CONTRIBUTED PAPERS

Diffusion-controlled corrosion of agitated vessels containing oil-water emulsions

G.H. Sedahmed, A. Hosny, E. Khamis, S. Kandil and M. El-Maghrabi
The rate of diffusion-controlled corrosion of the copper walls of a cylindrical agitated vessel in acidified FeCl 3 solution was studied by measuring the weight loss and the increase of Cu 2+ concentration with time using iodometry. Variables studied were impeller rotation speed, physical properties of the blank solution and oil concentration in the emulsion. The rate of dissolution of copper was found to increase with increase in impeller speed according to the equation: K = a V0.1, where K is the mass transfer coefficient, a' is a function of oil concentration; V is the linear velocity of the impeller. The mass transfer coefficient of the corrosion process in blank solution was related to other variables by the equation: Sh = 0.000575 Re0.1 Sc0.33, where Sh is the Sherwood number, Re the Reynolds number and Sc Schmidt number. This equation could be used in the design stage, to calculate the thickness of the vessel which covers a certain life span in service under a given set of operating conditions. Agitated vessels suffer less corrosion than oil free solution. The rate of corrosion was found to decrease by an amount ranging from 71 per cent to 97 per cent depending on oil concentration in the emulsion. This behaviour was attributed to the wetting of the vessel wall by a hydrophobic layer of oil which impedes the reaction between acidified FeCl3 and the vessel wall. corrosion behaviour of equipment handling oil-water emulsions. In the petroleum industry, oil-water emulsions are encountered during secondary and tertiary mining of oil from lean wells and during chemical treatment of oil with aqueous solutions containing chemicals which remove objectionable components such as mercaptans, dissolved salts and aromatics from crude oil before distillation[1]. rotation speed of the impeller and physical properties of the solution and oil concentration in the emulsion on the diffusion-controlled corrosion of the wall of the agitated vessel. To this end the study was conducted using the diffusion-controlled dissolution of copper in acidified FeCl 3 . CopperFeCl 3 system has been used as an accelerated technique which simulates practical diffusion-controlled corrosion [3-5].

"Corrosion is frequently controlled by the diffusion of dissolved oxygen"

Chemical treatment of oil is usually carried out in agitated vessels, which suffer from corrosion as a result of the presence of an aqueous phase, containing electrolytes and dissolved oxygen along with the dispersed oil droplets. Under such conditions corrosion of the agitated vessel is frequently controlled by the diffusion of dissolved oxygen on to the wall of the agitated vessel[2]. The object of the present work is to study the effect of different parameters such as

Introduction
Although much work has been done on the corrosion behaviour of metallic structures handling crude oil such as pipelines, storage tanks and heat exchangers, little has been done on the
4 Anti-Corrosion Methods and Materials

The apparatus consisted of 250cm 3 cylindrical glass container of 7ccm diameter and 12cm height. The container was fitted with a stirrer which consisted of a stainless steel shaft and stainless steel impeller at its end. The shaft and impeller were isolated by epoxy resin. The impeller was of the turbine type with three blades. The impeller diameter was 2.5cm, the distance between the impeller and the tank bottom was fixed at 1cm. The ratio between impeller diameter and tank diameter was 1:2.8. The impeller was driven by a variable speed motor having a horse-power of 0.6. The rotation speed, which ranged from 500 to 11,500 rpm, was controlled by a variac and was measured by an optical tachometer. The wall of the container was lined with a cylindrical copper foil of 7cm diameter and 7cm height with purity of 99.99 per cent. The foil back facing the beaker wall was isolated with epoxy resin. Before each run, the container was filled with 100cm3 acidified FeCl 3 solution of the composition 2gm/l Fe3+ N HC1, ranged from 0.01 to 0.5. Corrosion of the copper foil in

Experimental technique

Vol. 42 No. 1, 1995, pp. 4-7, MCB University Press, 0003-5599

acidified FeCl 3 was allowed to take place for 30 minutes at different impeller rotation speeds. The rate of corrosion was determined by the loss in weight method and by measuring the increase of Cu 2+ concentration with time using iodometry[6]. Each run was repeated twice using a fresh solution or a fresh emulsion at 25C. All solutions were prepared from A.R. grade chemi cals and doubly distilled water. Viscosity and density of the solution were measured by an Ostwald viscometer and pyknometer respectively[7]. The oil used to prepare the emulsions was Egyptian Balaeim crude oil having the characteristics shown in Table I. The oil concentration in the emulsion ranged from 3 per cent to 15 per cent. Emulsions were stabilized mechanically by agitation. Rheological measurements showed that all emul sions used were Newtonian in nature. Temperature was 25 1C during experiments. All experiments with oil emulsion were conducted using a blank solution of the composition 2gm Fe 3+ + 0.1 N HCl.

For a batch reactor like that used in the present work, the rate of diffusion con trolled corrosion of the vessel wall in FeCl3 is given by:

which on integration gives: Vs ln C0/C= KAT

(2)

Figure 1 shows that the present data fit equation (2) quite well; the mass transfer coefficient of the corrosion process under different conditions was obtained from the slope of ln C0/C versus t. Figure 2 shows the effect of impeller speed on the mass transfer coefficient of the dissolution of the vessel wall in acidified FeCl 3 at different velocities and at different concentration of HC1 solution. The mass transfer coefficient increases by increasing the impeller speed according to the equation: K= aV0.7 (3) where V is the linear velocity of the impeller (V = r); r is the radius of the impeller; is the angular velocity = 2 rps. The velocity exponent (0.7) in equation (3) denotes a turbulent flow mechanism and agrees with the results of previous studies on mass transfer in agitated vessels[8,9]. An overall mass transfer correlation was envisaged for the blank solution in terms of the dimensionless groups Sh, Sc and which are usually used in correlating mass transfer data under forced convection. Figure 3 shows that the mass transfer

and 4460 < Re < 104322 fit the equation: Sh = 0.000575 Sc0.33 Re0.7 (4) with an average deviation of 6 per cent. Impeller diameter was used as a characteristic length in calculating Sh and Re. The diffusivity D was taken from the literature[4]. Equation (4) can be used in practice to predict the rate of diffusion-controlled corrosion of the walls of agitated vessels. In industry, corrosion of agitated vessels walls are often controlled by the diffusion of dissolved oxygen to the wall of vessel. Sometimes, the rate of corrosion is

Results and discussion

Diffusion-controlled corrosion of the agitated vessel in blank solution is as shown in Table I.

Text Specific gravity at 20C Viscosity Redwood number 1 at 37.8C at 30.0C at 25.0C at 20.0C Pour point (max.) C Vapour pressure kg/cm Sulphur content Salt content Carbon residue Water content Sediments Wax content Asphaltenes Ash content Total acidity Hydrogen sulphide ppm wt. Mercaptan sulphur ppm wt.
2

Results 0.878 70.000 86.000 104.000 132.000 -4.000 0.320 1.900 0.002 6.240 0.050 Nil 2.290 3.580 0.020 0.057 Nil 36.800

%wt % wt % wt % volume % wt % wt % wt %wt

Table I. Properties of the crude oil used in emulsion preparation

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controlled by the diffusion of the corrosion product away from the vessel wall as in the case of steel - H 2 SO 4 system where the rate of corrosion is controlled by the diffusion of FeS0 4 away from the steel wall[10]. Equation (4) can be used in the design stage, to calculate the thickness of the vessel which covers a certain life span in service under a given set of operating conditions. Figure 4 shows that corrosion distribution is almost uniform at the wall of the agitated vessel, the fluctuation of the mass transfer coefficient at different wall heights is negligible and lies within the range of experimental error. The uniformity of corrosion reflects a uniformity of the hydrodynamic conditions at the wall of the agitated vessel. Diffusion-controlled corrosion of an agitated vessel containing oil-water emulsions is as follows: Figure 5 shows the effect of oil concentrations (volume percentage) on the mass transfer coefficient of the corrosion of the tank wall in an acidified FeCl3 solution for different impeller rotation speeds. The mass transfer coefficient of the corrosion process decreases - then remains constant and finally decreases again with further increase in oil concentration. Figure 6 depicts that the decrease in the mass transfer coefficient with increasing oil concentration ranges from

71 per cent to 97 per cent. Figure 6 also indicates that the percentage decrease in the mass transfer coefficient is independent of the impeller speed. The decrease in the mass transfer coefficient with oil concentration may be attributed mainly to the wetting of the vessel wall by an hydrophobic layer of oil which impedes the reaction between acidified FeCl3 and the vessel wall. It is also probable that the presence of oil droplets dispersed in the aqueous phase hinder the diffusion of Fe 3 + to the depolarizer wall of the vessel with a consequent reduction in the mass transfer coefficient and the

rate of corrosion. The present finding is in agreement with the finding of other authors[11] who found that the corrosivity of crude oil increases with increasing its water content. The authors measured the corrosivity of crude oils mined from the wells where water, H2S, acidic salts such as MgCl2 and CaCl,, naphthenic acids, mercaptans and other sulphur compounds exist in the oil. Figure 7 shows that despite the lowering in the mass transfer coefficient in the presence of oil, the relation between the mass transfer coefficient and impeller speed is represented by the equation:
K= a
V0.7
(5)

where a is a function of the oil concentration. The higher the oil concentration, the lower the value of a the fact that the velocity exponent in equation (5) is still 0.7 shows that the presence of oil does not change the diffusion-controlled mechanism of the corrosion reaction.

Conclusion
(1) The rate of diffusion-controlled corrosion of agitated vessels as expressed in terms of the mass transfer coefficient (K) was found to increase with increasing impeller speed according to the equation:
K = a V0.7

The rate of corrosion was found to be almost uniform all over the
6 Anti-Corrosion Methods and Materials

wall of the c y l i n d r i c a l agitated vessel. (2) T h e rate of the diffusioncontrolled corrosion of agitated vessels can be predicted from the dimensionless equation: Sh = 0 . 0 0 0 5 7 5 R e 0 . 7 Sc0.33 (3) Agitated vessels containing crude oil-water emulsions were found to suffer less corrosion than oil-free solution. The rate of corrosion was found to decrease by an amount ranging from 71 per cent to 97-per cent depending on oil concentra tion in the emulsion.

4. Poulson, B . and R o b i n s o n , R., Corrosion Science, Vol. 26 No. 265, 1986. 5. Poulson, B., Corrosion Science, Vol. 30, 1990. 6. Laitinen, H.A., Chemical Analysis, McGraw-Hill, 2nd ed., New York, NY, 1972. 7. Findly, A . and Kitchner, J.A., Practical Physical Chemistry, 8th ed., Longmans, London, 1965. 8. E i s e n b e r g , M . , Tobias, C.W. and Wilke, C.R., Journal of the Electro chemical Society, Vol. 101 No. 806, 1954. 9. Poulson, B., Corrosion Science, Vol. 23 No. 391, 1983. 10. Ellison, B.T. and S c h m e a l , W.R., Journal of the Electrochemical Society, Vol. 125 No. 524, 1978. 11. Holser, R.A., Prentice, G., Pound, R.B. and Guanti, R., Corrosion, Vol.46 No. 764, 1990.

Appendix. List of symbols A a,a' C0 C d D rps rpm r V Sh Sc Re area of the dissolving surface constants initial concentration of FeCl 3 concentration of FeCl 3 at any time t. impeller diameter diffusivity of F e + + + revolutions per second revolutions per minute impeller radius linear velocity of the impeller V= r sherwood number (Kd/D) Schmidt number /pD) Reynolds number (pVd/) solution viscosity solution density angular velocity ( = 2 rps)

References 1. Nelson, W.L., Petroleum Refining Engineering, McGraw-Hill, New York, NY, 1987. 2. Uhlig, H., Corrosion and Corrosion Control, John Wiley & Sons, New York, NY, 1963. 3. Poluboyartseva, L.A., Zarubin, P.I. and Novakovskii, V.M., Prikl. Khim, Vol.36, 1963, p. 1264.

Further reading Pickett, D., Electrochemical Reactor Design, Elsevier, Amsterdam, 1977.

G.H. Sedahmed and A. Hosny are in the Faculty of Engineering, Chemical Engineering Department. E. K h a m i s , S. Kandil and M . E l - M a g h r a b i are in the Faculty of Science, Chemistry Department, Alexandria University, Alexandria, Egypt.

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