22 - Carbonate - Fluid Design

Acid Formulations
Copyright 2009, NExT, All rights reserved

CARBONATE RESERVOIRS
Basic reaction between HCL and limestone

2HCL + CaCO3 CaCL2 + H2O + CO2
1000 lit 220 kg 245 kg 40 lit
15%
1m3 HCL 15% dissolves 220kg or 81dm3 of CaCO3

HCl 15 % 28 %
Calcite 222 g/l 437 g/l
Dolomie 204 g/l 403 g/l
2
Acid… Which acid
• Most of the acid treatment on carbonated reservoir are
performed with HCl
• In most cases 15 – 20 - 28 % HCl is pumped. (15X – 20X -
28X) VITESSE DE REACTION / CONC. HCl
11
10
VITESSE REACTION (lb/ft2/sec x 10E4)
0
0 5 10 15 20 25 30 35
CONCENTRATION % HCl
3
Acid formulations
• HCl - Primary acid for • Acid and alcohool

carbonates
• Organic acids: • Emulsified acids
• Less dissolution capacity
• Higher temperatures
• HCl / organic blends
• Acid dispersion • Viscosified acid system
• Spearhead to prevent organic
deposit
4
Main characteristics
CO2 m3/m3
Acid Density kg/m3 of CaCO3 Used acid
(15,6°C) density (SCF/BBL)
disolved
HCl 7,5 % 1,037 106 1,1 24 (134)

HCl 15 % 1,0749 222 1,17 50 (278)
HCl 20 % 1,10 300 1,23 68 (379)
HCl 28 % 1,147 437 1,34 98 (550)
Acetic 10 % 1,0125 88* 1,08 20 (111)
Acetic 12 % 1,0154 101* 1,08 23 (127)
Formic 9 % 1,02 98 1,08 22 (123)
5
Main characteristics
REACTION PRODUCTS AND PROPERTIES OF HYDROCHOLORIC ACID

(Numbers based on 1000 gallons of acid or
the reaction of 1000 gallons of acid)
Hydrochloric Acid 7.5% 15% 20% 25% 28%
Density acid in lbs/gal 8.644 8.961 9.169 9.385 9.521
Specific gravity of acid 1.037 1.075 1.100 1.126 1.142
Gallons of water in acid 959 914 879 845 822
Lbs of CaCO3 dissolved (as calcite) 888 1843 2512 3213 3652
Cu ft of CaCO3 dissolved 5.25 10.9 14.9 19.0 21.6
Lbs of dolomite dissolved 824 1700 23115 2960 3267
Cu ft of dolomite dissolved 4.6 9.5 12.93 16.56 18.8
Lbs of CO2 formed 391 811 1105 1414 1607
Gallons of H2O formed 19.2 39.7 54.2 69.5 78.8
Approx. gallons of spent acid water 1011 1020 1025 1032 1035
Viscosity of acid (water = 1) 1.14 1.33 1.59 1.7 1.87
Viscosity of spent acid (water = 1) 1.35 1.94 2.69 3.40 3.90
Specific gravity of spent acid 1.096 1.175 1.233 1.295 1.34
Density of spent acid in lbs/gal 9.14 9.79 10.28 10.79 11.17
Concentration of spent acid as calcium chloride 11% 20% 26% 32% 36%
6
Organic Acids
• Three formulations used in the field

• Aqueous acetic acid
• Nonaqueous acetic acid
• Formic acid
7
Aqueous Acetic Acid
Advantages
• Can be inhibited for use at high temperature and
extended exposure time
• Slow reaction rate with carbonates
• Effective control of ferric irons at less than 125o F.
• Complexes Aluminum
8
Aqueous Acetic Acid
• Concentration
• 10% of glacial acetic acid in water
• freezing point = 62o F
• (70% acetic acid) - freezing point = -3o F
• can be used when freezing is a problem
• Specific Inhibitor
9
Non aqueous Acetic Acid
• Glacial acetic acid in kerosene or diesel

• Advantages
• Effective in removing water block
• Water sensitive formations
• Deep penetration
• Glacial acetic acid in kerosene or diesel
• Inhibition
• Non corrosive until contacting water
• Specific inhibitor is recommended
10
Formic Acid
• Concentration - up to 9%
• Slow reaction with carbonates
• Intermediate between HCl and Acetic Acid
• Inhibited for use up to 350o F
• Also used as preflush to organic mud acid
• Compatible with mutual solvents and most other additives
used with HCl
• Limitations
• Concentration > 9%
• Precipitation of calcium formate
11
Intensified Acid
• 15% HCl and 0.25% HF

• Used in dolomitic limestone (CaCO3 <60%)
• Beware of CaF2
12
Acid Dispersion
• Primary use is for removal of Hydrocarbon

commingled hydrocarbon and
scale deposits
• Paraffin
• Calcite
• Minimize acid-oil
incompatibility problems
• Dissolve carbonates
• Some viscosity (diversion) Acid
• Specific blending procedure
using two tanks and a choke
13
Acid Dispersion
• Blend aromatic solvent with any acid blend

• HCl
• Organic acid
• Need a dispersing agent
• Use corrosion inhibitors that are appropriate for the acid
system
14
Other Acid Systems
• Gas Well Acids

• Acid + 67% Methanol (by volume)
• Slow reaction rate
• Lowers surface tension
• Increases vapor pressure
• Improves spent acid clean up
• Acid Retardation
• Applications
• Dry gas wells and gas storage wells
• Temperature up to 250o F
15
Gas Well Acid Surface Tension
Surface Tension DYNE/CM
Temp = 77 F
Volume Percent of Alcohol in Solution
16
Viscosified Acid

Acid Systems: Interaction with Rock
Regular HCl SGD
Emulsified HCl
VES-HCl
SPE 71693 SPE 80225

18
Acid Emulsions
• Problem: Hydrochloric acid (HCl) does not

penetrate (wormhole) more than a few
inches into the formation in high
temperature wells.
• Benefits:
• Improved damage bypass via deeper wormhole
penetration in high temperature wells
• Deeper live acid penetration.
• Superior corrosion inhibition due to the oil outside
phase
19
Acid emulsion
Hydrocarbon
• Hydrocarbon external emulsion
• 15% to 30% hydrocarbon
Acid
• Up to 28% HCl
• Stable emulsions can be formulated for
~350F
• Effective diffusivity ~400 times lower than HCl [Li,
et. al., 1993].
• Leak-off control is achieved by emulsion and by
reduced effective reaction rate.
20
Emulsion Reaction Retardation
• Emulsion is significantly retarded with respect to HCl.
TABLE 4
RETARDATION FACTORS (RF)
HCl Laminar Flow

conc. (Re < 1800)
250°F 300°F 350°F

(121°°C) (149°°C) (177°°C)
15% 16.5 18 19
28% 15 16.5 17.5
21
Emulsion Stability
• Emulsion is stable for approximately one hour at 350oF.

• Emulsion stability improves corrosion inhibition.
Stability of Emulsion at Bottomhole
Static Temperatures
Temperature Required Time for 50%

° F [ ° C] Emulsion Break
250 [121] >12 hr
275 [135] 6 hr
300 [149] 4 hr
325 [163] > 2 hr
350 [177] ~1 hr
22
Emulsified Acida
• Emulsified Acid is Stable at Ambient Conditions

• > 15 Times Retarded
• Enhanced Core Permeability by > 40 Fold
• Shear-thinning Fluid
• No injectivity Problems
• Acceptable Corrosion Rates
• Minimum Amount of Additives
a. Nasr-El-Din et al., SPE 71693, 2001 23

Conclusions
• Acid emulsion is a highly retarded emulsified HCl acid

system used for:
• Improved damage bypass via deeper wormhole penetration in
high temperature wells
• Deeper live acid penetration
• Behaves as a viscosified acid and add a diversion mechanism
• Applications
• High temperature matrix stimulation of carbonate formations
i.e. temperature range 250oF-350oF
• Acid fracturing of high temperature carbonate reservoirs.
24
Gelled acid for diversion
It is possible to viscosify HCl solutions using :

• Specific polymers called Self Gelling Diverters : SGD
• They break with the PH
• Viscous elastic surfactant : VES
• They break with the oil produced during flow back
25
Self-gelling diverter
• Low viscosity if pH < 2 , µ µ

= 20 cp
• Crosslinks when pH = 3 , µ =
1000 cp
• Rigid crosslinked gel
• Breaks back when pH = 4 , µ
= 15 cp pH
2 4
26
Live Acid Spent acid gel

µ
pH
2 4
27
• Self-selective treatment
• No damaging, solid particles in the fluid system : flowed
back from the well along with the spent acid
• Applications :
• First applications in carbonates
• Used also in sandstone but with mixed results
• Best formulation : low acid strength in SGD stage - high
acid strength in neat acid stage
28
VES acid
• Viscoelastic Surfactant-based Leakoff Control Acid

• Polymer-Free
• Solutions of the Same Surfactant & HCl
• Low Viscosity System
• Control Leak-off Effectively
• No Metal Cross-linker (Eliminates Hydroxide and
Sulfide Precipitation) a
• Gel Breaking is Controlled
a (Nasr-El-Din et al., SPE 75257, 2002)

29
VES in HCl Solutions
CaCO3 + 2HCl ---> CaCl2 + CO2 + H2O
spent
acid
Worm-like Micelle
Monomers
30
VES-HCl: Gelling & Breaking
Live VES Acid + Spent Acid + Mutual Solvent
31
Viscosity of Live VES-HCl Solutions
250
200
Viscosity @170 s-1
150
100
Used in the Treatment

50
0
0 5 10 15 20 25 30
HCl Concentration (%)
7 vol% VES; Fann 35 @ RT

32
VES Fluids: Complete Break
Worm-like Micelle
Mutual Solvent
Breaking
Contact with hydrocarbons
Dilution with injection water Spherical Micelles
33
SELF GELLING AGENT
• Self gelling diverters

• Low viscosity if pH < 2, µ
= 20 cp
• Crosslinks when
pH = 3, µ = 1000 cp
• Rigid crosslinked gel
µ
• Breaks back when
pH = 4, µ = 15 cp
pH
2 4
34
QC : question raised
• Procedure of breaking of polymer

• Damage on low perm (critical for polymer)
• Damage of Wormhole sides?
• Face plugging with polymer
• No/little damage to wormhole with SGD and VES.
• Low FIP for both systems with liquid
• Influence of H2S
• Usage in gas wells
35
Comparison Emulsified acid and gelled acid
• Emulsified acid creates longer wormholes

• In situ gelled acid creates shallow wormholes
• Utilizing both acids can achieve deep, and wider
wormholes.
• It is recommended to increase the concentration
of iron control chemicals in the in-situ acids to
account for iron present in the formation and iron
that is produced by corrosion.
• Finally, in-situ gelled and emulsified acids are
retarded acids. It is therefore recommended to
increase the soaking time in the formation to
ensure complete spending of these acids.
SPE 65386: Jack D. Lynn, Saudi Aramco, H. A.
Nasr-El-Din, Saudi Aramco 36
Non acid solution using EDTA
• Used as formation clean up or breakdown fluid in
formations that may be damaged by acid
• Contain strong chelating and clay suspending
agents
• Not recommended below 100o F
• May be shut in or immediately returned
37
EDTA applications
• HEDTA can be formulated to match temperature and

reactivity
• Low corrosion rate
• Prevent problem associated with mobile silica
• Candidates:
• Gas wells
• Acid sensitive formations
• High temperature wells - Applicable > 400oF
38
Acid formulation selection
• The selection of the acid formulation is a trade off between

price, equipment availibility and the need for an improved
diversion system
• Acid placement is improved due to the retardation effect and
the viscosity of the formulation
• To improve the acid placement mechanical diversion
techniques can be combined with viscosified acid
formulations
39

22 - Carbonate - Fluid Design

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22 - Carbonate - Fluid Design

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Acid Formulations

Copyright 2009, NExT, All rights reserved

Basic reaction between HCL and limestone

1m3 HCL 15% dissolves 220kg or 81dm3 of CaCO3

Calcite 222 g/l 437 g/l

Dolomie 204 g/l 403 g/l

• HCl - Primary acid for • Acid and alcohool

HCl 7,5 % 1,037 106 1,1 24 (134)

REACTION PRODUCTS AND PROPERTIES OF HYDROCHOLORIC ACID

• Three formulations used in the field

• Glacial acetic acid in kerosene or diesel

• 15% HCl and 0.25% HF

• Primary use is for removal of Hydrocarbon

• Blend aromatic solvent with any acid blend

• Gas Well Acids

Volume Percent of Alcohol in Solution

Copyright 2009, NExT, All rights reserved

Regular HCl SGD

SPE 71693 SPE 80225

• Problem: Hydrochloric acid (HCl) does not

• Emulsion is significantly retarded with respect to HCl.

HCl Laminar Flow

250°F 300°F 350°F

• Emulsion is stable for approximately one hour at 350oF.

Temperature Required Time for 50%

• Emulsified Acid is Stable at Ambient Conditions

a. Nasr-El-Din et al., SPE 71693, 2001 23

• Acid emulsion is a highly retarded emulsified HCl acid

It is possible to viscosify HCl solutions using :

• Low viscosity if pH < 2 , µ µ

Live Acid Spent acid gel

• Viscoelastic Surfactant-based Leakoff Control Acid

a (Nasr-El-Din et al., SPE 75257, 2002)

CaCO3 + 2HCl ---> CaCl2 + CO2 + H2O

Live VES Acid + Spent Acid + Mutual Solvent

Used in the Treatment

HCl Concentration (%)

7 vol% VES; Fann 35 @ RT

• Self gelling diverters

• Procedure of breaking of polymer

• Emulsified acid creates longer wormholes

• HEDTA can be formulated to match temperature and

• The selection of the acid formulation is a trade off between

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