International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016) Reducing Crude Oil Viscosity Using Diluents Kulkarni A.D#1 and Wani K.S*2 # Maharashtra Institute of Technology, Kothrud, Pune-411038, India SSBT College of Engineering and Technology, Bambhori, Jalgaon-425001, India * Abstract- Viscosity reduction of crude oil for its efficient transportation through cross country pipelines is of prime importance in the petroleum industry. One of the methods is to blend the crude oil with light hydrocarbons and organic solvents. The method is easy to implement and is widely used for transporting heavy crude oils and bitumen. A number of diluents like condensates, light oils, naphtha, middle distillates and organic solvents are used. The resultant viscosity depends on number of factors like the composition of crude oil, properties of diluent, oil/diluent ratio and the interaction between crude oil and the diluent. This requires a good mathematical model for accurate viscosity prediction. A number of models available in the literature have been discussed in this paper. Also an empirical model based on experimentation for viscosity reduction of crude oil diluted with n- hexane at different temperatures has been developed. The model gives fair accuracy in a limited operating range. Key words: Flow Assurance, Hydrocarbons, Viscosity Reduction, Crude Oil Dilution, Crude Oil Transportation I. Introduction Transportation of crude oil through pipelines is a major flow assurance challenge. This is attributed to crude oil composition, density, viscosity and ambient temperature conditions. Increased viscosities due to the above factors lead to large pressure drops, increased pumping costs, blocked pipelines and production loss. This is true for heavy as well as medium density crude oils. Heavy oil (API < 20) and extra heavy oil (API < 10) have high proportion of asphaltenes and paraffins compared to low molecular weight hydrocarbons. During transportation these asphaltenes and paraffins tend to get unstable and precipitate causing multiphase flow and clogging of pipelines. Estimated losses are in the range of millions of dollars annually [1].Commonly used methods for remediation or prevention include mechanical methods, thermal treatment and chemical methods. Along with these, dilution of crude oil is one of the most widely used methods for overcoming the above problem. This paper reviews the method of crude oil dilution in detail. II. Crude Oil Dilution Dilution of crude oil is the oldest method (since 1930s) and can be accomplished by using condensates ISSN: 2231-5381 obtained in natural gas production; light oils; light hydrocarbons; organic solvents like methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), etc; alcohols like pentanol, hexanol, etc; gasoline and middle distillates like kerosene. A dilution ratio of 0 –20 % for heavy crude oil and 25 to 50% for bitumen is enough to carry out the method successfully [2]. A. Advantages and Disadvantages Dilution has number of advantages. It reduces the viscosity of crude oil thereby facilitating its transportation through pipelines. It avoids high pressure drops and reduces the pumping cost. Furthermore dilution helps the desalting and dehydration operations downstream. The method also suffers certain disadvantages. Transportation of solvent requires an additional pipeline along with the crude oil pipeline. This demands considerable capital and operational investment in pumping and pipeline maintenance. Separation of solvent and returning it to oil production site requires the creation of a separate facility. Choice of the solvent is also affected by the oil composition. This is due to the compatibility issues between the asphaltenes and paraffins present in the oil with the solvent. If due care is not taken, deposition of asphaltenes and paraffins can cause further problems. Availability of the diluents in the desired quantity is also an important issue. Moreover, prediction of solvent/oil ratio for achieving a required reduction in viscosity is difficult as the number of governing parameters is large and inconsistent such that simple mixing rules are ineffective. B. Diluents (i) Natural gas condensates-Being the lightest hydrocarbon component, dissolution of heavier components and subsequent reduction in the viscosity is facilitated by natural gas condensates. This was a widely used method since 1930s. But the popularity dropped after 80‟s due to the following reasons. Firstly the availability of condensates depends on the demand of natural gas. Secondly, with the increased heavy oil recovery, the existing production of condensates is insufficient. Thirdly, the distance between the condensate production site and the oil production site is a major issue. Lastly, asphaltenes are not properly soluble in condensates. This may results in flocculation which leads to partial plugging of pipelines. http://www.ijettjournal.org Page 85 International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016) (ii) Light oils-Crude oils having API gravity between 35 and 42 can be used for dilution. But these suffer similar disadvantages as condensates like availability and compatibility with asphaltenes. (iii) Naphtha- Hydrocarbons ranging from C6 to C12 form the naphtha fraction of crude oil distillates. It has low density which leads to efficient dilution of crude oil. It has good compatibility with asphaltenes owing to the presence of aromatic content in it. It is easily recyclable and reusable. (iv) Organic solvents/ distillates- Gasoline and kerosene have been used as distillates owing to their good solvent properties. Gasoline also helps to improve the octane number in downstream processing. Yaghi and Benami [3] have shown that 15% kerosene mixed with heavy oil at 50°C achieves the same viscosity reduction achieved by 20% kerosene at room temperature. Use of Methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME) and dimethyl ether (DME) have been considered [4]. Recovery of DME is easier as compared to other solvents. Argillier et al [5] have shown that alcohols are more effective in reducing the viscosity. Hasan et al [6] have found that 10% ethyl alcohol reduced viscosity of crude oil by almost 80% at 250C.This can be due to interaction between the hydroxyl groups and asphaltenes. (v) Carbon dioxide- In some recent developments, R.Hu et al [7] have studied the effect of carbon dioxide on the heavy crude oil. They have found that crude oil saturated with carbon dioxide undergoes significant reduction in viscosity at a given temperature and pressure. C. Prediction of Resultant Viscosity of the Crude oilDiluents Mixture When oil and diluents are mixed together, the resulting viscosity depends on the dilution rate, viscosities and densities of oil and diluents. It is observed in general that lower the viscosity of the diluents, lower is the viscosity of the blended mixture. A number of correlations have been developed till date for prediction of resultant viscosity. But the accuracy of these relations is limited owing to the number of parameters involved in them. Gateau et al [8] have discussed few such relationships. The classical Arrhenius equation has been modified by Lederer to represent the viscosity of a mixture. V o log 1 Vo log log s o V V V V s o s o Where Vo, o, Vs and s are the volume fractions and viscosities of oil and solvent respectively and is an empirical constant varying between 0 and 1. ISSN: 2231-5381 A generalized expression for has been developed by Shu [9] to predict the viscosity crude oil diluted with light hydrocarbons. 17.04( o s ) 0.5237 o 3.2745 s 1.6316 ln o s Where, ρo and ρs are densities of oil and solvent respectively. Viscosity reduction is affected by the concentration of asphaltenes in maltenes. There exists a critical concentration above which there is entanglement of the colloidal particles which results in increasing the resultant viscosity of crude oil. Reduction in viscosity can be achieved by limiting the entanglement. This can be achieved by increasing the interaction between solvent and the polar part of the crude oil viz. asphaltenes which reduces the interactions amongst the asphaltenes themselves. These molecular interactions can be measured with the help of the solubility parameter t as given by the Hildebrand and Scott theory. The solubility parameter is a representation of the combined effect of the dispersion forces (comprising of London forces and van der Waals forces), polar interactions and hydrogen bonding. Hansen parameter takes into account the above factors. n V i i i 1 Where, is the Hansen parameter of the mixture i is the Hansen parameter of the pure solvent „i‟ Vi is the volume fraction of the solvent „i' in the mixture Using the above theory, Gateau et al [8] have proved experimentally that dispersion forces have negligible effect on asphaltene aggregation whereas polar interactions and hydrogen bonding have appreciable effect. With mixtures of solvents like 2-butanone, butyronitrile, butryraldehyde and ethyl acetate with naphtha and nonane, they have proved that the solvent with more polarity gives better viscosity reduction. This was concluded from the observation that the polar parameter p has less value in naphtha based solvent mixtures as compared to nonane based solvent mixtures. This means that the polar sites of asphaltenes in naphtha are more accessible to the polar solvents leading to higher efficiency and better viscosity reduction. Also using small angle X-ray scattering (SAXS) they have shown that polar solvents like hexyl alcohol can reduce the gyration radius of the asphaltene particles and the relative viscosity of http://www.ijettjournal.org Page 86 International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016) Motahhari et al [10] have used Expanded Fluid (EF) viscosity model for predicting the viscosities of 3 to 30 % by weight condensate diluted heavy oils and bitumen at temperatures up to 1750C and pressures up to 10 MPa. % change for S1 % change for S2 100 % Change in Viscosity the crude oil mixture. This is attributed to the ability of the polar solvents to establish hydrogen bonding with asphaltenes and thus reducing the interactions amongst the asphaltenes themselves. They also found that there was no specific relationship between the hydrogen bonding parameter and viscosity reduction efficiency. Thus, the candidate solvents for a particular application can be selected using the Hansen‟s theory. 90 80 70 60 50 40 30 35 45 55 65 75 Temperature (deg C) III. Experimental Using a diluent of single type in two different proportions, it is proposed to predict the reduction in viscosity of a crude oil at different temperatures. A. Materials and Methods Mixtures of crude oil (35 0API) and commercially available n- hexane (MERCK) as a diluent were taken in proportions of 10 % (Sample S1) and 20 % Sample S2) by weight for experimentation. Viscosities for the mixtures were measured at different temperatures ranging from 400C to 650C with the help of a U-tube viscometer kept in a temperature controlled bath. Viscosities for pure crude oil (Sample S0) were also measured and the percentage changes in viscosity for the mixtures were calculated. Fig.2. Changes in Viscosities of the Mixtures A non-linear regression model is proposed to relate the reduction in viscosity (V) with respect to temperature (T) and concentration (C) of the diluent. V = TC The parameters , and are found using non-linear regression routine in MS-EXCEL. The values found were as follows: =5024.1 = -0.9 = 0.314 Hence the model becomes V = 5024.1(T-0.9C0.314) B. Results and Discussion As seen from Fig. 1, the reduction in viscosity is a function of temperature and the concentration of the diluents. The experimental results and the model predicted results are given in Table 1 to evaluate the performance of the developed model. TABLE 1 REDUCTION IN VISCOSITY: ACTUAL VS. MODEL PREDICTED V = f (T, C) S0 S1 S2 T (0C) C (Weight Fraction) Viscosity Reduction: Actual (%) Viscosity Reduction: Model Predicted (%) % Deviation 65 60 55 50 45 65 60 55 50 45 0.1 0.1 0.1 0.1 0.1 0.2 0.2 0.2 0.2 0.2 52.586 56.445 71.482 76.294 76.622 71.346 74.910 86.395 88.873 89.848 56.941 61.195 66.179 72.107 79.279 70.787 76.074 82.271 89.640 98.556 -8.282 -8.415 7.417 5.488 -3.468 0.784 -1.555 4.774 -0.863 -9.692 Viscosity (cP) 80 60 40 20 0 35 45 55 65 75 Temperature (deg C) Fig.1. Viscosity vs. Temperature ISSN: 2231-5381 http://www.ijettjournal.org Page 87 International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016) Reduction in Viscosity (%) 110 100 90 80 Actual 70 Model 60 50 35 45 55 65 75 Temperature (deg C) can be easily transported at lower temperatures. This will reduce the requirement of heating and thermal insulation for the transportation pipelines necessary to keep the oil below WAT. With 20% diluent concentration, a reduction of around 90% is observed, indicating a lesser requirement of diluent for medium density crude oil. The observation is supported by the results given by Hasan et al [6]. This will result in an overall reduction in the operating cost. The model parameters and indicate that viscosity reduction is inversely proportional to temperature and directly proportional to concentration. The lesser value of underlines the importance of diluent concentration in the overall viscosity reduction. The maximum deviation for the actual and the model predicted values for viscosity reduction is around 10% which gives a fair accuracy of the predicted results. Fig. 3. Reduction in Viscosity vs Temperature Reduction in Viscosity (%) [IV] Conclusion The method of dilution of crude oil for its efficient transportation has been discussed along with its 110 advantages and disadvantages. Amongst the various diluents used commercially, mixtures of polar solvents 100 with naphtha gives better efficiency in viscosity reduction of the crude oil. Resultant viscosity of the 90 crude oil-diluent mixture depends on the dilution ratio, asphaltene concentration, solvent polarity and 80 Actual hydrogen bonding capability. This is demonstrated by 70 number of models as seen from the literature. From Model the experimentation performed using a single diluent 60 for given crude oil, it is observed that an optimum concentration of the diluent is required to achieve the 50 desired viscosity reduction. An empirical model 0 0.1 0.2 0.3 relating viscosity reduction with temperature and Concentration of diluent (Weight Fraction) diluent concentration has been developed. The model gives good accuracy for prediction of viscosity reduction. The model can work in a limited range owing to the lesser number of data points used for Fig. 4. Reduction in Viscosity vs Diluent Concentration generation. It can be tuned to greater accuracy with rigorous experimentation involving varying A steep change in the slope of the graph for viscosity concentration ranges with different diluents. Also the versus temperature gives the value of the wax method of dilution if used independently can prove to appearance temperature (WAT) for a crude oil. As be expensive due to the large volumes of diluents seen from Fig. 1, the WAT for sample S0 (crude oil) is required. The quantity of diluents can be reduced if between 550C-600C, for sample S1 (Crude + 10% n- the method is used in conjunction with other viscosity hexane) is between 500C-550C and for sample S2 reduction methods like heating or magnetic field (Crude + 20% n-hexane) it is between 450C- conditioning. These possibilities need to be explored 500C.Thus the WAT reduces with increasing diluent further. concentration. However as seen from Fig.1, the variation is slopes for S1 and S2 at the point of inflection is less indicating that further increase in the REFERENCES concentration of the diluents will not reduce the WAT appreciably. Hence there lies a maximum value for [1] W.W.Freiner, M.Zainuddin and R.Venkatesan, Organic Deposits in Oil and Gas Production, Society of diluent concentration in the crude oil above which the Petroleum Engineers, 2010. dilution is ineffective. This is in accordance with the [2] A.Hart, “A review of technologies for transportation of values given by Martinez-Palou et al. [11] which lie heavy crude oil and bitumen via pipelines”, Journal of between 20-30%. Petroleum Exploration, Production and Technology, vol.4, pp.327-336, 2014. Also as seen from Fig. 2, the % change in the [3] B.M.Yaghi and A.Al-Bemani, “Heavy crude oil viscosity is greater at lower temperatures and at higher viscosity reduction for pipeline transportation”,Energy diluent concentrations. This indicates that crude oil Sources, vol.24, pp. 93-102, 2002. ISSN: 2231-5381 http://www.ijettjournal.org Page 88 International Conference on Global Trends in Engineering, Technology and Management (ICGTETM-2016) [4] [5] [6] [7] [8] [9] [10] [11] J.L.Anhorn and A.Badakshan, “MTBE: A carrier for heavy oil transportation and viscosity mixing rule applicability”, Journal of Canadian Petroleum Technology, vol.33, no.4, pp.17-21, 1994. J-F. Argillier, L. Barre, F. Brucy, J-L. Dournaux, I. Henaut, and R. Bouchard, “Influence of Asphaltenes Content and Dilution on Heavy Oil Rheology”in proceedings of SPE International Thermal Operations and Heavy Oil Symposium, Venezuala, SPE 69771, pp.1-8, 2001. S.W.Hasan, M.T.Ghannam and N.Esmail, “Heavy crude oil viscosity and rheology for pipeline transportation”, Fuel, vol.89, pp.1095-1100, 2010. R.Hu, J.P.Crawshaw, J.P.Martin-Trusler and E.S.Boek, “Rheology of diluted heavy crude oil saturated with carbon dioxide”, Energy and Fuels, vol.29, no.5, pp.2785-2789, 2015. P.Gateau, I.Henaut, L.Barre and J.F.Argillier, “Heavy Oil Dilution”, Oil and Gas Science and TechnologyRev.IFP, vol.59, no.5, pp.503-509, 2004. W.R.Shu, “A viscosity correlation for mixtures of heavy oil, bitumen and petroleum fractions”, Society of Petroleum Engineers Journal, pp.277-282, June 1984. H.Motahhari, F.F.Schoeggl, M.A.Satyro and H.W.Yarranton, “Viscosity prediction of solvent-diluted live bitumen and heavy oil at temperatures up to 175 0C”, Journal of Canadian Petroleum Technology, pp.376390, September 2013. R. Martinez-Palou, M. Mosqueira, B.Zapata-Rendon, E.Mar-Juarez, C. Bernal-Huicochea, J. Clavel-Lopez and J.Aburto, “Transportation of heavy and extra-heavy crude oil by pipeline: A review”, Journal of Petroleum Science and Technology, vol 75, pp.274-282, 2011. ISSN: 2231-5381 http://www.ijettjournal.org Page 89