High Temperature Carbonate Fluid U820

A carbonate matrix stimulation

engineering solution
$SSOLFDWLRQV Low pH chelating agent fluids based on U106 (field mix U820) can be used
to produce wormholes and increase the permeability of limestone and
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dolomite formations. We have demonstrated that chelating agent
FDUERQDWHV formulations can be formulated into efficient solvents for acidizing limestone
cores, over a wide range of pH values. Dominant wormholes were produced
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at temperatures as high as 200 oC (400 oF). Predictions of optimal flow rates
VFDOHIURPQRQ using the Damkçhler number equations are close to the observed values of
FDUERQDWHIRUPDWLRQV the current study.
಴ %HQHILWV The mechanism involves:

฀ Stable to 400 oF
CaCO3 + 2 H+ = Ca2+ + CO2 + H2O (1)
฀ Acid solutions can be
inhibited to 400 oF with
0.4% A272 with no CaCO3 + Na3HEDTA = NaCaHEDTA + Na2CO3. (Equations 1 and 2
addition of intensifiers are both operatives at low pH, while only equation 2 is operating at pH 12.
The low pH solvents appear to be very effective and efficient matrix fluids at
฀ Has been used high temperatures where HCl (and organic acids) are too aggressive to
successfully in produce efficient wormholes at typical flow rates for most matrix treatments.
U820 (pH 4) should be used for temperatures > 300 oF and U821 (pH 2.5) at
MudSOLV temperatures < 300 oF.. Wormholes also have been proven to 400 oF using
formulations for filter very moderate pumping rates. See Below. Based on comparisons of
cake clean up wormhole morphology, a solution of U820 used to stimulate limestone at 350
oF appears to be equivalent to 15% HCl used at 150 oF and the same
฀ Wormhole formation pumping rate. The 15% HCl solution (or organic acids would be much too
documented to 400 oF aggressive at 350 oF and would cause general face attack). The only real
alternative would be SXE-HT.
฀ Formulations have
The chelating agent formulations have lower viscosity values compared to
not formed sludge in
emulsified acid and should be easier to place using coiled tubing. In addition,
contact with waxy these fluids can be inhibited with small amounts of special formulations to
crude and Fe(III) iron produce very low corrosion rates, even at high temperatures. These
materials should be more efficient than the organic acid blends, based on the
)HDWXUHV data reported here for acetic acid and formic acid, which are too reactive at
350 oF to produce efficient, dominant wormholes.
฀ :RUPKROHIRUPDWLRQ
PRGHOHGZLWK
6WLP&$'( Core Flood at 400 F, 50% U106
6HYHUDOSDWHQWVLQ 400
DSSOLFDWLRQVWDJH 350
฀ 63(SDSHUV 300 pH 4, 10 mL/min

DQG
Perm (md)

250 4 12
pH 2.5, 15 mL/min
GHVFULEH 200
WHFKQRORJ\ 150 pH 12, 5 mL/min

2.5
100
50
0
40 50 60 70 80 90 100
Time, min
 Comparison of Viscosity

25
20 50%U106/pH 4

Viscosity, cP
15
SXE-HT 15% HCl
10
5 Poly.
(50%U106/pH 4)
0 Poly. (SXE-HT
0 100 200 300 400 15% HCl)
Temp. oF

EXTRODINARY CORROSION PROTECTION

The U821 formulations are unique fluids that have proven to cause much less sludge formation in the
presence of ferric iron and waxy crude oil. Figure 3 show the break out of acid in contact with a
Colombian crude oil and U820 containing 2000 ppm Fe(III).
Corrosion inhibitor schedules have been developed for U820/U821 that includes carbon steel, coiled
tubing and 13 Cr tubing and allows treatments to be performed to 400 oF.

Effect of Additives on Corrosion Inhibition

U820 - 400F - 4 hours
0.05
0.05
Corrosion Rate (lb/ft2)

0.04
0.04
N8 0 13 % C r
0.03
In h i b i t o r C o n c e n t r a t i o n
0.03
N 8 0 a n d 13 % C r : 0 . 4 % In h A 2
0.02
0.02
0.01
0.01
0.00
None 0.5% F75N 0.5% F103 5% U66 5% U067
Additive
 Fluid Selection - Efficiency Criterion

8
U820

HCl
HAc
Pump Rate (bbl/min)

6 EDTA

3
U821
HFc
2

1
No Fluid Available
SXE
50 100 150 200 250 300 350 400
Temperature (°F)