Fluid Selection

Outline
• Selection criteria
• Hydrochloric acid
• Hydrofluoric acid systems
• Mud Acid
• Organic Mud Acid
• Clay/XE Acid
Matrix Fluid Selection Criteria
• Formation mineralogy • Permeability
• Sensitivity • Nature of damage
• Deconsolidation
• Mobility of induced
• Precipitation damage
• Fines release
• Produced Fluids
• Reactivity
• Chemical composition
• Sludge / Emulsions
• Surface area • Gas wells
• Rock Structure • Temperature
• HCl solubility / carbonates • Corrosion
• Clay distribution • Penetration
• Bottomhole pressure
HCl Preflush
HCl Fluid Selection Guide for All Temperatures

>100 md 20-100 md <20 md

<10% silt and <10% clay 15X 10X 7.5X

all other combinations of

silt and clay composition 10X 7.5X 5X

4-6% chlorite/glauconite, use <20md Guidelines with 5% Acetic Acid

6-8% chlorite/glauconite, use 10% Acetic Acid preflush to Mud Acid + 5% L400
>8% chlorite/glauconite, use 10% Acetic Acid and Organic Mud Acid
<2% Zeolite, use 10% Acetic Acid in all HCl systems
2-5% Zeolite, use 10% Acetic Acid preflush
>5% Zeolite, contact Regional Tech Center
X and Super X (HCl)
• Solution of hydrogen chloride gas in water
• Field concentrations are between 7.5 wt% and 36 wt%
16000 35
Volume of CO2 (ft3)
14000 Limestone Dissolved (lbm)
Limestone Dissolved (ft3)
30

12000
25
10000
20
8000
15
6000
10
4000

2000 5

0 0
0 5 10 15 20 25 30
HCl Concentration (wt %)
Sandstone Acidizing: HCl Preflush
Gallons of 15% HCl Required per foot height

Porosity HCl Solubility (%)

(%) 2 4 6 8 10 12 14 16 18

15 20 40 60 80 100 120 140 160 180

20 19 38 57 76 95 114 133 152 171
25 18 36 54 72 90 108 126 144 162
30 17 34 51 68 85 102 119 136 153
35 16 32 48 64 80 96 112 128 144
Hydrofluoric Acid Systems
• Mud Acid (HCl-HF)
• Organic Mud Acid
• Formic-HF
• Citric-HF
• Retarded Acids (HBF4)
• Clay Acid
• XE Acid
Schlumberger Mud Acid
• Nine HCI-HF formulations in Mud Acid selection Guide
• Dissolves siliceous minerals
• Dowell offered the first commercial Mud Acid Service in 1940
in the (U.S. Gulf Coast)
• Efficient

+
HF
or
HCl Y1 Mud Acid
Sandstone Acidizing
• Methods to prepare Mud Acid
• Dissolving Y-1 (Ammonium Bifluoride) in HCl solution:
• Blending 20% HF solution to HCl
• Blending 25% HCl - 20% HF solution with Water or HCl
• Methods to prepare Organic Mud Acid
• Dissolving Y-1 (Ammonium Bifluoride) in HCl solution
• Add enough HCl to completely react with Y-1
• Add L36 last
• Blending 20% HF (H200) and L36 into fresh water
Sandstone Acidizing rw rd
• Use StimCADE for proper job
design
• Rule of thumb
kd ki
• Best success rates: 125-200
gal/ft « 4 ft radially
• Use of Preflush and
Overflush Small injection volumes
• Flowback as soon as
possible

perm increase Large injection volumes

perm decrease
Retarded Mud Acid
• Inhibits fines migration
• Clay stabilizer
• Limited HF available ==>
deeper penetration
• Reduced probability of
precipitation

fused clay
after treatment
Sandstone Acidizing Formulations
• Clay Acid: Retarded HCl:HF formulation using Fluoboric Acid
• Organic Clay Acid: Retarded Organic:HF formulation using Fluoboric Acid
• Both have similar mechanism to generate HF and retard its reaction (to enable
deep live acid penetration)
• NH4HF2 + H2O ⇔ NH4OH + HF
• 4HF + H3BO3 ⇔ 3H2O + HBF4
• HBF4 + H2O ⇔ HBF3(OH) + HF
• HBF3(OH) + H2O ⇔ HBF2 (OH) 2 + HF
Temperature (F) % Hydrolysis of %HF
Clay Acid

70 4.89 .085

176 7.30 .130

212 8.54 .150

Amount of Clay Dissolved by HBF4
20
18
Grams of Clay Dissolved

147 OF
16
180 OF
14
95 OF
12
10
8
6
4
2
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36
Time (Hours)
Improved Penetration with Clay Acid
800
Permeability, % Change

Clay Acid
600 12% HCl - 3%HF

400

200
1st 6 in.
Unconsolidation
0
0 10 20 30 40
Distance From Inlet (in.)
Kaolinite Observed With SEM
 Water Sensitivity Test Frio Sand
Untreated Treated
% of Original Permeability % of Original Permeability
140 140

120 120

100 100

80 80

60 60

40 40

20 20

0 0
0 5 10 15 20 25 30 35 40
0 5 10 15 20 25 30 35
Pore Volumes Pore Volumes
Distilled Water
Compatible Brine
Clay Acid
 Two Clay Acid Formulations

• Regular Clay Acid 130o F to 300oF

• Clay Acid LT 100o F to 130o F

Sandstone Acidizing Formulations
• Mud Acid: HCl:HF
• Dissolves clays at specific temperatures
• pH rise can result in precipitation of hydrated Si
• Organic Clay Acid: Organic acid:HF
• Chelates Al
• HCl sensitive clays do not degrade and increase pH
• Requires formation preconditioning if migratory clays are
present Mineral Max. T in HCl (deg F)
z Zeolites 75
z Chlorites 150
z Illite 190
z Mixed Layer 200
z Smectite 200
z Kaolinite 250
Experimental Method
• Sequential Acid Spending
Testing Results
Sequential acid spending on 90% 100 mesh sand and 10% zeolite
Silicon concentration in spent acid solutions, 200oF
0.4 OC Acid
Sandstone Acid
0.35 9/1 mud acid
Si Concentration (Molar)

Clay Acid
0.3 3/1 mud acid

0.25

0.2

0.15

0.1

0.05

0
1 2 3 4
Sequential Reaction ----->
Clay Acid as Overflush to Mud Acid
• To eliminate rapid production decline caused by fines
migration
• Clay Acid main application
• 1/4 BPM per 4 ft perforation
• Well should be brought back to production slowly, using a
small choke
NH4Cl w/ U66 HCl or DAD
30-60 gal/ft 30-60 gal/ft

Clay Acid Mud Acid

100-125 gal/ft 100-150 gal/ft
Client Publications on Clay Acid
• Mobil - SPE 8399
• Arco - SPE 11722
• Exxon - SPE 9387
• Tenneco - SPE 14820
• AGIP - SPE 20623
• Statoil - SPE 24991
• Statoil - SPE 31077
• Ashland - IPA
• Maraven - SPE 38955
Special Systems
Special Systems for Special Cases
• Drilling mud damage removal • Acid sensitive formations
systems
• BDA
• Water sensitive formations
• MSR • Gas wells/tight formations
• Alcohol based acids • High corrosion environments
• Gas Well Acid • High sludge tendencies
• Alcoholic Acid • Recovery of whole mud
• Organic acids
• Non-acidic solvents
• NARS
• CLEAN SWEEP
• MudSOLV
• Sour well acids
• FeS Acid
• ScaleSOLV
Breakdown Acid (BDA)
• Designed primarily to open or “breakdown” the producing
interval prior to a Fracturing job
• Formulation
• HCl 7.5% - 15%
• EZEFLO F-78 5 gal/1000 gal
• Inhibitor: A261
• Features
• Good dispersion and suspension of both formation silts and
clays used in drilling muds
• Other Applications
• Cementing: to remove filter cake
• Squeeze: spearhead fluid
Mud and Silt Remover (MSR)
• Acid Solution + Clay Suspending
30
Agent (F78) + Chelating Agent
(L41 or U42) 25
• Applications
• Removal of drilling mud 20
damage*
Settling 15
• Workover fluid* Time
• Breakdown fluid* (min) 10
• Notes:
5
• *Temperature > 200o F
F75N instead of F78 0
• *Do not overdisplace MSR No 5 gpt 100 MSR
123, flowback immediately Add F78 ppt 100
L41
MSR Fluid Selection

Carbonate Sandstone
Low Iron Conc. High Iron Conc. Low Iron Conc. High Iron Conc.
<1000ppm >1000ppm

MSR 100 MSR 150

1. MSR 100 1. MSR 150
2. MSR 123 or 2. MSR 123 or
MSR 100 + MSR 100 +
Mud Acid Mud Acid
Formulations
• MSR 100
• Most Common

• MSR 150
• 150 lb. L41 (or U42) + 5 gal F78 / 1000 gal HCl 5% - 15%

• MSR 123
• 50 lb. L41 (or U42) + 100 gal U66 + 5 gal F78 / 1000 gal 12-3 Mud
Acid
MUDCLEAN OB Mud Removal System
• Water based system for OBM
clean-up Mud removal from
• Used in conjunction with acid natural fractures
• Removes OBM
• Reducing OBM viscosity
• Dispersing fines
• Water-wets the formation
• Typically staged with MSR100
• MUDCLEAN OB is first stage
Gas Well Acids
• Acid + 67% K46 Methanol (by volume)
• Slow reaction rate
• Improved clean up
• Applications
• Dry gas wells and gas storage wells
• Temperature up to 250o F
• Formulations (mud acids only used in sandstone)
• Gas well acid: 67% K46+HCl (34-37%)
• Gas well mud acid: 67% K46+8% HCl+3% HF
• Gas well super mud acid: 67% K46+8% HCl+6% HF
Gas Well Acid Surface Tension
Surface Tension DYNE/CM
Temp = 77 F

Volume Percent of Alcohol in Solution

Organic Acids
• Four Formulations used in the Field
• Aqueous Acetic Acid
• Nonaqueous Acetic Acid
• Formic Acid
• Organic Mud Acid (discussed in Sandstone Fluids)
• Organic Clay Acid
Organic Acids
10000

1000

100
15% HCl
9% Formic
10% Acetic
10

0.1
(ft3) (lbm) Cx
Volume of CO2 Limestone Relative Reaction
Dissolved Rate
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
Aqueous Acetic Acid
• Concentration
• 10% of glacial acetic acid (L-400) in water
• L-400 - freezing point = 62o F
• L-401 - (70% acetic acid) - freezing point = -3o F
• L-401 can be used when freezing is a problem
• Inhibitor = A-186
Formic Acid
• Concentration - up to 9%
• Slow reaction with carbonates
• Intermediate between HCl and Acetic Acid
• Inhibited for use up to 350o F
• Inhibitor: A-186
• Also used as preflush to organic mud acid
• Compatible with mutual solvents and most other additives
used with HCl
 NARS 200 and 201
• Non-Acid Reactive Solutions (NARS)
• Used as formation clean up or breakdown fluid in formations that may be
damaged by acid
• Clean up fluid in old wells
• Non damaging to water or acid sensitive formations
• Contain strong chelating and clay suspending agents
• Do not have upper temperature limit
• Not recommended below 100o F
• May be shut in or immediately returned
• No corrosion inhibitor needed
• Mix water: fresh water
CLEAN SWEEP
CLEAN CLEAN CLEAN
SWEEP I SWEEP II SWEEP III
Main Solvent Xylene Toluene Methanol

Paraffin/Asp XXX XXX

Remove X X XXX
water block
Dissolve X X X
carbonates
Shrink some X X X
iron bearing
minerals
Remove XXX XXX X
emulsions
Summary
• Acid formulation selection
• Maximizes stimulation effect
• Minimizes collateral damage
• Optimizes cost
• Neat acids and brines are used for
pre- and post-flushes
• Mud Acid is a mixture of HCl and HF
optimized for the following
• Mineralogy
• Temperature
• Permeability
• Organic Mud Acid is used when low
corrosion is required and/or when
asphaltic sludges may form
• Retarded mud acids utilizing fluoboric
acid are very effective in removing
formation damage and stabilizing
formation fines.
• HBF4 generates HF at a slow rate
• HBF4 causes fusion of platelets and
reduction of CEC.
• A shut-in period is required following
injection of HBF4
• HBF4 is less damaging to formation
integrity than HCl/HF acid.
• Fluoboric acid minimizes silica
precipitation.
• Organic-fluoboric formulations have
been developed for sensitive formations