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Asphaltene: A General Introduction

Jianxin Wang
P & Sc Group PRRC, New Mexico Tech Oct. 18, 2000

Outline
What is asphaltene? Why to study asphaltene? How to characterize asphaltene stability in crude oil?

Asphaltenes are the most heavy and polar components in crude oil
Crude oil

Saturates

Aromatics

Resins

Asphaltenes (0-20%)

S
nonpolar

molecular weight, polarity & aromaticity

Separating asphaltene from crude oil


ASTM D2007-80: Mixing crude oil / n-C7 (or n-C5) = 1 / 40 Aging for two days Filtering through 0.22 m filter paper

Separated asphaltene amount is determined by precipitant molecule size


50 40

Asph. (wt%)

30

20

10

10

12

Chain-length of n-alkane precipitant

Separated asphaltene amount is also determined by precipitant/oil ratio


8 7

Asph. (wt%)

6 5 4 3 2 1 0 2 5 10 20 50

Mars-pink
100 200 500

n-C7 / oil ratio

Furthermore, separated asphaltene amount is also time-dependent


5.8 5.6

Mars-pink/nC7=1/10

Asph. (wt%)

5.4 5.2 5 4.8 4.6 4.4 4.2 1 2 5 10 20 50 100 200

Aging time (days)

Asphaltene is a compositional continuum


n-C7 asph.

Molecular weight

n-C5 asph.

polarity = N, S, O aromaticity =

Polarity & aromaticity


Long, R.B.: "The Concept of Asphaltenes," Chemistry of Asphaltenes, J.W. Bunger and N.C. Li (eds.), ACS, Washington, DC (1981) 17-27.

Typical asphaltene molecular properties


H/C = 0.8 - 1.4 Molecular weight: depends on solvent and concentration monomer = 500 - 1000 micelles = 1000 - 5000 Heteroatoms: acting as polar functional group S=0.5-10 wt%; N=0.6-2.6 wt%; O=0.3-4.8 wt% Metal elements: Ni, V, Fe

Hypothetical polycyclic structures for asphaltene molecules

OH N S S N N S S S O

Speight, J.G.: "A Chemical and Physical Explanation of Incompatibility during Refining Operations," Proc. 4th Intl. Conf. on the Stability and Handling of Liquid Fuels, US Dept. Energy, 169 (1992).

Asphaltene? Like a sea monster

Differences between asphaltene and wax

Asphaltene Dissolves in heptane: Crystalline: Melting point: No No No

Wax Yes Yes Yes

Buckley, J.S.: "Asphaltenes: Separating Fact from Fiction," SPE Distinguished Lecture Slides (1998-99).

Outline
What is asphaltene? Why to study asphaltene? How to characterize asphaltene stability in crude oil?

What if asphaltene flocculates ?


fouling production facilities

plugging reservoir

Asphaltene Flocculation
poisoning refinary catalysts altering wettability

Stability is determined by crude oil solvency


Composition
- gas injection; - phase separation; - incompatible chemicals; - mixing of crude streams; - etc.

Asphaltene stability

Temperature Pressure

High asphaltene content is not necessary to associate with high risk of trouble
troublesome
100

troublefree
asphaltenes resins

80

Weight %

60

40

aromatics saturates

20

10 11 12 13 14 15 16 17 18 19

Oil # from Venezuela oil fields


Carbognani, L. and Espidel, J.: "Characterization of Solid Deposits from Production Facilities. Identification of Possible Causes of Deposits Formation," Vision Technologica, Vol. 3, No. 1, 35-42.

Asphaltene trouble is associated with RI


troublesome
1.55

troublefree

1.50

PRI

RI
1.45

Low RI
1.40 1 2 3 4 5 6 7 8

High RI
9 10 11 12 13 14 15 16 17 18 19

Oil #
Buckley, J.S.: "Asphaltenes: Separating Fact from Fiction," SPE Distinguished Lecture Slides (1998-99).

Outline
What is asphaltene? Why to study asphaltene? How to characterize asphaltene stability in crude oil?

For a given crude/precipitant, flocculation occurs at a critical RI


RI
stable
onset

crude oil

PRI
redissolved

maltene

alkane

flocculated

Volume fraction
Buckley, J.S.: "Asphaltenes: Separating Fact from Fiction," SPE Distinguished Lecture Slides (1998-99).

Asphaltene stability varies with solvent RI


High RI

In a "good" solvent, asphaltenes are not strongly attracted to one another.

In a "poor" solvent, asphaltenes attractive forces are enhanced.

Low RI

Buckley, J.S.: "Asphaltenes: Separating Fact from Fiction," SPE Distinguished Lecture Slides (1998-99).

RI measurement
sample

GPR-11-37

Sodium-D light beam

refractometer
RI accuracy = 0.0001 T: 10 ~ 70 C

total internal reflection

n=

1 sin( )

Procedure for onset detection


Prepare a series of mixtures with varying oil/precipitant ratios in sealed vials Aging for 24 hours Observe asphaltene precipitation, if any, under microscope Once onset is detected, record volume ratio and measure the refractive index (RI) for mixture

Asphaltene flocculates under microscope (1)

3 2

Asphaltene flocculates under microscope (2)

PRI vs. time (Lagrave)


1.50 1.49 1.48

n-C15

PRI 1.47
1.46 1.45 1.44

n-C9

n-C5

particle onset aggregate onset


0 2 4 6 8 10 12 14 16 18

Time (day)

Volume ratios of precipitant to oil at onset


4

Vprecipitant / Voil (ml/ml)

3
A-93 A-95 Lagrave Lost Hills Mars-pink Tensleep

10

12

14

16

Chain-length of n-alkane

RI at onset (PRI) for crude oils


1.52 1.50 1.48
A-93 A-95 Lagrave Lost Hills Mars-pink Tensleep

PRI

1.46 1.44 1.42 1.40

10

12

14

16

Chain-length of n-alkane

Simple correlation of PRI vs. precipitant


1.52 1.50 1.48

Crude oils average r = 0.992


A-93 A-95 Lagrave Lost Hills Mars-pink Tensleep

PRI

1.46 1.44 1.42 1.40 10

11

12

13

14

15

16

17

vp

Conclusions
Asphaltene molecules are polyaromatics with side chains. They exist in crude oils as monomer and micelles equilibrated to each other. The sizes of asphaltene micelles fall in colloidal range. Asphaltene flocculation occurs when oil solvency is reduced. Flocculated asphaltene could have detrimental effects on oil production, transportation and refinary process. Refractive index (RI) is a simple, readily measurable parameter for characterizing crude oil solvency with respect to asphaltene stability.