STIMULATION LABORATORY

PROCEDURES
Procedure A02: EMULSION AND SLUDGE TESTING PROCEDURES

EMULSION AND SLUDGE PREVENTION TESTING

INTRODUCTION

Emulsions are always a major concern in acidising treatments. Downhole they can
cut production rates. At surface, they can be very hard to treat. Emulsion prevention
is better than treatment.

This procedure is intended for the evaluation of demulsifying agents used in acid
treating fluids. The test is based on American Petroleum Institute Recommended
Procedures Number 42, a standard procedure for testing de-emulsifying agents
(surfactants). The main difference being the inclusion of Fe3+ (ferric iron), to
represent the amount dissolved from the tubulars in the well and the mixing
equipment.

Fines (Silica/bentonite) are added to the acid in order to simulate the fines that the
acid will pick up from the formation rock. Fines and iron help to stabilize emulsions
that form between acid and reservoir fluids. Both of these contaminants (unhelpful
products) are added to the live acid so as to give a worst case scenario for any
system under test.

Note: If formation rock is available, it can be disaggregated and used instead

of the prescribed simulated fines mixture of silica flour and bentonite..

When a suitable de-emulsifying agent and/or anti-sludge agent has been selected (if
necessary). The concentration should be optimised to provide a balance between
cost and performance.

SAFETY

Goggles, gloves and protective clothing should be worn when working with acid.
Care needs to be taken when pouring hot acid into bottles. Breathing acid vapors
should be avoided. Vessels containing acids should be covered when not in use.

Other additives e.g. corrosion inhibitors, iron control agents used in the acid
treatment design should be handled according to the Material Safety Data Sheet.

EQUIPMENT

• 2 litre plastic beakers

• Graduated, wide-mouthed glass bottles, 100 mL or 200 mL capacity, with lids.
• Measuring cylinders
• Water bath
• CaCO3
• FeCl3.6H2O (ferric chloride hexahydrate)
• Various sizes of disposable syringes
• Wire Screen, 100-mesh
• Timer
• Safety gloves
• Record Sheet
• 100-mesh sieve
• Wash bottle containing hot water.

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 STIMULATION LABORATORY
PROCEDURES
Procedure A02: EMULSION AND SLUDGE TESTING PROCEDURES
MATERIALS

• Acid sample containing the same additives and same concentration as the
proposed field treatment
• Fresh crude oil samples filtered through a 100-mesh sieve to remove any solids
or naturally produced sludge.
• Silica flour: bentonite clay mixture (50:50 by weight) or crushed formation core
• Silica flour: bentonite clay mixture (90:10 by weight) or crushed formation core
• CaCO3 (calcium carbonate - marble chips)
• FeCl3.6H2O (ferric chloride hexahydrate)
• De-emulsifiers, Anti-Sludge Agents

1.0 MATERIALS PREPARATION

1.1 Live Hydrochloric Acid and HF-HCI (Mud Acid)

Prepare 500 mL of live hydrochloric acid and HF-HCI (Mud Acid), containing
the same concentration of additives and acid as for the proposed field
treatment, excluding demulsifier.

1.2 Spent Hydrochloric Acid and HF-HCI (Mud Acid)

1.2.1 Spent HCI

Prepare one litre (minimum) of live acid sample containing all additives in the
same concentration as the proposed treatment. Spend acid on an excess of
marble chips (keep adding chips until reaction ceases). Spending should be
complete in 2 to 4 hours. Decant the acid with the suspended fines into a
clean plastic container.

Note: The acid could be spent on crushed formation core, but generally
the low carbonate content of sandstones will mean using an excessive
amount to spend the required quantity.

1.2.2 Spent HCI-HF

Prepare 2 liters of live acid sample containing all additives in the same
concentration as the proposed treatment. Spend acid on 1 litre of silica flour-
bentonite clay mixture (50:50 weight percent). Spending should be
completed within 2 to 4 hours. Decant the acid with the suspended fines into
a clean plastic container.

Note: The acid could be spent on crushed formation core, but an

excessive amount may be to required dependant on the Alumino-silicate
content of the sandstone.

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 STIMULATION LABORATORY
PROCEDURES
Procedure A02: EMULSION AND SLUDGE TESTING PROCEDURES

2.0 PROCEDURE

The testing is normally performed at ambient temperature. However, it may

be carried out at bottom hole temperature, up to 200°F (93°C), if requested.
When working at temperatures other than ambient be careful to slowly
release the cap of the test bottle to ensure the hot contents do not spray out.

2.1 Live Acid Emulsion Test

2.1.1 25:75 Acid : Crude Oil Test

1. Measure 25 mL of live acid solution and pour into a glass bottle.

2. Disperse 1.25 g silica flour:bentonite (90:10) into the bottle containing

HCI. Disperse 1.25 g silica flour:bentonite (50:50) into the bottle
containing HCI-HF (could be replaced with crushed formation core).

3. Measure 75-ml crude oil and add to each of the acid dispersions.
Seal and cap the bottle then shake vigorously for 45 seconds.

4. Start the timer (place sample in water bath, if required). Record the
volume breakout of the acid phase at the elapsed time intervals
indicated on the record sheet (1, 2, 4, 6, 10, 15, 30 minutes etc.).

5. A 90% breakout of the acid phase within 15 minutes or less is

required.

2.1.2 50:50 Acid : Crude Oil Test

Note: Keep all of the test bottles below for the Sludge Test (Section 3.0)

1. Measure 50 mL of live acid solution and pour into a glass bottle

2. Disperse 2.50 g silica flour:bentonite (90:10) into the bottle containing
HCI. Disperse 2.50 g silica flour:bentonite (50:50) into the bottle
containing HCI-HF (could be replaced with crushed formation core).
3. Measure 50 mL crude oil and add to the each acid dispersion. Seal
and cap the bottle then shake vigorously for 45 seconds.
4. Start the timer (place sample in water bath, if required). Record the
volume breakout of the acid phase at the elapsed time intervals
indicated on the record sheet (1, 2, 4, 6, 10, 15, 30 minutes etc.).
5. A 90% breakout of the acid phase within 15 minutes or less is
required.
6. Repeat this test for each acid, excluding the silica flour:bentonite
mixture, but adding 3,000 ppm Fe3+ (0.73 g FeCl3.6H2O) instead to
each acid. Once again a 90% breakout of the acid phase within 15
minutes is required.

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 STIMULATION LABORATORY
PROCEDURES
Procedure A02: EMULSION AND SLUDGE TESTING PROCEDURES

2.1.3 75:25 Acid : Crude Oil Test

1. Measure 75 mL of live acid solution and pour into a glass bottle.

2. Disperse 3.75 g silica flour:bentonite (90:10) into the bottle containing
HCl. Disperse 3.75 g silica flour:bentonite (50:50) into the bottle
containing HCI-HF (could be replaced with crushed formation core).
3. Measure 25mL crude oil and add to each acid dispersion. Seal and
cap the bottle then shake vigorously for 45 seconds.
4. Start the timer and the place sample in water bath, if required. Record
the volume breakout of the acid phase at the elapsed time intervals
indicated on the record sheet (1,2,4,6,10,15 and30 minutes etc).
5. A 90% breakout of the acid phase within 15 minutes or less is
required.

If there tests indicate a stable emulsion has formed, run a series of screening
tests following the above procedure, to select the most effective de-
emulsifying system.

2.2 Spent Acid Emulsion Test

2.2.1 25:75 Acid :Crude Oil Test

1. Measure 25 mL of spent acid solution, as prepared in Section 1.2.1 for

HCl or Section 1.2.2 for HCI-HF and pour into a glass bottle.
2. Measure 75 mL of crude oil and add to each acid. Seal and cap the
bottle then shake vigorously for 45 seconds.
3. Start the timer and record the volume breakout of the acid phase at
the elapsed time intervals indicated on the record sheet (1,2,4,6,10,15
and 30 minutes etc).
4. A 90% breakout of the acid phase within 15 minutes or less is
required.

2.1.2 50:50 Acid :Crude Oil Test

1. Measure 50 mL of spent acid solution, as prepared in Section 1.2.1 for

HCl or Section 1.2.2 for HCl-HF and pour into a glass bottle.
2. Measure 50 mL of crude oil and add to each acid. Seal and cap the
bottle then shake vigorously for 45 seconds.
3. Start the time and record the volume breakout of the acid phase at the
elapsed time intervals indicated on the record sheet (1,2,4,6,10,15
and 30 minutes etc).
4. A 90% breakout of the acid phase within 15 minutes or less is
required.

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 STIMULATION LABORATORY
PROCEDURES
Procedure A02: EMULSION AND SLUDGE TESTING PROCEDURES

2.1.3 75:25 Acid :Crude Oil Test

1. Measure 50 mL of spent acid solution, as prepared in Section 1.2.1 for

HCl or Section 1.2.2 for HCl-HF and pour into a glass.
2. Measure 50 mL of crude oil and add to each acid. Seal and cap the
bottle then shake vigorously for 45 seconds.
3. Start the timer and record the volume breakout of the acid phase at
the elapsed time intervals indicated on the record sheet (1,2,4,6,10,15
and 30 minutes etc.).
4. A 90% breakout of the acid phase within 15 minutes or less is
required.

If these tests indicate a stable emulsion has formed, run a series of screening
tests following the above procedure, to select the most effective de-
emulsifying system.

3.0 SLUDGE TEST

Some crude oils in contact with acid produce an insoluble precipitate known
as sludge, even though the acid system may not exhibit emulsion tendency.
The following procedure is useful to demonstrate the tendency of sludge to
form under laboratory conditions.

3.1 Sludge Test Procedure

1. Place the samples used for emulsion testing in Section 2.1.2 (with and
without Fe3+) in a water bath at bottom hole temperature or 150°F for
not less than 4 hours, preferably 24 hours.

2. Remove the test mixtures from the water bath and slowly pour through
a clean, 100-mesh sieve or wire screen.

3. Visually check the screen for presence of large globules of sludge or

flakes or sludge, after the test mixture has passed through.

4. If solids are present, wash the screen alternately with hot water. This
will remove emulsions and paraffin but will not remove sludge caused
by acid.

5. Report the result in the remark section on the reporting sheet

according to the definitions below.

6. If sludge has formed select an anti-sludging agent and repeat all the
emulsion and sludge testing.

No sludge - No solid particles retained on the screen

Trace - A very low amount of particles on the screen
Moderate - Particles obviously present
Heavy - Many large particles present.

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 STIMULATION LABORATORY
PROCEDURES
Procedure A02: EMULSION AND SLUDGE TESTING PROCEDURES

4.0 SAND PACK TESTING FOR ACID ADDITIVE COMPATIBILITY

Surfactants (de-emulsifiers) and mutual solvents can prevent emulsions.

These chemicals react differently with various crude oils and formation
minerals. The above procedure for Emulsion Testing does not always
accurately model what occurs downhole. In reality some of the de-mulsifiers
may preferentially absorb into mineral surfaces. This absorption prevents the
surfactants from being available in the acid-fluid from where formation
damaging emulsions can form. Emulsions may occur because little
surfactant/de-emulsifier or mutual solvent remain in the acid system.

The following procedure is more similar to downhole conditions. The acid is

drawn through a sand pack rather than being mixed with sand. After the de-
emulsifier (and/or anti-sludge agent) in the treating fluid has been optimised
following the emulsion tests, the fluid is passed through a sand pack and the
emulsion test is repeated. If results similar to the previous tests are not
achieved (i.e. 90% acid breakout in 15 min or less) then mutual solvent is
added or the non-emulsifier concentration is altered until the specification is
met.

4.1 Equipment and Materials

• One 9 cm OD Buchner filter funnel

• One 9 cm OD Whatman No. 4 filter paper
• One sidearm flask
• Stock solution of 3% NH4Cl
• Graduated glass bottles with lids
• Vacuum pump or water aspirator
• Water bath
• Pack material: Formation core material for packing material or a
mixture of 10wt% illite-bentonite + 10wt% 100-mesh sand. (If the
mineralogy indicates a higher percentage of clays, feldspars,
carbonates, etc. the pack formulation may be adjusted accordingly).

4.2 Procedure

1. Mix 100 mL of the acid system to be tested (HCl or Mud Acid). The
acid system should contain all of the additives recommended for the
field treatment, including the optimized de-emulsifier concentration
and 3,000 ppm Fe3+ (1.22 g of FeCl3.6H2O).

2. Prepare a filter pack by placing 200 mL (one inch deep) of the

blended pack material or formation core material into a Buchner
funnel containing one No.4 Whatman filter paper. Wet the filter
paper before adding the pack material.

3. Water-wet the sandpack with 50 mL 3% NH4Cl. Be careful not to

saturate the pack with NH4Cl in order to minimize dilution effects.

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 STIMULATION LABORATORY
PROCEDURES
Procedure A02: EMULSION AND SLUDGE TESTING PROCEDURES

4. Place the Buchner filter funnel into the sidearm flask, apply vacuum
and filter the acid system.

5. Collect 50 mL of filtered acid into a clean 200 mL graduated glass

bottle. Add 50 mL of oil that was preheated to the bottom hole
temperature of the well (BHT).

6. Shake the oil/acid mixture vigorously for 45 sec. Be careful to release

the top slowly to allow pressure release prior to placing the bottle in a
hot water bath set at BHT.

7. Monitor the % acid breakout with time using the record sheet. The
breakout time and other parameters noted on the record sheet should
be noted.

8. Keep the sample and perform the sludge test Section 3.0 to determine
sludging tendency.

9. The results should be similar to those noted during the emulsion test
procedure Section 2.1.2. Otherwise alter de-emulsifier and/or anti-
sludge agent.

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 OIL / ACID EMULSION BREAKOUT RECORD SHEET
COMPANY: REPORT RE

FIELD:

WELL: TEMPERATUR

ACID:

OIL/ACID RATIO
DEMULSIFIER/SLUDGE CONTROL
CONCENTRATION (gal/1000 gal)
% BREAKOUT OF ACID PHASE (min) live spent live spent live spent
1
2
4
6
8
10
15
30
60 ( 1 hour)
180 (3 hours)
440 (24 hours)
EMULSION FORMED (YES / NO)
% EMULSION
FINES/SOLIDS *
INTERFACE **
OIL ADHERING TO GLASS IN ACID
PHASE***
SLUDGE****

REMARKS
* - Preferential wetting of fines/solids: OB =oil wet bottom, OO = oil-wet oil phase, WB= water wet bottom.
** - Interface: S= sharp, R= ragged, D= diffuse
*** - Oil amount: S = small , M =medium, L= large
**** - N=NO, T=TRACE, M-MODERATE, H=HEAVY

ECA Stimulation worksheet Rev D - Aug 2000