: (i) Use of four falls and a pin made of high-quality steel assures the accuracy of test pieces and prevents fitting errors. High testing load is applicable because of the point contact. Formation of boundary oil film is easily made. (ii) The apparatus is free from friction heat because of the pendulum type. (iii) Measuring is simple but accurate and easily reproducible. The main particulars were as follows: test ball, 3/16-in. (4.75-mm) JIS B 1501 high class; test roller pin, diameter X length 2.0 i.d., (+0 to -0.012) X 30 mm; material, SK 3 (JIS G 4401); hardness, HRC 60-66; cycle of pendulum swing, ca. 4 s; maximum pendulum swing, 0.7 rad; test load (maximum hertz/stress), 15000 kg/cm2; temperature of test oil, room temperature to 300 "C (Nihon Junkatsu Gakkai, 1987). Welding loads (kgf-cm-2)were measured on a Soda-type four-ball lubricating oil testing machine a t 200 rpm. This testing machine and friction tester mentioned above have been officially authorized by the Agency of Industrial Science and Technology of Japan as JIS K 2519 and 2219. The main particulars were as follows: test ball diameter, 3/4-in.steel ball (JIS B 1501) (high class, 1-pm tolerance); revolution of spindle, 150-1500 rpm; temperature of test oil, room temperature to 200 "C; hydraulic cylinder diameter, 80 mm; maximum load on the test ball, 1000 kg; pressure of the hydraulic pump, 0-20 kg/cm2; overall dimensions, 1700 mm (diameter) x 650 mm (width) X 1600 mm (height); weight, 450 kg. The machine is obtained
0888-5885f 8912628-1264$01.50/@ Q 1989 American Chemical Society
Ind. Eng. Chem. Res., Vol. 28, No. 8, 1989 1265 Table I. Cutting Fluid Characterization of Various Derivatives of Undecanoic Acid
R for fatty acid (RC9HlBCOOH)
pH 8.4 8.5 8.6 9.0 8.8 8.8 9.4 9.4 8.9 9.6 8.8 8.0 9.1 8.8 8.5 8.0 8.5 9.0 8.7 8.6 8.7 8.4
NHzb CHSCONH CsHsCONH CH3S02NHb CBHSSO2NHb 2% triethanolamine water only milky emulsionC clear-type soluble oilc chemical grinding fluidsC
9.0 9.4
rust-inhibition testa 24 h 48 h 72 h 7 7 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
10 8
8 7
7 6
7 8.3 9.0 9.6
1 6 8 9
friction coeff
surface tension, dyn/cm
0.101 0.090 0.103 0.140 0.121 0.122 0.113 0.131 0.146 0.145 0.130 0.203 0.131 0.131
42 43 44 45 42 41 39
55
welding load, kgfmcm-' 10 19 16 12 10 11 12 10 12 12
0.105 0.108 0.129 0.104 0.103 0.153 0.117 0.098
39 40 46 53 49 45 41 32 42 31 42 44 45 43
0.157 0.141
42 40
10 11
0.38 0.48 0.13 0.12 0.25
65 72 38 35 58
4 3 12 14 5
12 14 12 15 13 6 16 13 14 17
nAqueous solutions of water (100 parts), sample (1.0 part), and triethanolamine (2.0 parts) were used. The method is a corrosion test with cast iron chips. bThese samples were not dissolved in water. cThese are commercial samples. dNaph is naphthyl.
from Shinko Engineering Co., Ltd. (Tokyo) (Nihon Junkatsu Gakkai, 1987). Surface tensions (dyn/cm) were measured at 25 "C with a Du Nouy tensiometer. Practical tests were performed as follows. The cutting conditions were as follows: machine, band sawing machine; cutting sample, connecting rod S 40C (hardening); cutting velocity, 200 m/min. Cutting fluid A is a mixture of sebacic acid (10 wt %), triethanolamine (20%), and water (70%). Cutting fluid B is a mixture of ll-phenoxyundecanoic acid (11) (10 wt %), triethanolamine (20%), and water (70%). These samples were used as a 5% aqueous solution for testing. The grinding conditions were as follows: machine, surface grinder; peripheral wheel speed, 1800 m/min; raw steel, S-45C; grinding tool, WA-46JV; depth setting, 0.02 mm. Sample C is a mixture of 11-phenoxyundecanoicacid (11) (10 wt % ), triethanolamine (20% 1, and water (70%). Sample D is a mixture of sodium nitrite (lo%), triethanolamine (20%), and water (70%). These samples were diluted 50-fold with water for testing.
Results and Discussion The authors previously reported that 11-((carboxymethy1)thio)undecanoic acid, 10,ll-(dichloromethy1ene)undecanoic acid (Watanabe et al., 1985), and 10,ll-epoxyundecanoic acid (Watanabe et al., 1988) all have excellent properties for rust inhibition. The authors prepared many fatty acid derivatives having a functional group a t the w-position of undecanoic acid. This paper describes the effect of different functional groups in a fatty acid with
respect to their characteristic properties in water-soluble cutting fluids. The derivatives of undecanoic acid were prepared from w-bromoundecanoic acid (I) and o-aminoundecanoic acid by using popular chemical reactions. For example, 11phenoxyundecanoic acid (11) was prepared from the reaction of w-bromoundecanoic acid (I) and sodium phenoxide:
C6H60Na
Br(CH2)&OOH C6H50(CH2)loCOOH I I1 Other derivatives of undecanoic acid were similarly prepared. Aqueous solutions of triethanolamine salts of these fatty acid derivatives were evaluated as cutting fluid additives, and the results are listed in Table I. We have found that the triethanolamine salts of these fatty acids containing an ether, nitrile, hydroxyl, acetyl, or mercapto group at the w-position have excellent antirust and antiwear properties. Thus, aqueous solutions of the salt from triethanolamine (2%) and compound I1 (1%)demonstrated excellent corrosion resistance in a test with cast iron chips. The load capacity of this solution was about 12 kgf.cm-2 a t 200 rpm. The load capacity should be as high as possible, a desirable value being more than 10 kgf-cm-2. These new additives described above for water-based cutting fluids were not previously known. Some practical cutting tests with these water-based fluids provided the following results. By use of a cutting fluid containing 11-phenoxyundecanoic acid (11) (sample B), the number of abrasive cut-off pieces was about 25000. However, by use of a cutting fluid (sample A) containing
Ind. Eng. Chem. Res. 1989, 28, 1266
1266
sebacic acid and no compound 11, the number of abrasive cut-off pieces was only 10000. By use of our new griding fluid coolant (sample C, compound 11), loading did not occur after 20 min. However, by use of a sodium nitrite solution system (sample D), loading occurred after 14 min.
Watanabe, S.;Fujita, T.; Sakamoto, M. Epoxides of Unsaturated Fatty Acids as Anti-rust Additives in Water-Based Cutting Fluids. J . Am. Oil Chem. Sac. 1988,65, 1311-1312.
* To whom correspondence
should be addressed.
Chiba University. t NEOS Center Research.
Literature Cited
S. Watanabe,*st T. Fujita,’ M. Sakamoto’ I. Shirakawa? H. Kawaharaf
Fieser, M.; Fieser, L. Reagents for Organic Synthesis; Wiley-Interscience: New York, 1967; Vol. I. Holmes, P. M. Factors Affecting the Selection of Cutting Fluids. Ind. Lubr. Tribol. 1971, No. 2, 47-55. Nihon Junkatsu Gakkai Junkatsu Handbook; Yokendo: Tokyo, Japan, 1987; pp 394-400 (this book is written in Japanese. English translation is: Handbook of Lubrication; Society of Japan Lubrication Engineers). Watanabe, S.; Fujita, T.; Yoneshima, T. New Additives Derived from Fatty Acids for Water-Based Cutting Fluids. J. Am. Oil Chem. SOC. 1985, 62, 125-127.
Department of Applied Chemistry Faculty of Engineering Chiba University Yayoicho, Chiba, Japan 260 a n d N E O S Center Research Ohikemachi, Koseicho, Kohgagun Shiga-ken, J a p a n 520-32 Received for review February 21, 1989 Accepted June 19, 1989
CORRESPONDENCE Comments on “Simulation and Optimization of an Industrial Ammonia Reactor” Sir: In a recent paper on the simulation of an industrial ammonia reactor, Elnashaie et al. (1988) used the Wilke effective diffusivity formula (cf. their eq 16) 1 - xi, D: = i = 1-3 (1) n Xi,
c-
in the calculation of the effectiveness factor inside the catalyst particle. However, eq 1 is strictly applicable for the determination of the effective diffusivity of a transferring component, i, in a mixture of stagnant (i.e., nontransferring) components. In the ammonia synthesis process, none of the three components present in the gaseous mixture, N2 (11, Hz(2), and NH, (31, can be considered to have a vanishing flux. Indeed, the ratio of the molar flux of component i, Ni, to the mixture molar flux zi = Ni/(Nl + N 2 + N3) i = 1-3 (2) is determined by the reaction stoichiometry to be =
72;
22
= 3/;
0.15, X i g = 0.65,
X3,
= 0.20
(5)
With the pair diffusivities values (at 298 K and 100 kPa) of
Dlzo= 78,
D13O
= 23,
023’
= 78 mm2/s
(6)
we find from the Wilke formula (eq 1) that
j=1,j#iDjiO
21
XI,
23
= -1
(3)
The appropriate expression for the effective diffusivity of any component with stoichiometrically constrained fluxes can be easily derived from the Maxwell-Stefan diffusion equations (cf. Kubota et al. (1969)):
DIo = 50, Dzo = 78,
D30
= 54 mm2/s
(7)
while from the Kubota et al. formulation (eq 4) we get
Dl0 = 41, DZo= 138, D,O = 43 mm2/s
(8)
In particular, the effective diffusivity of hydrogen is significantly higher because of stoichiometry considerations, and the reaction rates will consequently be altered to a significant extent. It is to be noted that intraparticle diffusion effects are apparently important in ammonia synthesis as witnessed by an effectiveness factor of 0.4 at the entrance to the reactor. We conclude that, for a proper simulation of the ammonia synthesis reactor, the appropriate expression (eq 4) for the effective diffusivity has to be used. Registry No. NH,, 7664-41-7. Literature Cited Elnashaie, S.S.; Abashar, M. E.; Al-Ubaid, A. S. Simulation and Optimization of an Industrial Ammonia Reactor. Znd. Eng. Chem. Res. 1988, 34, 2015-2023. Kubota, H.; Yamanaka, Y.; Dalla Lana, I. G. Effective Diffusivity of Multicomponent Gaseous Reaction Systems. Application to Catalyst Effectiveness Factor. J. Chem. Eng. Jpn. 1969,2, 71-75.
Equation 4 in general will give significantly different values for the effective diffusivity than the Wilke formula (eq 1). To demonstrate this, let us calculate the effective diffusivities by the two formulas at the following compositions:
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0 1989 American Chemical Society
