EXPERIMENTAL TECHNIQUES

FOR DETERMINATION OF
SOLID PHASE FORMATIONS
AND GEL STRENGTHS

PETE 694
FALL 2009
 Topics
• Construction of hydrate phase diagrams
• Measurement of Wax Appearance
Temperature
• Determination of total asphaltenes
• Stability tests on asphaltene
• Gel strength measurements
• Practical examples of application for
TAPS (ISOPE presentation)
 Hydrate phase behavior rig

Temperature rating from -94 to 392°F and pressure upto 3000 psia.
 Procedure
• Sapphire cell is loaded with gas and brine of
representative composition and salinity
• System is pressurized and maintained at a given
value and cooling begins
• Cell contents are continuously recorded with a
video camera
• Hydrate formation is visually observed – this gives
one data point at a set pressure and temperature at
which hydrates form
• Visual observation is also verified using pump
pressure data – pump maintaining constant
pressure would suddenly react to hydrate formation
as significant amount of gas is consumed and vice
versa
 Visual Observations of Hydrate
Dissociation in 2% Brine at 1500
psia; gas is 99% methane

54.4oF 54.4oF 54.5oF 54.6oF

Hydrate Dissociation 4% Brine at 900 psia
7

6
Pump cc's Used to
Maintain Pressure

3
44.5oF
2

0
38 40 42 44 46 48 50 52 54
Temperature oF
 Hydrate phase diagram for pure
methane and 2% brine
3500
Pressure, psia

3000
Measured
2500 CSMHYD
2000 DBR
1500
1000
500
0
20 30 40 50 60 70

Temperature, deg F
Hydrate phase boundary of NG
1600
Equilibrium between hydrate, water & gas
1400

1200
Pressure, psia

Pipeline operating conditions?

1000 Safe operating
conditions
800

600
Changes in pipeline
operating conditions?
400
Pipeline operating conditions?
200
25 30 35 40 45 50 55
Temperature, deg F
 Wax characterization
• WAT/WPT – wax appearance or
precipitation temperature – appearance of
first wax crystal as temperature is reduced
• Other related terms used:
– Wax Dissolution Temperature – disappearance
of the last wax crystal
– Pour Point – lowest oil pumpability temperature
– Cloud point – sometimes synonymous with WAT
– Gel point
• Gel strength measurement
Typical waxy oil behavior
 Oil samples used for wax
studies
• Dead oil (stock tank oils) used quite
frequently – will give a conservative
estimate because light ends are absent
• Live oil is also used but experimental
conditions are somewhat difficult to
control/handle
 Experimental techniques
• ASTM D3117 visual observation of wax –
method is good for colorless samples
(applicable for very light volatile oils or
condensates)
• CPM – cross polar microscopy
• DSC – differential scanning calorimetry
• Viscosity measurements versus
temperature
• Filter plugging – dynamic tests (various
designs)
 ASTM D3117

Electric
Motor
Retort
Stand Stirrer

Thermometer

Sample
Tube

Transparent
Glass Flask
Containing
Dry Ice

The Koehler Apparatus

CPM
 Viscosity measurement
14.0
12.0 Measurement for tridecane; instantaneous
Viscosity (cp)

change in viscosity trend

10.0
8.0
6.0
4.0
2.0
0.0
-10.0 -5.0 0.0 5.0 10.0 15.0 20.0
Temp (C)
Crude oil
 Filter plugging

Figure 1. Apparatus for the measurement of WAT under simulated pipeline (dynamic) conditions.
 Filter

From To HG
IP

Transducer

From
CP To Drain

To
CP

The Flow Loop of the Dynamic Solid Deposition Test Apparatus

IP = Isco Pump, HG = Heise Gauge, CP = Circulating Pump (Prep-100 Pump)
 0.14

0.12
Differential pressure, MPa

0.10

0.08

0.06

0.04

0.02
WAT = -31.7oC

0.00
-15 -20 -25 -30 -35 -40

Temperature, oC
 Gel strength
MODELS USED:
Data
(1) LVDV-II+
Collecting
Julabo
(2) LVDV-II+CP
Computer Viscometers (3) RVDV-II
System
 Cone Sample Cup

Small Sample
Adapter
CP40 Spindle

SC18 Spindle

Sample Cups and Spindles

Custom Designed
Vane Spindle
 80 o
50% BPGTL @ -20 F
(LV viscometer)
60
% VMTC

40

20 ts = 76% VMTC
= 97.81 dyne/cm2
0
0 10 20 30 40
T ime (min)
Wax modeling
• Wax Appearance Temperature (WAT) modeling by an EOS
is basically treated similar to, for e.g., a bubble point
calculation, as described by Ahmed (2007) on a stock
tank or dead oil or as suggested by Pedersen et al. (2014)
to perform a normal VLE calculation followed by a SLE
calculation on the equilibrium liquid phase:
• Basis is n moles of feed splitting into nL and nS moles of
liquid and solid respectively
n = nL + nS or in terms of individual components Zin = XinL +
SinS
Left hand side is total moles of component “i” in the feed
that splits into moles of that component in the liquid and
solid phases respectively 25
 Contd.
All mole fractions sum up to 1, i.e., n n n

Z
i 1
i  1;  X i  1;  Si  1
i 1 i 1
If calculations are done on the basis of 1 mole of feed, then
1 = nL + nS or in terms of individual components Zi = XinL + SinS
Defining the equilibrium ratio, Ki = Si/Xi or Si = KiXi, Zi = XinL + KiXinS

Zi K i Zi
Xi  Si 
n L  KinS n L  KinS

When wax forms, nS  0, i.e., nL = 1; such that Si=KiXi (because feed is liquid). The
below summation should equal 1 at the correct/converged values of Ki’s
n

K X
i 1
i i 1

26
 Contd.
Ki is also defined in terms of the ratio of fugacity coefficients of individual
components in the mixture:

 iL
Ki  S
i

The fugacity coefficients of individual components are determined from the

functional forms of PR or SRK EOS; however, before that step in order to begin
the iterative process, the initial estimates can be obtained from various
equations suggested by Pedersen et. al. (2014) and Ahmed (2007).
The fluid composition heavy end needs to be defined in terms of wax formers
and non-formers under the assumption that only C7+ components can form
wax, and only some part of each component splits into a wax former and non-
former.

27
 Contd.
Pedersen et. al. (2014) suggested the following functional form:

   ρ  ρ P

0.1915

Zi  Zi 1  1.074  0.0006584M i 
S total i i
 ; Zitotal  ZSi  Zinon
  ρi  
P
  

Zitotal is the total mole fraction of a given component, which is split into solid
forming and non-forming. ρ i is the density of a normal paraffin of the same
P

molecular weight as carbon number fraction i, calculated from the following

empirical equation:
ρ  0.3915  0.0675LN(Mi )
P
i
If Zsi results in a negative value the wax content is assumed to be equal to
zero, Pedersen et. al. (2014).

28
 Class Exercise on wax
Molar composition, molecular weight and specific gravity of various
components for a separator liquid drawn from a test separator at 600 psi and
110oF are provided in the table below. A sub-sample of this separator liquid
was transferred to a PVT recombination cell at 600 psi and ambient
temperature after the sample had been sitting in the lab for a long duration.
This oil is known to be waxy in nature and it is suspected that in the transfer
process wax precipitated and all of it remained in the separator liquid sample
bottle while 100% of the liquid portion was successfully transferred to the PVT
cell.
(a) Report the composition of the wax remaining in the separator liquid sample bottle
following the transfer process.
(b) Also determine the composition of the liquid transferred to the PVT cell.

29
Contd.
Component Sep. liq., comp., Mol. Wt., Density,
mole% gm/gm-mole g/cc
Nitrogen 0.301
Hyd. Sul. 0.013
Car. Diox. 0.052
Methane 0.691
Ethane 0.832
Propane 2.580
Isobutane 1.313
N-Butane 4.073
Isopentane 3.351
N-Pentane 2.069
Hexanes 4.847
Heptanes 5.525 103.90 0.7201
Octanes 6.082 120.77 0.7474
Nonanes 4.848 128.73 0.7683
Decanes 5.323 133.94 0.7947
Undecanes 4.760 144.83 0.8024
Dodecanes 4.275 156.75 0.8146
Tridecanes 4.159 171.59 0.8258
Tetradecanes 3.849 179.13 0.8376
Pentadecanes 3.684 196.41 0.8449
Hexadecanes 3.548 203.51 0.8480
Heptadecanes 2.957 214.04 0.8457
Octadecanes 2.288 223.34 0.8501
Nonadecanes 2.385 253.77 0.8645
Eicosanes+ 26.195 398.90 0.9559
100.000
30
 Asphaltene characterization
• Static asphaltene test to determine total
asphaltene content in a given oil or
condensate sample
• Asphaltene stability tests to determine the
solubility power of oil with regards to
asphaltenes
• SDS system for asphaltene studies
STATIC ASPHALTENE DEPOSITION
PROCEDURE:

(1) ASTM D2007-80/IP 143

(2) Mixed 20 ml crude oil and 800
ml of precipitant and aged for 2 Vacuum
days. Shook it at least twice. Source

(3) Filtered through 0.22 micron

filter paper.
(4) Re-dissolved residue in toluene.
(5) Filtered again through 0.22 Mass
micron filter paper. Balance

(6) Re-precipitated the asphaltenes

Glass
by adding excess volume of the Filtration
original precipitant. System
(7) Dried the asphaltenes in the
hood for several days.
Static Asphaltene Deposition Test Apparatus
(8) Calculated mass of asphaltenes
per 100 ml of crude oil.
 2.0

Asph. (g/100 ml)

1.5
1.0

0.5
BPGTL
0.0 n-Pentane
n-Heptane
ASPHALTENE STABILITY TEST
A

A :- Thermometer
B :- Cannon-Fenske viscometer
C :- Constant temperature bath
C
D :- Stop clock

Apparatus for Asphaltene Stability Test

PROCEDURE:

(1) Condition: Atmospheric

(2) Sample contained certain cc of toluene per gram
of crude oil.
(3) Measured the time for sample to flow freely from
“C” to “E”.
(4) Titrated 0.05 cc of n-heptane into the sample.
(5) Continued the process until sufficient data was
obtained.
(6) Plotted square of effluent time against titrated
volume of n-heptane, and obtained the
asphaltene flocculation point from this plot.
(7) Prepared a plot of titrated volume of n-heptane
at the onset of asphaltene flocculation against the
concentration of toluene in the test fluid.
(8) Positive intercept implied asphaltene stability in The Cannon-Fenske Viscometer
the pure ANS crude oil (Dandekar et al, 2000).
(cc per gm of crude oil)
Floc. Onset Point 1.2

0.8
y = 0.625x + 0.6625
0.4 2
R = 0.8929

0.0
0.0 0.2 0.4 0.6
Vol. of Toluene per gram of Crude Oil (cc/g)
South American oil