Paraffin Deposition in
Petroleum Production
100
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Carbon Number
Fig. 1-Typical oil composition vs. carbon
number.
Introduction
Precipitation of solids, generically called
''paraffins, ' ' is a well-recognized· produc-
tion problem. The severity and nature of the
problem can be predicted by use of accurate
composition of the c7 + fraction and prin-
ciples of solution thermodynamics.
Paraffin problems commonly result from
cooling and subsequent precipitation of high-
molecular-weight hydrocarbons during tran-
sit from the reservoir to the surface. Paraffin
deposits form on the wall of downhole tubu-
lars and in low-velocity zones near entrances
and exits of chokes, collars, or similar re-
strictions in the flow path. Costly preven-
tive chemical treatments or remedial
workover procedures are required to cut
away the paraffin deposit with mechanical
knives or scrapers. As an alternative, hot oil
can be used to melt these deposits.
Even more significant, but generally un-
addressed, is the problem of backpressure
on the reservoir caused by paraffin deposits
in the production tubing, which decreases
the fluid withdrawal rate and defers produc-
tion. Heavy hydrocarbons can also precipi-
tate within the reservoir, reducing the
permeability at distances that are untreata-
ble from the wellbore, thereby posing a large
production restriction.
Precipitation of solid paraffin is actually
an example of fluid/solid phase equilibrium.
It is explained in terms of established prin-
ciples of thermodynamics of solutions-i.e.,
the solution of higher-molecular-weight
hydrocarbons in lower-molecular-weight
hydrocarbons that act as a solvent. 1-4
1024 - --------------------------------------------------------------------------October 1989•JPT
Norman F. Carnahan, SPE, Rice U.
Simply put, high-molecular-weight solids
precipitate ":'henever anything occurs that
decreases the carrying capacity of the fluid
solvent. Three classes of problems associat-
duction are supercritical fluid phenomena in
the reservoir; temperature changes in the
production tubing; and pressure and temper-
""'~~ ature changes in surface facilities, gather-
ing systems, and trunklines .
50 60 70
Supercritical Solvent Effects
in the Reservoir
In deep, hot reservoirs, fluids have
equilibrated over geologic time. The reser-
voir temperature typically exceeds the crit-
ical temperature of several of the light ends,
such as methane and ethane, and associated
nonhydrocarbon gases, such as nitrogen and
C0 2 . These '' supercritical'' components
are known to act as effective solvents5-7 for
heavy ends. The most notable application of
supercritical-solvent extraction technology
is the decaffeination of coffee with C0 2 .
Similar applications demonstrate the general
affinity of supercritical fluids for macro-
molecular solutes.
When a well begins producing hydrocar-
bons and associated fluids to the surface, a
pressure gradient is established, resulting in
flow of reservoir fluid through the porous
medium. The.· carrying capacity of the
supercritical-solvent fraction decreases dra-
matically as the pressure decreases in the
direction of the wellbore. Precipitation of
dissolved heavy ends, 8 in the reservoir
rock, is predictable. Accumulation of
precipitated heavy ends in the reservoir is
a plausible contribution to relative permea-
bility decrease with cumulative production.
Temperature Changes in
Production Tubing
Solids deposition in production tubing, the
most common example of the paraffin prob-
lem observed in production, is primarily a
result of decreasing temperature, which
_ Reliable sampling and compositional
causes a certain portion of the high-
molecular-weight fraction to precipitate. ·1 ,2
Mechanisms other than decreasing temper-
ature, such as pressure change, can reduce
the carrying capacity of the solvent fraction
Copyright 1989 Society of Petroleum Engineers
of the reservoir fluid during transit from bot-
tomhole to the surface. Pressure change re-
sulting in liberation of volatile light ends as
gas may prove to be a very significant mech- -
anism in terms of its impact on overall
recovery of oil and gas.
Pressure and Temperature /
Changes in Surface
Facilities and Pipelines
Precipitation of paraffin in surface equip-
ment results from lower fluid temperature
and from a decrease in fluid pressure. In
separators, precipitation results from flash-
ing and the resulting decrease in the amount
of light ends that are part of the solvent frac-
tion. Paraffin deposition in surface equip-
ment is a relatively minor technical problem
because it is easily accessible and most of
the heavier fraction has already precipitated
in the well bore and the reservoir.
Nonetheless, paraffin deposition in trunk-
lines and transmission lines exposed to se-
verely cold climatic conditions remains an
expensive aspect of getting oil to the mar-
ketplace, especially when pipelines are on
the ocean floor, such as at the Beatrice
field 9 in the North Sea and the Hibernia
field offshore Newfoundland, or in Arctic
regions, such as the Alaskan North Slope,
the Daqing and Shen-Yang fields in north-
ern China, and fields in Siberia.
Reservoir Engineering
of Paraffin Fluids
Today's reservoir fluid must be thought of
as a complex mixture of light ends (methane,
ethane, propane, butanes, pentanes, hex-
anes, etc.) and heavy ends (a near-
continuum of molecular weight fractions
characterized as distributions of paraffins,
naphthenes, aromatics, resins; bitumens,
asphaltenes, etc.). It is not sufficient to char-
acterize reservoir fluids simply in terms of
weight percent C 7+, ASTM D-86 Pour
Point, and API gravity.
analysis 10 of the reservoir fluid, _initially
and during production, are essen~1~l. Ac-
curate knowledge of fluid compositiOn en-
ables the engineer to forecast and define the
severity of paraffin deposition problems as-
sociated with production.

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-400
0 20 40 60
Carbon Number
Fig. 2-Solidification temperatures vs. carbon number for nor-
mal paraffin hydrocarbons.
Fig. 1 shows a semilogarithmic distribu-
tion of molecular weights (expressed as car-
bon numbers, in this example) for a sample
of west Texas (San Andres) crude oil. The
semilogarithmic distribution of carbon num-
bers or molecular weights is typical of many
naturally occurring petroleum fluids.
Fig. 2 illustrates a correlation of the
solidification temperature experimentally
determined for various high-molecular-
weight n-alkane paraffin hydrocar-
bons.ll-13 When a reservoir fluid cools to
temperature T, paraffin hydrocarbons hav-
ing solidification temperatures greater than
Ttend to precipitat~ from solution.:Similar
data exist-or can he experimentally deter-
mined for ilonparaffin hydrocarbons and
other components of reservoir fluids.
Fig. 3 illustrates the relation between the
temperature of a petroleum mixture, origi-
nally liquid at reservoir temperature, and the
cumulative percent of the total mixture that
precipitates as a solid for a North Sea crude
oil sample as reported by Pedersen et
al. 3,14
The modern approach to reservoir engi-
neering recognizes that accurate composi-
tional analysis of petroleum fluid~, together
with reliable experimental data for solidifi-
cation temperatures-heats of fusion, etc.-
for individual components, allows the en-
gineer to predict the amount and composi-
tion of solid_ that will precipitate from the
reservoir fluid.
Summary
1. Solids deposition mechanisms must be
more generally recognized and understood
to make better economic decisions concern-
ing the modem approach to petroleum reser-
voir development, production system design
JPT • October 1 9 8 9 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 1 0 2 5
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80
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u
60
Q.
Q
'i
;:
40
20
0
- 2 50 - 2 0 0 -1_5 0 -1 0 0
80 100
Fig. 3-Cumulative solids precipitation vs. temperature for a
North Sea crude oil (from Pedersen et a/.1 4).
for primary production, and enhanced
recovery.
2. Solids deposition is quantitatively pre-
dictable, based on accurate compositional
analysis of the whole reservoir fluid, espe-
cially the c7 + fraction, in terms of
paraffin/naphthene/aromatic (PNA) and
molecular weight distribution. Solution-
theory calculations show good correlation
between predicted and observed quantities
and composition of precipitated solids.
3. Solids deposition is manageable, based
on conventional, established principles of
solution thermodynamics, chemical addi-
tives, etc.
4. Solids deposition in petroleum produc-
tion consists of wax and asphaltene precipi-
tation, and is related to polymer solutions
(especially extraction of polymer fractions),
supercritical fluid extraction technology.
These phenomena are quantitatively predict-
able by means of the thermodynamics of
continuous high-molecular-weight mixtures
and thermodynamics of solutions.
Paraffin deposition is ( 1) an example of
fluid/solid phase equilibrium; (2) a result of
changes in "solvent capacity" of lighter
ends to dissolve heavy "solute" molecules
resulting from temperature changes in the
wellbore, pressure and temperature changes
in surface equipment and pipelines, and su-
percritical solvent phenomenon in the reser-
voir; (3) predictable when based on accurate
reservoir fluid composition analysis;
(4) manageable by use of conventional prin-
ciples of solution thermodynamics; and
(5) related to asphaltene precipitation, poly-
mer solution behavior, supercritical fluid so-
lutions, and thermodynamics of continuous
mixtures.
Accurate compositional analysis of the
c7+ fraction is the key to better engineer-
sPE Technology
Today sERIES
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- 50 0 50 100
Temperature, of
ing and-management of paraffin problems.
Together with principles of solution thermo-
dynamics, the composition allows quantita-
tive prediction of the nature and severity of
the problem and provides a useful method
for estimating the effectiveness of proposed
remedial measures.
References
1. Won, K.W.: "Thermodynamics for Solid-
Liquid-Vapor Equilibria: Wax Phase Forma-
tion From Heavy Hydrocarbon Mixtures,"
Fluid Phase Equilibria (1986) 30, 265-79.
2. Weingarten, J.S. and Buchner, J.A.:
"Methods for Predicting Wax Precipitation
and Deposition," SPEPE (Feb. 1988)
121-26.
3. Hansen, J.H. et al.: "A Thermodynamic
Model for Predicting Wax Formation in
Crude Oils," A!ChE J. (1988) 34, No. 12,
1937-42.
4. Carnahan, N.F.: "Solution Theoryfor High
Pour Point Paraffinic Oils," paper 36b
presented at the 1988 AIChE Natl. Meeting,
New Orleans, March 6-10.
5. Kim,-S. and Johnston, K.P.: "Clustering in
Supercritical Fluid Mixtures,'' A!ChE J.
(1987) 33, No. 10, 1603-11.
6. Campanella, E.A., Mathias, P.M., and
O'Connell, J.P.: "Equilibrium Properties of
Liquids Containing Supercritical Sub-
stances," A!ChE J. (1987) 33, No. 12,
2057-66.
7. Debenedetti, P.G. and Kumar, S.K.: "The
Molecular Basis of Temperature Effects in
Supercritical Extraction," AIChE J. (1988) ,
34, No. 4, 645-57.
8. Carnahan, N .F.: "Reservoir Fluids Classifi-
cation for EOR,'' Proc., DOE Regional
· Forum o~ Geoscience Research, Houston
(June 16-17, 1988).
(To Page 11 06)
Paraffin Depositio·n in
Petroleum Production
(From Page 1025)
9. Carnahan, N.F. : "Beatrice Field Develop-
ment: Productibn System a:nd Pipelines for
High Pour Point Waxy Cnide Oil in the North
Sea, " The Hansard (Official Publication of
the Houses of Parliament), London (1978) .
10. Green, J.B . et al.: " Analysis of Heavy Oils:
Method Development and Application to
Cerro Negro Heavy Petroleum;' ' Fossil Ener-
gy Series, NIPER-323 (DE89000746) (June
1989).
11. Schaerer, A.A . et al.: "Properties of Pure
Normal Alkanes in the C 17 to C 36 Range,"
1. Amer. Chern. Soc. (1955) 77, 2017-19.
12 . Broadhurst, M.G.: "Ah Anaiysis of the Solid
Phase Behavior of the Normal Paraffins ,'' 1.
Res. Nat!. Bureau of Standards-A, Physics
and Chemistry (May-June 1962) 66A, No .
3, 241-49.
l3. Motgan, D.L.: "Extension of Pitzer Cotre-
sponding States Correlations Using New
Vapor Pressure Measurements of the n-
Alkanes C 10 to C 28 ," PhD dissertation,
Rice U. , Houston ( 1989).
14. Pedersen, K.S. , Thomassen, P., and Fredens-
iund, A.: " Thermodynamics of Petroleum
.ty[ixtures Containing Heavy Hydrocarbons:
3. Efficient Flash Calculation Procedures
Using SRK Equation of State," Ind. &
Eng. Chern. Process Design & Development
(1985) 24, 948.
il06 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - O c t o b e r 1989 • JPT
General References
Abbasian , M .J. and Wei!, S.A.: " Phase
Equilibria: of Continuous Fossil Fuel Process
Oils ," AIChE 1. (1988) 34, No . 4, 574-82.
Chandler, ·D., Weeks, J.D., arid Andersen, H.C.:
" Vim der Waals Picture of Liquids and Phase
Transfom1ations," Science (1983) 220,787-94.
Riazi, M.R. and Daubert, T.E .: "Simplify Prop-
erty Predictions,' ' Hydrocarbon Processing
(March 1980) 115 . Carnahan
Vimalchand, P. and Donohue, M.D.: " Compar-
ison of Equations of State for Chain Mole- Norman F. Carnahan teache~ ~her­
cules," 1. Phys. Chern. (1989) 93, No. 10, modynamics at Rice U. and petroleum
4355-60. fl.uid properties and phase behavior at the
u. of Houston. As president of Carnahan
Yu, i.M., Wu, R.S ., and Batycky, J.P.: "Charac-
Corp.; a Houston-based international con-
terization Method for Bitumen Phase Behavior
Predictions," Proc. , AIChE Nat!. Meeting , . sulting engineering firm established in
~ 977; Carnahan assisted the development
New Orleans (March 1988) paper 36e.
of tt'le Beatrice field, the first high-wax-
content crude oil project in the North Sea.
Sl Metric Conversion Factor He has provided technical consulting for
op (°F-32)/ l.S = oC the Hibernia field, for heavy-oil and high-
pour-point-oil projects in the Alaskan
North Slope, North Africa, and China, .ana
Provenance . for numerous domestic and foreign EOR
This paper is SPE 19895. Technology To- projects. He holds a BS degree from ~he
day Series articles provide useful summary U. of Houston and a PhD degree fi"om the
information on both classic and emerging U. of Oklahoma, both in chemical engi-
neering. His engineering and research in-
concepts in petroleum engineering. Pur- terests involve the behavior of fluids and
pose: To provide the general reader with a fluid mixtures, including fluid/solid phase
basic understanding of a significant concept, behavior · and its relation to rheological
technique, or development within a specific properties of mixtures.
area of technology.
JPT