IBP2040_12 SIMPLIFIED METHODOLOGY FOR DETERMINING STABILITY IN MIXTURES OF CRUDE OILS Luciano M.

Stor1

Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP
This Technical Paper was prepared for presentation at the Rio Oi & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute’ opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings.

Resumo
Os compostos chamados de asfaltenos são a fração mais pesada e que apresentam um comportamento semelhante a de uma particula coloidal no complexo produto conhecido como petróleo, que é uma mistura formada por diferentes tipos de hidrocarbonetos, grupamentos funcionais e hetero-átomos como enxofre, nitrogênio, oxigênio e diferentes metais. Estes compostos normalmente se mantêm em suspensão no petróleo solvatados por compostos conhecidos como Resinas. Um grande problema na indústria do petróleo, que provoca elevados custos operacionais para diminuir o seu impacto, é o fenomeno conhecido como a floculação dos asfaltenos, que ocorre quando os asfaltenos deixam de estar solubilizados no meio oleoso e passam a agir como particulas sólidas com capacidade de se ligar a outros asfaltenos aumentando a sua massa. Estes problemas ocorrem devido a instabilidade ligada, principalmente a alterações nas temperaturas e pressões em regiões de produção ou de incompatibilidade química resultante da mistura com outros petróleos. A determinação experimental da instabilidade ou incompatibilidade é, relativamente, bem conhecida, porém poucos métodos atuam de maneira eficaz na predição de misturas potencialmente incompatíveis e que apresentam sérias restrições para avaliar o comportamento dos petróleos, quando eles contêm baixos teores de asfaltenos. Este trabalho propõe avaliar uma nova metodologia, simplifica todos os estudos até então desenvolvidos, fornecendo uma alternativa rápida, simples e com boa precisão para se determinar a compatibilidade de mistura e com a facilidade de não precisar das amostras e sim dados das propriedades físico-químicas dos petróleos envolvidos na mistura..

Abstract
Asphaltenes are the highest molecular weight components of the crude oil in which they are normally dispersed helded by resins. In special conditions, they could separate from crude oil and agglomerate to form a bulk-like structure. Such asphaltenes instability increases the operational costs, not only in upstream sector, where they are normally associated to changes in temperature and pressure conditions, but also in refinery process by chemical incompatibility from crude oils blends. There are few methods to predict incompatibility with good results, especially if one or more crude oils that is blended has very low asphaltenes content. In this work a new methodology was developed to predict instability, independent from asphaltenes content. The main objective of this work is given a tool for predicting the behavior of mixtures of crude oil and in terms of stability, using easily available crude oils data (parameters A and B of the equation Walther-ASTM, API gravity and asphaltene content) and does not require any additional laboratory information. With the use of the software STAB, developed by Petrobras for using with this methodology, is possible use a data base with different crude oils and even the crude blend use many crude oils is possible verify which is acceptable blend and also the better order to blended. And if the blend are not stable which oil has to increase its percentage in blend to become stable.

______________________________ 1 Master, Senior Process Engineer - PETROBRAS SA

Rio Oil & Gas Expo and Conference 2012

1. Introduction
The asphaltenes are the most complex structures in the crude oils, see Figure 1, the studies on colloidal properties of asphaltenes are motivated by their propensity to aggregate, flocculate, precipitate and be adsorbed on surfaces. The tendency of asphaltenes to participate in colloidal and interfacial phenomena is one of the great challenges of oil industry. Heavy and polar fractions such as asphaltenes, can accord this imbalance, to separate the mixture and becoming a solid phase in the oil phase, such as dispersed particles may cause problems of disposal.

Figure 1 – 4 samples of asphaltenes molecules. Thus, not only concentration, but mainly the nature, more polar or less polar, is a major factor for the stability of oil. In refineries, thermal changes or mixtures of different oils, the asphaltenes can lead to separate the oil, making them precursors of coke, and causing the deactivation of catalysts. Moreover, the presence of asphaltenes in the oil, the impact properties of oil, with phase changes, significant increase in viscosity and the tendency to coke formation. Still impacts strongly on the interfacial tension, which greatly affects in the desalted operation. There are different methods for checking or predicting the stability of mixtures of oils or finished products of petroleum, where the asphaltenes precipitation problems are also important, as industrial and marine fuel oil (bunker). These methods, aimed at predicting the future behavior of a given mixture, are usually very complex and unreliable results for crude oil because were developed for fuel oils with a high residual phase (high asphaltenes content). Or, require samples of different oils to be mixed for determining the flocculation of each parameter involved in the oil mixture, even if these parameters can be put into a database, yet the implementation of a methodology to control mixed oil would have to be cataloged before the point of flaking or toluene equivalent or similar data, of all oil that will be used in the formation of the Process Unit tank.

2. Methodology and Applicability
A petroleum "stable" can be described as a colloidal suspension, where the asphaltenes (micelles) are polar and the resinous component that surrounds them (Maltenes), is also polar (more aromatic), having a solubility between them. But if the oily medium is paraffin (polar), this stability no longer occurs allowing the asphaltenes precipitation, namely the instability of oil. However, when two or more oils are mixed and this mixture remains homogeneous during storage, producing no sludge on a significant scale, they are compatible. Already, the mismatch is the situation created by mixing two or more oil, whether stable or not, that in a given composition will form an unstable mix. The Farah-Stor Total Index (FSTI) is a model based on a large amount of experiments involving the studies of the Farah-Stor parameter and an Toluene Equivalent Modified, with an addition of extra asphaltenes in the toluene phase, because with very low asphaltenes content the determination of the flocculation point could be not easy determinated or given a false stability indication, how we can see in Figure 2, with a spot test. So as the composition of oil is the major factor for stability, the fact that not having asphaltenes in detectable concentration, it is not an indication 2

Rio Oil & Gas Expo and Conference 2012 of instability or stability and that the addition of asphaltenes "external" will change very little degree of stability of oil, these works are developed during the author's master's degree thesis, which was based on ideas of oil polarity reserve available against the demand necessary to keep the asphaltenes in suspension.

Figure 2 – A false stable indicative, and when add asphaltenes sows its real instable condition A very important notion must be observed: In spite of an oil is unstable or the oils blend indicate an instability, same times we don’t observe any operational problems, mainly due to mixtures with very low asphaltenes contend (in a range of 0.5%mm). But that does not mean that the mixture or oil are stable, it’s remain unstable but with no effective capacity to cause problems. 2.1. Why Use a Simple Correlation There are many different methodologies to check or prevent the instability in a blend; we have the traditionals as Spot Test or Hot Filtration Test (Determination of Total Sediment), some considering the petroleum composition as SARA (Saturate, Aromatics, Resins and Asphaltenes) and relationships between this composition as RAR (Resins and Asphaltenes reason) or CII (Colloidal Instability Index), etc. Even we have methodologies that use some correlations from the Solubility Parameter, as BMCI – TE, Hildebrand Parameter, SBN and IN, Heithaus Filtration, or equipmentsbuse to determinate the flocculation point automatically, as Turbiscan or Porla. See Figures 3 and 4.

Figure 3 – Use of Turbiscan to determinate the Stability of a crude oil.

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Rio Oil & Gas Expo and Conference 2012

Figure 4 – Use the Porla to determinate the floculation point of the same crude oil above

But all of them, besides their veracity in their results, need the sample in laboratory hands, mainly if we have several crude oils to blending. So to avoid these necessity, we improve the methodology developed during the author’s master degree thesis to gives with a reasonable precision the stability of crude oil blend, where is not necessary had the crude oils samples to make the stability evaluation.

3. FSTI Stability Control
One of the different stability control cross-checking used were the ASTM D4870, that we could noticed in the Figure 5. Besides that, we compare the FSTI with others stability test methods as the ASTM D4740, BMCI – TE, Flocculation Parameter and of course the FSI – TEm (Farah-Stor Index with modified TE).

Figure 5. Cross Checking the FSTI results with the D-4870 results So, with after all tests and results we can fix 4 stages of Stability, the first one is a high instability condition, where if have asphaltenes in certain amount we can have serious asphaltenes deposition problems (Condensates Oil have a high instability condition but alone it don’t have any serious deposition problem, but in a blend could cause). The second stage, we consider as instability risk condition, not as severe as the stage 1 but we could have problems. In the third stage we have a light stability condition or a little amount of asphaltenes could be flocculated but without impact the operation. The final stage are considered with a high stability condition, a save operation condition. See Table 1. 4

Rio Oil & Gas Expo and Conference 2012 Table 1 – FSTI – Stability Control FSTI FSTI > 38 30 < FSTI < 38 22 < FSTI < 30 FSTI < 22 The determination of a oil FSTI is obtained by the equation: FSTI = 137 – 7 x (API / (A/B)) Where: API – API gravity A and B – Walther-ASTM equation parameter For a blend the FSTI is determinate by equation: IFST m = [(137-7(API/(A/B))1 x %vol1 x (Asph1+ 0.15) ^ 0.5)] + ... + [(137-7(API/(A/B)) n x %vol n x (Asphn + 0.15) ^ 0.5)] %vol1 x (Asph1+ 0.15) ^ 0.5) + ... +%vol n x (Asphn + 0.15) ^ 0.5) Where: API – API gravity A and B – Walther-ASTM equation parameter Asph – Asphaltene contend 1 … n – Number of crude oils used in the blend Note: For oil with API gravity greater than 40, you should add the value of 0.50 instead of 0.15. Blend Condition High Stability Incipient Stability Instability Risk High Instability

4. Conclusions
These work will enable a quickly answer in terms of the blend stability, without samples to manipulated, easy calculate and very reasonable answer. And with that its possible reduces many operations problems caused by incompatible crude oils blends, as affecting desalting operation, deposition in heat exchangers, sludge formation in tanks, increasing maintenance costs of the refineries and terminals, reducing environment impacts from sludge disposal. To maximizes the results and facility operation, Petrobras are developing a new version of one own soft called STAB now in a fourth version for operation with the FSTI parameter, which is possible works with a Crude Oils Data Bank, 3D-Graphs, which are the right crude stability oil sequence blending, corrects the unstable formulation for a new one closer to stability situation with a minimum modification as possible in the original formulation, and more.

5. References
ANDERSEN, S. I.; SPEIGHT, J. G. Thermodynamic models for asphaltene solubility and Precipitation. Journal of Petroleum Science and Engineering, n 22, p - 53–66, 1999 ANDERSON, R. P. ; REYNOLDS, J. W. Stability and Compatibility of Residual Fuel Oils, NIPER EPRI GS-6570, Nov 1989 EVDOKIMOV, in: Bifurcated correlations of the properties of crude oils with their asphaltene content, FUEL nº 84, pags 13 – 28, 2005 FARAH, M. A, Caracterização de Frações de Petróleo pela Viscosidade. 2006, 238 f. Doctor Degree Thesis in Chemical and Biochemical Technology Process, Escola de Química, Universidade federal do Rio de Janeiro, Rio de Janeiro – RJ, 2006 GRIFFITH, M. G. E SIEGMUND, C. W. Controlling os Residual Fuel Oils. ASTM - Marine Fuels Symposium, Miami, Dez 1983. HEITHAUS, J. J. Measurement and significance of asphaltene peptization, Journal of the Institute of Petroleum, vol. 48, nº 458, 1962. HILDEBRAND, J.; SCOTT, R. Solubility of Non-Electrolytes, 3º ed., Reinhold, New York, 1949. STOR, M. L. Desenvolvimento de Metodologia para Previsão da Compatibilidade de Misturas de Petróleos. Master Thesis Degree in Optimization in Industrial Process, São Paulo SP, 2007. 5