IBP2048_12 EVALUATION ISOTHERMAL AND NO ISO-THERMAL PYROLYSIS OF ASPHALTENES 1 Ingrit C. Castellanos , Lina C. Navarro2, Carlos E.

Lizcano3, Jhon Pealoza3, Laura M. Daz1

Copyright 2012, Instituto Brasileiro de Petrleo, Gs e Biocombustveis - IBP Este Trabalho Tcnico foi preparado para apresentao na Rio Oil & Gas Expo and Conference 2012, realizado no perodo de 17 a 20 de setembro de 2012, no Rio de Janeiro. Este Trabalho Tcnico foi selecionado para apresentao pelo Comit Tcnico do evento, seguindo as informaes contidas no trabalho completo submetido pelo(s) autor(es). Os organizadores no iro traduzir ou corrigir os textos recebidos. O material conforme, apresentado, no necessariamente reflete as opinies do Instituto Brasileiro de Petrleo, Gs e Biocombustveis, Scios e Representantes. de conhecimento e aprovao do(s) autor(es) que este Trabalho Tcnico seja publicado nos Anais da Rio Oil & Gas Expo and Conference 2012.

Abstract
The increase in the content of residues or bottoms in crude oils, which that can pass from from 10 % in light oil to 50 % heavy and extra-heavy oil, pose interesting challenges for the industry, so its managing implies the development of alternatives to facilitate their use, in order to maintain to the maximum the performance and utilization thereof. The content of asphaltenes present in the crude oil determines the quality of thereof, which mainly associated with the API gravity and the viscosity. These compounds for their physical and chemical characteristics could be a source of novel products , thus obtaining gases and liquids which are subsequently used as part of the refining process of crude oil. In the Colombian petroleum institute has been developed the ECODESF process, a technology that improve the physicochemical properties of Colombian heavy and extra-heavy oils. The improvement obtained through the process, allows to obtain a principal product (DAO) with desirable characteristics and a solid by-product with high content of asphaltenes. By their physical and chemical characteristics, the solids obtained can be taken to a thermal cracking, for the maximum obtaining of gases and liquids. Through Thermogravimetry (TG), this article evaluated the thermal behavior of cracked solids to determine its kinetic reaction. The non-isothermal analysis allowed the conclusion that after 800 K the yield of the volatile products is invariable and the maximum temperature range in which maximum conversion is obtained between 770 and 800 K, according to the isothermal analysis.

1. Introduction
At present, the technologies to process heavy and extra-heavy crude oil become less undoubted and more specific still, when the reserves of these are the most representative worldwide (70%v). In Colombia, at the end of 2010, there was certified a reserve of 2.000 MMbbl, where the crude oil with gravity lower API than 10 compose 60%v. Inevitably, this type crude oil, containing compounds of low volatility, high molecular weight, high content of metal (manly Ni and V) and a highly aromatic structure. This type of characteristics refer to the asphaltenes, entities that according to their nature and composition demands a profound study that implies not only the problems caused in the stages of handling of the crude oil as production, transport and refining, but also including the use of the thereof. The Colombian petroleum company, ECOPETROL, through its research institute, the Colombian Petroleum Institute, has developed a technology, named ECODESF (Grosso, J.L, & al.), that improves the properties physicochemical properties of these types of crude oil for his manipulation in the transport area. In this process, the separation of the heavy fraction crude oil is performed by means of the interaction with a solvent of paraffinic character, composed mainly (70%v) pentane and isopentane, to moderate conditions of pressure and temperature. Once established these conditions, is achieved the precipitation of solids, which are composed principally for asphaltenes. These solids for physical and chemical characteristics have a high associate value for your use in processes of pyrolysis, combustion and / or gasification, since they present a high calorific value and a considerable concentration of maltenes. The thermal cracking process is a developed technology in the middle of the 20th century and commonly used today to convert oil residues into liquid distillable products, as well gas and coke, and whose aim is to guarantee that the conversion there is an increase in the obtaining of the liquids. Hence, the operation condition, make this process is versatile for a specific type of load, being the reaction temperature the most important variable in question. Furthermore,

______________________________ 1 Chemical Engineer UT TIP-PETROLABIN 2 Ph.D, Chemical Engineer ECOPETROL- ICP 3 M.Sc. Chemical Engineer ECOPETROL-ICP

Rio Oil & Gas Expo and Conference 2012 the Thermogravimetric Analysis (TG) is a technique for describing the behavior of the thermal decomposition of a sample under an oxygen free environment, and that through the quantification of the obtained products determine the kinetic parameters pyrolysis reaction carried out to find the appropriate temperature which obtains the major conversion of products (Gonaves & al.). The aim of this investigation is to define the kinetic variables to find the suitable temperature to which there is obtained the major conversion of volatile products by means of the isothermal and non-isothermal behavior.

2. Experimental Methodology
The physicochemical properties of the solids used in this study, presented in the table 1 are a part of the product obtained in the Deasphalting process, ECODESF. This technology was developed to pilot scale, with a processing capacity of 1 BPD extra heavy crude oil, with API gravity less than 8, 650000 cp viscosity to 30C and an asphaltenes content of 16%p. Table 1. Asphaltenes aggregates obtained in ECODESF process characterization Physical and chemical properties Density Calorific Molecular Weight Physical state, color and odor Saturated 4.1 % p 1.1 15798 2007 g/mL BTU/Lb g/mol C H O S N Resins 14.7 % p Proximate analysis 83.5 9.2 3.4 3.7 0.19 %p %p %p %p %p

Solid, dark brown to black, characteristic odor SARA ANALYSIS Aromatics 17.1 % p

Asphaltenes 64.1 % p

2.1 Non-Isothermal Pyrolysis For Termgravimetric study was weighed between 60 and 80 mg of sample, which was exposed in the thermobalance Thermax 300 model 2131, in a quartz sample holder. The analysis was carry out in a dynamic stage until the operating temperatures of 1073, 1123 and 1173 K, with a heating rate of 4, 8 and 12 K/min, as shows in the design of the table 2, with a flow of 5 ml/min of argon of 99.99 % purity. After reaching the maximum operating temperature, an isotherm is kept 30 minutes to complete the reactions to purge the system. Table 2. Experimental variables Variable Temperature (K) Heating Rate (K/min) Low 1073 4 Intermediate 1123 8 High 1173 12

2.2 Isothermal Pyrolysis In the isothermal evaluation tests was carried out at temperatures of 673, 723, 773 and 823 K respectively to a heating rate of 12 K/min. The argon flow rate was 5 mL/min of 99.99 % purity and the time of evaluation the runs was of 120 min to assure the complete development of pyrolysis reactions. All tests were performed with a delay time of 10 minutes to ensure the stabilization inside the reactor.

3. Results and Discussion

3.1 Non-Isothermal Pyrolysis The decomposition behavior Non-isothermal, evaluated in the solid products ECODESF process is presented in Figure 1 at different heating rates. Initially is accomplished to identify a temperature below 480 K, the elimination of water and the hydrogen sulfide, as result of thermal decomposition of thermally unstable groups. Subsequently, the isomerization of carbon and rupture of the aliphatic chains still present (malthenes), are characterized by the increase in 2

Rio Oil & Gas Expo and Conference 2012 weight loss close to 700 K, since in this range is eliminated most of the volatile material. One of the characteristics of the analysis DTG, is to visualize the thermal behavior in greater detail. Thus in this study it is achieved to visualize a global minimum symbolizing the temperature of maximum rate of decomposition, i.e. the temperature from which the maximum evolution of the products, where finally the residue is without certainly a highly poly-aromatic coke. This temperature range corresponds between 730 and 780 K approaches the studies realized by Amabalae, & al. Furthermore it was found as heating rate increases the yield of coke is becoming smaller, showing that at 4, 8 and 12 K/min the amount of coke represents 62, 66 and 56%p respectively. Thus indicating that the yield of the coke formed by the solid of ECODESF process constitutes a range between 50 and 70%p, establishing that to achieve a minimal conversion from these to coke is achieved at a higher heating rate.

120
I II III IV

1 0

100 -1 80
TG (%W)

-3 60 -4 40
(4 K/min) (8 K/min) 12 K/min

-5 -6 -7 -8 1080

20

d(%W)/dt(4 K/min) d(%W)/dt(8 K/min)

0 280

d(%W)/dt(12 K/min)

380

480

580

680

780

880

980

Temperature (K)

Figure 1. Non-Isothermal decomposition of solids obtained from ECODESF process As for the kinetic of the reaction, the pyrolysis of asphaltenes is a first order reaction for which describes the general conversion of the solids (Bozzano, G. and Give You, M.), where the rate constant is influencedx mainly by temperature through the Arrhenius's correlation as shows in the equation 1.
E a d = Ae RT (1 ) dt

DTG (%W/min)

-2

(1)

Where is the fraction volatilized, A, the pre-exponential factor and Ea, the activation energy. In this research where the reaction is isothermal, the temperature variation is given by T= To+t, therefore the application of the heating rate can be expressed as dT/dt=. Using this transformation, Eq. 1 can be converted into:
d A E = exp a (1 ) dT RT

(2)

The values of the kinetic variables shown in table 3 were determined from the Friedman method, since this method allows greater accuracy, because not including certain mathematical approximations (Hillier, J. and to.). The results obtained of the Ea show that the reaction is endothermic with values understood between 151 and 177 KJ/mol, this being the energy necessary for the pyrolysis of these solid, showing a behavior similar results to the studies realized by Rahmani and Gray. Finally, with regard to conversion to liquid and gas products, as the heating rate increases, the conversion becomes increases with values of 0.6, 0.7 and 0.8 % respectively (Figure 2). Thus indicating that the maximum conversion obtained was performed at a lower temperature of 800 K, showing unnecessary to take the reaction over this temperature. 3

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Table 3. Values of the Activation Energy and pre-exponential factor T (K) 1073 (K/min) 4 8 12 4 1123 8 12 4 1173 8 12 A (1/min) 5.9E+08 2.1E+08 1.8E+08 1.6E+10 1.9E+07 1.2E+08 5.4E+07 6.3E+08 3.0E+07 Ea (KJ/mol) 158.4 151.0 151.5 177.5 137.0 149.1 143.5 160.2 135.4

1 0.9 0.8 0.7

Convertion,

0.6 0.5 0.4 0.3 0.2 0.1 4 C/min 0 300 400 500 600 700 T (K) 800 8 C/min 900 12 C/min 1000 1100

Figure 2. Solids conversion at different heating rates 3.2 Isothermal Pyrolysis For the second phase of this study, made clear that according to the results of the non-Isothermal analysis, the pyrolysis of solids obtained from ECODESF process, is a process that depends on temperature, this being with less than 800 K. Therefore, the isothermal analysis reduces the temperature range of evaluation, to have a close approximation to the maximum temperature of conversion with a 12 K/min heating rate, following the goal of maximizing the conversion to volatile products. Figure 3 shows the variation of the weight found in the range of temperatures established (673-823 K). The proximity showing curves represented by temperatures 773 and 823 K, symbolizes that the variation of the weight is not significant after the temperature of the experimental design (823 K), because there is no change to obtain the volatile compounds (liquid and gas). This indicates that the conversion is achieved at a temperature equal to or below 773 K to obtain liquids and gas, thus confirming, the results of the non-isothermal analysis and developing the aim put forward at the beginning of this study. For the isothermal condition the Ea was 64.3 KJ/mol. Thus showing the energy necessary required to perform only some reactions (Lzaro , & al.) that involve primarily the loss of weight close to 600 K (temperature at which begins the formation of coke), compared with all reactions which complement the non-isothermal environment, since the stages of weight loss of water and volatiles are almost imperceptible.

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100 90 80 70 673 K 60
%W

50 40 30 20 10 0 40 60 80 100 120
Time (min)

823 K 773 K

723 K

140

160

180

200

Figure 3. Isothermal decomposition of solids obtained from ECODESF process

4. Conclusions
Pyrolysis of the solids obtained from ECODESF process, from the analysis thermogravimetric, showed that the maximum conversion is in a range of 750 - 780 K. The high values of the Ea are attributed to the content of maltenes presents, as the final products have a high calorific value after the thermal cracking. The heat required to achieve thermal decomposition of solids shows different values in the conditions Isothermal and Non-Isothermal, principally because the reactions in the isothermal environment it includes basically the formation of the heaviest compounds, in comparison with the non-isothermal condition which involves the elimination of the volatile compounds. An economic evaluation is recommended to assess the feasibility of this process in high scale.

5. Acknowledgement
At the Colombian Petroleum Institute Ecopetrol-ICP, for the support in the implementation of this investigation

8. References
AMABALAE, A. & al. Thermogravimetric studies on pyrolysis and combustion behavior of a heavy oil and its asphaltenes, Energy & Fuels, v. 20, p. 560-565, 2006. BOZZANO, G. & DENTE, M.; A Mechanistic Approach to Delayed Coking Modelling, European Symposium on Computer Aided Process Engineering, 2005. GONAVES & al. Influence of asphaltenes on coke formation during the thermal caracking of different Brazilian distillation residues, Fuel, v. 86, p. 619-623, 2007. GROSSO, J.L, & al. Final Report. Upgrading of heavy oils and heavy petroleum fractions using deasphalting process to moderate conditions of pressure and temperature, Ecopetrol-ICP, Sep. 1991. HILLER, J.; BESSANT, T; FLETCHER. Improved Method for the Determination of Kinetic Parameters from Nonisothermal Thermogravimetric Analysis (TGA) Data. Energy & Fuels, v. 24, p. 2841-2847, 2010 LZARO, M.; MOLINER, R. & SUELVES, I. Non-isotermal versus isothermal technique to evaluate kinetic parameters of coal pyrolysis, Journal of Analytical and Applied Pyrolysis, v. 47, p. 111-125, 1998. RAHMANI, S., & GRAY, M. Dependence of molecular kinetics of asphaltene cracking on chemical composition. Petroleum Science and Technology, v. 25, p. 141152, 2007 ZHAO, Y; MURRAY G. Molar kinetics and selectivity in cracking of Athabasca asphaltenes, Energy & Fuels, v. 15, p. 751-755, 2001. 5