# Dielectric spectroscopy of asphaltenes' solutions under high pressure

Roman M Balabin, Rustem Z Syunyaev

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Roman M Balabin, Rustem Z Syunyaev. Dielectric spectroscopy of asphaltenes' solutions under high pressure. Physics of Electronic Materials, Kaluga State University, May 2005, Kaluga, Russia. hal-05145206

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DIELECTRIC SPECTROSCOPY
OF ASPHALTENES' SOLUTIONS
UNDER HIGH PRESSURE

Balabin R.M., Syunyaev R.Z.

Russian State University of Oil and Gas named after I.M. Gubkin
Moscow, Russia
Leninsky Prospekt, 65, 117917

The paper studies asphaltene solutions in different solvents at different temperatures and pressures (up to 10,000 atm). The data were interpreted using different models of dielectric relaxation. The relaxation time and characteristic particle size were determined. The data obtained were used to analyze oil dielectric spectra. The paper discusses the application of fractal concepts to oil dispersed systems in general and asphaltene solutions in particular. Conclusions are made about the possibility of regulating the colloidal structure of asphaltene-containing systems.

An intensive usage of oil as the main raw material of modern civilization resulted in a great reduction of its reserves. Earlier no need for interest in the structure of oil was evident because of the usage of light (unstructured) oil.
Nowadays more and more heavy (structured) oils are used in industry and ideas of **colloid structure** of oil appear.

Oil systems consist of hydrocarbons (alkanes, naphthenes, arenes) and nonhydrocarbon compounds (mostly resins and asphaltenes). Element composition of oil varies greatly.

Oil dispersed systems can be called **semi-colloid** (by Ostwald's classification). They are sophisticated dynamic systems where same molecules can (under different conditions) combine into disperse medium or continuous phase.

Main associating molecules in oil are heteroatomic oil compounds – **asphaltenes**. There association leads to dispersion (disintegration) of the whole system that results in the division into disperse medium and continuous phase. Oil dispersed systems – systems with low-polarity or non-polar medium (oleodispersed systems) – are created. Even a slight change in environmental conditions can lead to the **reorganization of the internal structure** of the oil system in whole. Understanding of such changes is important for every process in oil industry. For this purpose understanding of asphaltenes structure and phase behavior is necessary.

The analysis of modern experimental data gave us ability to answer the question about asphaltenes composition. However asphaltenic structure differs from source to source. But some facts are obvious: asphaltenes consist of C (< 88%), H (< 10%) and heteroatoms (< 14%; ≈ 2% are metals). Asphaltenes can form **81%** of heavy oil.

Formation of **permolecular structures** in asphaltenes solutions is determined by **intermolecular interactions** of different kinds. Possibility of such interactions is a result of the presence of various functional groups. **Electronic heterogeneity** of asphaltenes can cause appearance of complexes with charge transfer. Physical property determining the ability of aggregation of asphaltenes is a **dipole moment** (from 3 to 7 D). Dipole-dipole interactions are playing the main part in asphaltenes associations.
Modern science uses **cluster conception** and models to describe different structured systems. Similar ideas and models are perspective in explanation of many processes of structuring in colloid systems and determination of correlation between macro- and microscale. Usage of these ideas in an oil field is a new task for petroleum and colloid science.

In works of I.R. Kuzeev a **hierarchic scope model** of oil dispersed systems is represented. Four scopes of the model are:

1) atomic-molecular

2) permolecular

3) a scale of an ensemble of structures

4) macroscale

Such method gives opportunity to describe any change of phase as a result of stepped structuring where lower level is a base for higher one. When applied this method gives the connecting parameter for the structure of any kind (a quantitative property of any fractal structure) – **fractal dimension**.

**Cluster-cluster** (fractal-fractal) **aggregation** is more realistic for colloid systems like oil/asphaltenes and can be used for understanding the mechanism of **sol-gel transition** (like **glass transition** of oil when unlimited cluster is formed).

Polarity of asphaltenes enables to use **dielectric spectroscopy** for examination of its solutions. It is demonstrated in our work.

Dielectric response analyzer, created by Physic department of Umea University (Sweden), was used in our research. Its dielectric cell made possible to carry out the experiment in a pressure range from $10^{-4}$ to 1.5 GPa and temperature interval from 250 to 320 K.

The plant is constructed from two separate blocks with different ranges (from $10^{-3}$ to $10^2$ Hz and from $10^2$ to $10^7$ Hz). The second one is an ordinary **HP 4192 A**, but the first one is made using special scheme. The connection is realized with common bus-bar **IEEE 488**.

Dielectric spectra of two concentrations (0.3 and 3 g/l) were measured in different solvents (benzene and toluene) under different temperatures (293, 312 K).
The pressure interval was from 1 to $10^4$ atm. Frequency ranged from $10^{-3}$ to $10^6$ with a step (common logarithm) 0.01-0.1.

Using results of experiment different dielectric response models were checked. The examined models are:

- Debye model

- Cole-Cole model

- Davidson-Cole model

- Havriliak-Negami model

- Jonscher “universal” (power) law

Using results of the analysis the **dependences on pressure** of models' parameters were found, **relaxation time** of particles in solid was estimated and their **characteristic dimensions**. Estimated values were compared with data received by independent methods. Energetic and thermodynamic aspects of asphaltenes behavior are discussed. That analysis rendered possible to make conclusions about possibility of colloid structure and **properties regulation** of asphaltenes' solutions and consequently oil.

The results of this work are necessary for analysis of dielectric spectrum of oil, which are made by authors under different temperatures (above and under the temperature of phase transition – **glass transition**) and pressures.

Печатается в 2009 году с дополнениями и исправлениями по:

Балабин Р.М., Сюняев Р.З. Dielectric spectroscopy of asphaltenes' solutions under high pressure. // Physics of Electronic Materials, PHYEM'05. – Калуга, 24–27 мая 2005 года / ФБГОУ ВПО «Калужский государственный университет им. К. Э. Циолковского». – Калуга: КГУ им. Циолковского, 2005.
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## ДИЭЛЕКТРИЧЕСКАЯ СПЕКТРОСКОПИЯ РАСТВОРОВ АСФАЛЬТЕНОВ ПРИ ВЫСОКИХ ДАВЛЕНИЯХ

Сюняев Р.З., Балабин Р.М.

научное направление – 3

форма доклада – у

г. Москва, 117437, ул. Ак. Волгина, 29-2-176

balabinrm@yandex.ru