SPE 121762

Lab and Field Study of New Microemulsion-Based Crude Oil Demulsifier for
Well Completions
Y. Yang, K.I. Dismuke, and G.S. Penny, CESI Chemical, a Flotek Company, and J. Paktinat, Universal Well Services

Copyright 2009, Society of Petroleum Engineers

This paper was prepared for presentation at the 2009 SPE International Symposium on Oilfield Chemistry held in The Woodlands, Texas, USA, 20–22 April 2009.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
In the petroleum industry, water and oil emulsion formation presents an on-going production issue receiving considerable
technical attention. Crude oil/water demulsification effectiveness has been tested using a new microemulsion-based
demulsifier (ME-DeM) with an environmentally improved formulation. This ME-based product, tested on a range of crude
oils, has been shown to be more effective than comparable commercially available non-ME based demulsifiers (DeM).
Results using ME based products for demulsification have demonstrated significant improvements in field tests. Additional
field studies are in preparation.

Introduction
Emulsion Generation and Stabilization
Water and oil emulsions have been the subject of numerous studies in the petroleum industry because of associated
operational issues requiring intervention and expense in production, recovery, transfer, transportation and refining processes.
A very good summary regarding “a state of the art review” of crude oil emulsions was presented by Sunil Kokai (Kokai
2002). Emulsions, defined as a combination of two or more immiscible fluids that will not easily separate into individual
components, which exist as droplets of colloidal sizes or larger, can lead to high pumping cost. In the case that water is
dispersed in an oil continuous phase, the emulsion is termed water-in-oil (w/o) emulsion and in the case that oil is dispersed
in a water phase, an oil-in-water (o/w) emulsion. If there is no stabilizer between the oil and water interface, the emulsion is
not thermodynamically stable. Coalescence of droplets can lead to destabilization of the emulsion (Holmberg, et al. 2007).
However components can accumulate at the oil and water interface which stabilize the interface hindering droplet
coalescence and the destabilization (demulsification) process. Materials, such as naturally occurring or injected surfactants,
polymers, inorganic solids, or wax, can lead to stabilization of the interface. Emulsification formation processes are also
influenced by fluid mixing, shear, turbulence, diffusion, surfactant aggregation (Miller 1988), steric stabilization (non-ionic
surfactants), temperature and pressure. Surfactants can form lamellar liquid crystals by the growth of multiple layers around
the dispersed droplets.
Emulsions can form when fluid filtrates or injected fluids and reservoir fluids mix, or when the pH of the producing fluid
changes. Asphaltene, resin and wax composition and concentration (Lissant 1988, Auflem 2002, Sifferman 1976, Sifferman
1980) are factors affecting emulsion creating and stabilization. In oils which contain significant amounts of asphaltene, the
asphaltene acts as a surfactant, creating emulsions that can be very difficult to destabilize.

Interfacial tension can be reduced using surfactants which enhance the thermodynamic stability of an emulsion and allowing
creation of small droplets. Studies have concluded that emulsion stability is not totally dependent on the interfacial tension
value but on the interfacial film properties (Berger, et al. 1988, Posano, et al. 1982) and have shown that lowering the
interfacial tension is conducive to emulsion stabilization, but if too low, can lead to destabilization. Surfactants, polymers
and adsorbed particles can create strong interfacial films. Increased interfacial film stability also results from greater surface
and bulk viscosity. These factors can limit film thinning and rupture by affecting the properties of interfacial viscosity and
elasticity.
2 SPE 121762

Demulsification Mechanism and Influencing factors

Destabilization of emulsions results when the interfacial film between the dispersed-phase can be eliminated leading to
droplet coalescence and subsequent separation of the oil and water phases. Mechanisms of emulsion destabilization include
creaming and sedimentation as a result of differences in water and oil densities, flocculation, coalescence, and Ostwald
ripening which results from diffusion of the dispersed phase through the continuous phase (Holmberg, et al. 2007, Auflem
2002). Interfacial tension and interfacial rheological studies show that the kinetics of demulsiifier adsorption at the water-
crude oil interface correlated to the phase separation rate and demulsifers concentration impacts elasticity at the interface
(Goldszal and Bourrel 2000, Key and Gutierrez 1999). Coalescence involves interfacial film thinning leading to film rupture.
Film thinning will be enhanced by lower viscosities of the fluid in the interfacial film. Demulsifier adsorption at the water-
crude oil interface has been correlated to the relative solubility of the demulsifier in the oil and water phases or RSN. More
recently work has shown that many oils have a preferred alkane carbon number (PACN)(Berger, et al. 1988). Effectiveness
of a treatment is governed by the speed that the demulsifier gets to the oil-water interface and then by the action taken once at
the interface. Decreasing interfacial viscosity, flow behavior at fluid interfaces (Freeman 1999), is believed to play a key role
in the demulsification process. Temperature and pressure have been studied and shown to influence the stability of
emulsions (Osasha and Al-Shiwaish 2006). Higher temperatures have an influence on the interfacial tension and viscosity,
lowering both by a significant factor. In some cases the temperature alone destabilizes the emulsion. The greatest concern is
where the bottom hole temperature does not destabilize an emulsion. In these cases chemical intervention becomes a
necessity to alleviate the problem.

Key properties of any chemical based demulsifier must address the factors stabilizing the emulsion while driving
demulsification mechanisms. Destabilization is accomplished by reducing the interfacial tension at the emulsion interface.
In order to destabilize the interfacial film surrounding the dispersed water, a demulsifier should have strong attraction to the
interface, have balanced partitioning between the water and the oil phase, be able to diffuse through the emulsion efficiently
and be able to promote film thinning. Demulsifier should be ability to help flocculate dispersed phase droplets. Where solids
are stabilizing the interfacial film, demulsifiers should be able to alter the wettability of the solids allowing them to be
incorporated into the continuous phase (Auflem 2002).

Chemistry: Surfactants types and desired demulsifier properties

Emulsion destabilization can be accomplished by mechanical, electrical and chemical methods. Mechanical and electrical
methods such as heating, electrostatic precipitation and filtration are available. Several advantages are offered by chemical
demulsification when compared to those methods. Chemical demulsification requires lower capital investments and
provides flexibility in change and modification to address changing emulsion properties. Many chemical demulsifiers have
been developed and are commercially available.
Demulsifier additives have been developed using a broad range of chemistries and destabilization mechanisms: organic
compounds such as surfactants and solvents; polymers, copolymers and resins; inorganic materials such as salts and acids;
and enzymes. One of the old standard and least expensive chemistries includes nonyl phenol ethoxylates and more
sophisticated nonyl phenol and t-butyl phenol formaldehyde condensation materials with ethylene and propylene oxide
(resins). These provide a nonionic with solubility in both phases. Other common nonionics include ethoxylated propylene
glycol with molecular weights of 2 to 4000, ethylene and propylene oxide copolymers and oxyalkylated amines. The general
structures of some selected non-ionic surfactants are shown below. Other chemistry methods include using anionic and
cationic materials. An example of a commonly used anionic material is a dialkyl naphthalene sulfonate with salts such as
dihexyl amine to draw the surfactant into the oil phase. If asphaltenes are present, a common treatment is to add oil soluble
phosphate esters or the use of opposing sulfonates and amines. Many times a fines stabilized emulsion requires the use of
acids in combination with the demulsifier to be effective. The most commonly used acid for wetting colloidal oil wet solids
has been dodecyl benzene sulfonic acid (DDBSA). Common acids such as citric are also effective if the solids are water
wet. Solvents that have been commonly used include aromatics with xylene and toluene and the most common co-solvents
are materials similar to ethylene glycol monobutyl ether (EGMBE). With the drive to use environmentally friendly materials,
the phenols and aromatic solvents are used less often (Dalmazzone and Noik 2001). Non-toxic polysiloxane surfactants have
been the subject of recent studies (Dalmazzone et al. 2005). Some of the more common nonionic materials used for
demulsification are shown below.
SPE 121762 3

Sorbitan Alkanoate

R(OCH2CH2)n0H

Alkoxylates

Fatty alcohol ethoxylate

Fatty acid ethoxylate

CH3
I
HO(CH2CH2 0)×(CHCH2O)y(CH2CH2O)zH
Block Copolymers

Alkyl phenol ethoxylate

Nonyl phenol ethoxylate

Fatty amide ethoxylate

Oxyalkylated amines
In conducting this work, several types of products have been studied including a range of surfactants, block copolymers,
solvents, salts and acids. This paper focuses on microemulsion based surfactant systems with various nonionic demulsifiers,
compared to the same systems without the microemulsion and with commonly used linear and nonyl phenol based
ethoxylates.
Microemulsion
Microemulsions are solutions of oil, water and surfactants which are thermodynamically stable and optically isotropic,
4 SPE 121762

existing in at least three different microstructures. Small dispersed phases of oil and water are separated by a thin layer of
amphiphile (a chemical compound possessing both hydrophilic and lipophilic properties). Microemulsion domains of water
and oil having droplet dimensions of approximately 10-100 nm are stable, whereas emulsions, which have considerably
larger droplet sizes (1-10 micron), are unstable. Unlike emulsions which require considerable mixing energy,
microemulsions can form spontaneously. Benita gives a comparison of differences between macroemulsions, nano or
miniemulsions, and microemulsions (Benita 2005), stating that the free energy gain (based on the extent to which the
surfactant lowers the interfacial tension between the two phases and the change in entropy of the system) is sufficient to keep
droplets intact and stable. Given the small droplet size of microemulsions, the internal surface is high requiring higher
amounts of surfactants than emulsions. Several variables are important in formation and controlling the microstructure and
behavior of microemulsions including surfactant type and concentration, hydrocarbon solvent characteristics and
concentrations, and co-surfactant type and concentration. A range of microemulsion formulations have been made and
patented for use in oilfield applications including drilling and cementing operations, hydraulic fracturing, acidizing,
remediation, demulsification, and cleaning (Purslely, et al. 2008). The specific formulations developed can be oil or water
external microemulsions. The microemulsion based demulsifier detailed in this paper is specifically formulated to be a water
external microemulsion. Oil external microemulsion based demulsifiers have also been developed and successfully tested,
the results of which are not discussed in this paper. Microemulsions have been studied for demulsification properties
previously (Dantas et al. 2001, Bourrel, et al. 1979).

Experimental
Characterization and Test Methods
Several excellent overviews of demulsification techniques, characterization techniques and laboratory reviews have been
written. One example is “Characterization of Demulsifiers” by R.J. Mikula and V.A. Munoz in Chapter 2 of Surfactants –
Fundamentals and Applications in the Petroleum Industry, Ed. Laurier Schramm, 2000 (Mikula and Munoz 2000).
In this study, microemulsion based demulsifiers have been characterized for surface tension, droplet size distribution,
interfacial tension with various crude oils, and demulsification properties.
Demulsifier formulations were screened for emulsion separation at using blended 1:1 crude oil and treatment fluid mixtures
(see details below). Crude oils from a wide range of field locations have been analyzed for oil and water content, solids,
emulsion, API gravity, paraffin content, asphaltene content, pour point and interfacial tension.
Static and dynamic surface tension measurements were made using Kruss 100 Wilhelmy plate and Sita bubble tensiometer,
respectively. A Dispersion Technologies DT 1200 Acoustic spectrometer was used to determine ultrasound attenuation
spectra and droplet size distribution (Zelenev 2009).

Interfacial tension (IFT) and densities were determined for five selected crude oils at simulated downhole conditions. IFT
tests were conducted using the DuNouy Ring technique keeping the solutions and oil in a water bath slightly above the test
temperature, using an insulated cup during the test.

Several types of products have been used in this study including a range of surfactants, block copolymers, solvents, salts and
acids. Surfactants which have been investigated include alcohol and polyol ethoxylates, modified polyol ethoxylates,
ethylene oxide/propylene oxide (EO/PO) block copolymers, amine and polyamine ethoxylates, phenol ethoxylates and others.
This paper focuses on microemulsion systems with various nonionic based demulsifiers.

Comparative demulsification screening test were run to determine the efficiency of separation of various demulsifiers with
individual crudes over a range of temperatures (typical data will be presented at 70 F and 160 F). The treatment fluid
consisted of 50 ml of 2 w% KCl to which the desired concentration of demulsifier was mixed. For screening purposes, 50 ml
of oil and 50 ml of the treatment fluid were blended at a uniform mixing speed for a specified time (typically 15 seconds) in a
Waring blender. This mixture was transferred immediately to a graduated cylinder and water/oil separation was measured as
a function of time. Water breakout was plotted as % Demulsification versus time.
Demulsifiers were tested under simulated fracture flow conditions (Paktinat et al. 2005). Test fluids were flowed through a 6
ft long column filled with a mixture of sand and shale. Sample ports were located every foot along the column. Three
surfactant systems were flowed through the column, samples obtained at each sample port and demulsification test
performed. The surfactant systems included the following: Microemulsion based fluid, nonyl phenol surfactant system, and
an alcohol ethoxylate surfactant system. Demulsification rates of three crude oil emulsions were tested with fluid samples.
Demulsification rate versus sample location are plotted.

Two demulsification field tests were conducted on Colorado tight oil and gas wells using a microemulsion based formulation.
Production data for both oil and gas are summarized below.
SPE 121762 5

Results
Laboratory
Characteristics of the microemulsion based demulsifier, referred to as Microemulsion Demulsifier (ME-DeM) are listed in
Table 1. Analysis of the acoustical spectra (Figure 1) indicate a bimodal particle size distribution with a large fraction of
material in the microemulsion range (droplets under 100 nm) and a smaller portion in the emulsion range (droplets above 1
micron).
   Table 1:          
   Characteristics of MicroEmulsion Demulsifier (ME‐DeM)      
              
   Particle size distribution  Distribution Bimodal
Volume % in     
            nanometer range          73.0 
            Average droplet size  4.5 nm         
            Droplet distribution 1.5‐8.5 nm

Volume % in micron 
range           27.0 
Average droplet size         2 micron
Droplet distribution 1‐3.5 micron
   Surface tension (bulk)   (Wilhelmy plate) 27.6 dyn/cm (Dynamic)  27.0 dyn/cm
Surface tension diluted 
   (0.2 v% ME‐DeM in 2w% KCl)  (Wilhelmy plate)  36.6 dyn/cm  (Dynamic)  35.5 dyn/cm 
   Shelf life  120 ⁰F     > 4 months
      ‐16  ⁰F     > 4 months

ME‐DeM Particle Size Distribution 
(PSD): Bimodal Solution
3.5
3
PSD (wt. based)

2.5
2
1.5
1
0.5
0
1.00E‐03 1.00E‐02 1.00E‐01 1.00E+00 1.00E+01

Microns
Figure 1: Particle size distribution of ME-DeM

Seven crude oils, primarily light crudes, from different field location were tested using the microemulsion based demulsifier.
Selected characterization analyses of the crude oils are shown in Table 2. API gravity varied between about 32 and 44
degrees. Field locations included 4 European, 1 Asian and 2 North American. Three samples contained solids between 0.1
and 1.0 w%. When mixed with 2% KCl brine without any treatment fluid, all crude oils tested tended to form stable
emulsions easily, in part, due to the asphaltene and paraffin content. Asphaltenes ranged between 1 and 5 w% and paraffins
ranged between 0.8 and 12.2 w%.
6 SPE 121762

   Table 2:                       
    Analysis of crude oils as received                  
                         
   Sample Designation  A  B  C  D  E  F  G   
                            
   Water (vol. %)  0  0  0  0  0  0  69   
   Oil (vol. %)  100  99.9  100  100  100  99.8  25   
   Solids (vol. %)  0  0.1  0  0  0  0.2  1   
   Emulsion (vol. %)  0  0  0  0  0  0  5   
                            
   API gravity (deg )  39.4  43.4  32  36  37  38.2  33.8   
Density (g/ml)  0.8563       0.7708  0.8242  0.8214  0.8179   
   Paraffin (weight %)  0.8  9.6  8.0  8.1  5.1  12.2  11.5   
   Asphaltenes (weight %)  2  1.4  3.6  4.4  4.8  2.2  1   
Pour Point (⁰ F)  <‐20  <‐20  50  20  0  25  35   
Interfacial tension (dyn/cm) @   
     0.0 w% ME‐DeM (2% KCl, 160 F)  20.6  20.8  19.79  19.45  23.62   
     0.1 w% ME‐DeM (2% KCl, 160 F)  3.62  3.51  5.06  8.01  6.72   
     0.2 w% ME‐DeM (2% KCl, 160 F)  4.26  4.92  5.52  6.36  3.95   
    

The water/oil demulsification effectiveness of the microemulsion was compared to that of a non-microemulsion demulsifier
(DeM) using the same surfactant. The DeM is a commercially available blended non-ionic based product developed for use
in stimulation and demulsification treatments. This product is known to provide strong water wetting properties, interfacial
tension reduction and uses the same non-ionic surfactant as the ME-DeM. Typical test results, as seen with Crude B, are
shown in Figure 2. With no demulsifier added, baseline results at 70 F show only 20% water breakout after 10 minutes.
The microemulsion based formulation initiated water breakout immediately upon mixing and increased water breakout to
96% in the first three minutes and was completed in 4 minutes. The DeM initial demulsification was slower and increased to
84% in 4 minutes. Complete demulsification with DeM took 2.5 times longer than the ME-DeM. Higher demulsification
rates are possible with the microemulsion because of reduced particle size and associated ability to diffuse through the
emulsion efficiently giving lower interfacial viscosities or elasticity allowing faster thinning.

Crude B
100

80
% Demulsification

60
Crude B at 70F, 0.2% ME‐DeM

40 Crude B baseline at 70F

Crude B at 70F, 0.2 w% DeM 
20 eqv 

0
0 2 4 6 8 10

Time (min)

Figure 2: Demulsification efficiency versus time for DeM compared to ME-DeM treatments
SPE 121762 7

Crude A which contained 2% asphaltenes and 0.8% paraffins was effectively treated at low temperature (70 F) using 0.2
w% of ME-DeM. Complete demulsification was achieved in 13 minutes at 70 F and less than 5 minutes at 160 F.

Crude A
100

80
% Demulsification

Crude A, 2% 
60 KCl water 
baseline, 70 F
40

20 Crude A,0.2 
w%, 70 F

0
0 10 20 30
Time (min)

Figure 3: Effective demulsification treatment at low temperature

Demulsification tests were run on a Crude C which contained 3.6% asphaltenes and 8.0 % paraffins. Baseline test indicated
very stable emulsion formation at low and high temperature. Initial tests at 70 F were used to estimate the best
concentration (Figure 4) for demulsification. Although high concentrations of the ME-DeM appear to initiate demulsification
process more rapidly, 0.2 w% yielded the maximum results after 50 minutes. Higher temperature test (Figure 5) results were
similar to those at 70 F. There were both slight increases in the initial rate of demulsification and overall efficiency.

Crude C
100
% Demulsification

80
Crude C, 0.2% ME‐
60
DeM, 70F
40 Crude C, 0.5% ME‐
20 DeM, 70F
0 Crude C, 1.0% ME‐
0 50 100
DeM, 70F

Time (min)
Figures 4: Crude C with 0.2% ME-DeM at 70 F
8 SPE 121762

Crude C
100
% Demulsification
80
Crude c, 0.2% ME‐
60
DeM,70F
40 Crude C, 0. 2% ME‐
DeM, 160F
20
Crude C, Baseline, 
0 160 F and 70 F
0 20 40 60 80 100

Time (min)
Figure 5: Crude C with 0.2% ME-DeM at 70 F and 160 F

In preparation for demulsification field trials, screening tests were run to determine the best method of fluid treatment for the
demulsification application. ME-DeM was added to either oil or water to determine the most effective method of treatment
injection. Crudes B, D and E were tested. Figure 6 shows the effect of mixing the ME-DeM treatment into oil or water
phase prior to running the demulsification test. Significantly better results were obtained by incorporating the ME-DeM into
an aqueous based carrier than by an oil based carrier.

Crude B
100

80
% Demulsification

60

40

20

0
0 10 20 30 40 50 60

Time (min)

ME‐DeM Treatment in Oil Phase ME‐DeMTreatment in Water Phase

Figure 6: ME-DeM treatment fluid pre-blended into water or oil prior to demulsification test

Further, in preparation for demulsification (remediation) field test, Figures 7 and 8 compare blending the ME-DeM treatment
fluid at 0.2% with differing amounts of the base fluid prior to demulsification. This work is to simulate addition of ME-DeM
in downhole conditions with limited mixing capabilities. In these tests, three aspects differ from the standard
demulsification test method: 1) instead of adding the ME-DeM treatment to 50 ml of aqueous solution before mixing with 50
ml of oil the crude oil, then creating the emulsion, the treatment was added to only ½ of the water (25 ml versus 50 ml) and
SPE 121762 9

the water in oil emulsion was created using 25 ml of untreated water and 50 ml of crude ; 2) the ME-DeM treatment is added
to the balance of the water (25 ml), then mixed with the emulsion; and 3) a milder, slower agitation rate is used when the
treated water is mixed with the emulsion. A slight but minor reduction is initial rate is observed, however no efficiency is
lost in this process.

Crude E
100
Crude E, 0.2% ME‐
% Demulsification

80
DeM, 160 F
60
40 Crude E, 2.0% KCl 
water, 160 F
20
0 Crude E,ME‐DeM 
0 5 10 15 20 Remediation 
Simulation, 160 F
Time (min)

Figure 7: Crude E Remediation simulation blending 0.2% ME-DeM in 2.0% KCl

 

Crude D
100

80
% Demulsification

60 Crude D,0.2% ME‐DeM, 160 F

40 Crude D, ME‐DeM Remediation 
Simulation, 160 F
Crude D, 2% KCl Baseline, 160F
20

0
0 5 10 15 20
Time (min)

Figure 8: Crude D Remediation simulation blending 0.2% ME-DeM in 2.0% KCl

Seven crudes are arranged in order of descending asphaltene concentration (Table 3). Crude oils with higher concentrations
of asphaltenes formed very stable water in oil emulsion at 70 F. In addition to asphaltene concentrations, Table 3 lists the
paraffin content, IFT (interfacial tension) at 160 F with and without ME-DeM, and summarizes the general demulsification
effectiveness using 0.2 w%. ME-DeM demonstrated excellent demulsification characteristics at 160 F for all concentrations
of asphaltenes. The interfacial tension of each water-in-oil emulsion is significantly reduced using 0.2 w% ME-DeM. As
10 SPE 121762

evidenced by the API gravity and impact of temperature, ME-DeM should be able to diffuse through the emulsion to the
water and oil interface readily, increasing destabilization. At lower temperatures and asphaltene concentrations above 4%,
0.2 w% ME-DeM was not sufficient to effectively destabilize the emulsion.
                                   
   Table 3: Summary of ME‐DeM effectiveness at high and low temperature          
                                   
Pour 
   Crude  Pt.  API  Asphaltene  Paraffin  Asph./Par.  Time to max. %     IFT @ 160F  IFT @160    
Demulsification
      (⁰F)  gravity  ( wt.%)  ( wt.%)     (min)  No   w/ 0.2%     
                     70F  160F  ME‐DeM  ME‐DeM    
                                   
   E  0  37  4.8  5.1  0.94  No demul.  3  23.62  3.948    
   D  20  36  4.2  8.1  0.52  No demul.  10   19.45  6.357    
   C   50  32  3.6  8  0.45  94% 50 min  80  19.79  5.520    
Not 
   G  35  33.8  2.2  12.2  0.18  90% 15 min  7  Not tested  tested    
   A  <‐20  39.4  2  0.8  2.50  13 min  < 5   20.60  4.261    
   B  <‐20  43.4  1.4  9.6  0.15  4 min  < 5   20.80  4.917    
Not 
   F  25  38.2  1  11.5  0.09  13 min  < 5   Not tested  tested    
                                   

Lab and field study of Northeastern US

Some wells in the northeastern region of the US produce some oil or condensate along with gas. The oil can create
emulsions that block or diminish production. Three such formations are the Speechley, Balltown and Bradford. A lab study
was conducted to determine the effectiveness of the common non-emulsification agents used based on nonionic alcohol
ethoxylates (AE) and nonyl phenol alkoxylates and formaldehyde resins (NP). These common NE agents were compared to
the ME-DeM. Tests materials were flowed through a 6 ft shale column described earlier. The fluid was collected at the 1 to
6 ft ports. An emulsion test was run on the effluent from each port on the 3 oils. Figures 9-11 show the time to achieve a
100% break versus the effluent port and DeM surfactant type.

Speechley Oil
(Brine-oil control break time without DeM of 6:23)

4:19
3:50
Break Time (min:sec)

3:21 0.2% ME
2:52
DeM

2:24 0.2% NP
1:55
1:26
0.2% AE
0:57
0:28
0:00
0 2 4 6 8
Length of Column (ft)

Figure 9: Speechley break time vs. ft traveled down a 6 ft shale column

Figure 9 shows that the oil and water break time at ambient temperature without demulsifiers of 6 min 23 sec. With the
addition of NP as the demulsifier the break time at port 1 was 3:50 and decreased to near 1 min at ports 3 to 6. The addition
of AE resulted in break times of 2:52 down to 30 seconds at ports 4 to 6. The profile indicates that the demulsifier was at too
SPE 121762 11

high of a concentration since it became more effective once a portion of the material was adsorbed to the shale. The ME
DeM broke the emulsion from 1 min down to 30 seconds at ports 2 to 6.
Balltown oil is shown in Figure 10. The oil and water break time at ambient temperature is 9 min 17 sec. With the addition
of NP as the demulsifier the break time at port 1 was 1 to 2 min at ports 2 to 3 and increased to over 4 min at port 6. The
addition of AE resulted in break times of 2:24 at port 1, increasing to 6 to 7 min at ports 3 to 6. This profile indicates that
0.2% DeM was necessary to break the emulsion. As the material adsorbed onto the shale diminishing the concentration, the
emulsion break times increased dramatically. The ME DeM broke the emulsion from 1 min 12 sec down to 30 sec at ports 3
to 6. This shows that the ME DeM is an effective demulsifier even after flowing 6 ft into a shale column. In fact it may be
possible to reduce the concentration and maintain effectiveness in this case.

Balltown Oil
(Brine-oil control break time without DeM of 9:17)

8:24

7:12
Break Time (min:sec)

0.2% NP
6:00

4:48 0.2% AE

3:36
0.2% ME
2:24 DeM
1:12

0:00
0 2 4 6 8
Length of Column (ft)

Figure 10: Balltown oil break time vs. ft traveled down a 6 ft shale column

Figure 11 shows that the Bradford oil and water break time at ambient temperature without demulsifier is 8 min 01 sec.
With the addition of NP as the demulsifier the break time at port 1 was 2:50 and decreased to near 1 to 1.5 min at ports 2 to 6.
The addition of AE resulted in break times of 4 to 5 min down to 1.5 to 2.5 min at ports 4 to 6. The profile indicates that the
demulsifier was applied at too high of a concentration since it became more effective once a portion of the material was
adsorbed onto the shale. The ME-DeM broke the emulsion from 1:30 down to 1 min at ports 2 to 6.
Bradford Oil
(Brine-oil control break time without DeM of 8:01)

6:00
Break Time (min:sec)

4:48 0.2% AE

3:36 0.2% NP

2:24
0.2% ME
DeM
1:12

0:00
0 2 4 6 8
Length of Column (ft)

Figure 11: Bradford oil break time vs. ft traveled down a 6 ft shale column

Field Results
Demulsification field tests were conducted using a microemulsion based formulation in Colorado on a tight oil and gas well
(Well 1). The well was on a severe decline and becoming uneconomical because of near wellbore issues including
emulsions, paraffins and formation fines migration. The well was producing approximately 60 barrels of oil per month
12 SPE 121762

(BOPM) and 1 million cubic feet per month (MM CFPM) of gas. The well was treated with a microemulsion based
demulsifier. Following the treatment, oil production increased to 150 BOPM and gas production stayed at 1 MM CFPM.
The production improved from an erratic production pattern to more consistent as seen on the decline curves. Gas-to-oil ratio
was reduced by about 50%. The demulsification treatment allowed the well to continue over a year without any workover.

Figure 12: Well 1 Oil and Gas production before and after ME demulsification treatment.

A second Colorado based tight oil and gas well (Well 2) produced a highly paraffin rich oil which was on a sharp decline.
Near wellbore paraffin build up was occurring in spite of a formation temperature around 250 F. A microemulsion based
treatment was completed which improved production dramatically and moved the decline curve well above the projected
trend lines. Oil production improved from 20 BOPM up to 300 BOPM and gas production increased from 200 to 900 MM
CFPM. This enhanced effect on the oil and gas radically altered the trend lines creating a new operating efficiency. In
addition, the produced crude oil no longer needed to be treated in order to be sold and reduced operating expenses.
SPE 121762 13

Figure 13: Well 2 – Oil and Gas production before and after ME demulsifier treatment

Summary
Crude oil-water demulsification effectiveness has been tested using a new microemulsion (ME) based demulsifier with an
environmentally improved formulation. This ME based product, tested on a range of crude oils, has been shown to be more
effective than comparable commercially available non-ME based demulsifiers. Comparative data indicates the
microemulsion based demulsifier initiates and completes the emulsion destabilization process more rapidly than the
comparable non-microemulsion demulsifier. Excellent demulsification results have been obtained for crude oils which
contain asphaltene and paraffins. For all most crudes tested, using a 0.2 w% treatment concentration reduces the interfacial
tension from 19-24 dyn/cm to about 4-6 dyn/cm. Efforts continue to characterize various problem crudes. This work
indicates that once the appropriate demulsifier has been identified, its performance can be improved by formulating it into a
microemulsion. Field results using ME based products for demulsification purposes have demonstrated significant
improvements in oil and gas production. Additional field demulsification studies are in preparation. Microemulsion based
demulsifiers products for oil treatment applications have been formulated.

Conclusions
1. Microemulsions (ME) with improved demulsification efficiencies and improved environmental properties have been
created from standard non-ME emulsifiers.
2. Microemulsion based demulsifiers initiated and completed emulsion destabilization more rapidly than comparable
non-ME emulsifiers.
3. Demulsifier products based on microemulsions have demonstrated significantly improved oil and gas production in
well demulsification tests.
4. Once the appropriate demulsifier has been identified, its performance can be improved by formulating it into a
microemulsion.
5. Microemulsions can be formulated for either oil or water based treatments.
14 SPE 121762

Acknowledgements
The authors would like to thank Linda Ellena and Andrei Zelenev of the CESI research group, The Woodlands, TX, for
conducting the surface tension measurements and the particle size analyses and Richard Fox, CESI Executive Account
Manager, for many helpful discussions regarding field applications. Also we wish to thank Stephen Andrews, Bill Ray and
Earl Parnell, all of CESI Technical Support Group, Marlow, OK, for crude oil analyses.

References
Auflem, I.H., Influence of Asphaltene Aggregation and Pressure on Crude Oil Emulsion Stability, Thesis,
Dept of Chemical Engineering, Norwegian University of Science and Technology, June 2002.
Benita, S., Microemulsions for Solubilization and Delivery of Nutraceuticals and Drugs, in
Microencapsulation, Methods and Industrial Applications, 2nd Edition, 2005, pp. 350-352.
Berger, P.D., Hsu, C., Arendell, J.P., SPE16285, Designing and Selecting Demulsifiers for Optimum Field
Performance on the Basis of Production Fluid Characteristics, November 1988, pp. 522- 526.
Bourrel, M., Graciaa, A., Schechter, R.S., Wade, W.H., The Relation of Emulsion Stability to Phase
Behavior and Interfacial Tension of Surfactant Systems, J. Colloid Interface Sci, 1979, 72, 161.
Dantas, T.N.C., Neto, A.A.D., and Moura, E.F., Microemulsion Systems Applied to Breakdown Petroleum
Emulsions, Journal of Petroleum Science and Engineering 32 (2001) 145-149.
Dalmazzone, C., Noik, C., SPE 65041, Development of New “Green” Demulsifiers for Oil Production,
Presented at 2001 SPE International Symposium on Oilfield Chemistry held in Houston, TX, Feb 13-16,
2001.
Dalmazzone, C., Noik, C., Komunjer, L., SPE 80241, Mechanism of Crude-Oil/Water Interface
Destabilization by Silicone Demulsifiers, presented at the 2003 SPE International Symposium on
Oilfield Chemistry, Houston, TX Feb. 5-8, 2003.
Freeman, J. F., Introduction to Rheology, Chapter 1 in Rheological Methods in Food Process Engineering,
2nd Edition, 199, pp. 53-55.
Goldszal, A., Bourrel, M, Demulsification of Crude Oil Emulsions: Correlation to Microemulsion Phase
Behavior, Ind. Eng. Res., 2000, 39 (8), pp 2746-2751.
Holmberg,K., Jonsson,B., Kronberg, B., Lindman, B., Emulsions and Emulsifiers in Surfactants and
Polymers in Aqueous Solution, 2nd Ed.Chapter 21, 2007, pp. 451-471.
Key, S., Gutierrez, S., SPE 50744, Demulsifier Effects on Interfacial Rheological Properties of Asphaltene
Films Absorbed at Oil/Water Interface, Presented at the 1999 SPE International Symposium on
Oilfield Chemistry, Houston, Tx, Feb 16-19 (1999)
Kokai, S., SPE 77497, Crude-Oil Emulsions: A State-Of-The-Art Review, presented at the 2002 SPE
Annual Technical Conference and Exhibition, San Antonio, 29 Sept.- 2 Oct (2002).
Lissant, K.J., Emulsification and Demulsification – An Historical Overview Colloids and Surfaces, 29 (1988)
1-5.
Mikula, R.J., Munoz, V.A., Characterization of Demulsifiers, in Surfactants – Fundamentals and
Applications in the Petroleum Industry, Chapter 2, Ed. Laurier Schramm, 2000.
Miller, C.A., Spontaneous Emulsification Produced by Diffusion – A review, Colloids and Surfaces, 20
(1988) 89-102.
Okasha, T.M., and Al-Shiwaish.A. J. A., Investigation of the Effect of Temperature and Pressure on
Interfacial Tension and Wettability of Shu’aiba Reservoir, Saudi Arabia, GEO 2006 Middle East
Conference and Exhibition; 27-29 March, 2006; Manama, Bahrain.
Paktinat,J., Pinkhouse, J., Stoner, W., and Penny G.,SPE 97365 Case Histories: Post-Frac Fluid Recovery
Improvements of Appalachian Basin Gas Reservoirs, Presented at the 2005 SPE Eastern Regional
Meeting Morgantown, WV, 14-16, Sep 2005.
Posano, H.L., et al., Consideration of Formation and Stability of Oil/Water Dispersed Systems, JAOCS (1982), 59, No. 8,
360-363.
Pursley, J.T., Holcomb, D.L., and Penny, G.S., US Patent No. 7,380,606, Composition and Process for Well
Cleaning, June 3, 2008.
Sifferman, T.R., SPE 7409, Flow Properties of Difficult-To-Handle Waxy Crude Oils (1976).
Sifferman, T.R., Flow properties of Waxy Udang Crudes, presented at the Ninth Annual Convention of the
Indonesian Petroleum Association, May 27-28, 1980.
Zelenev, A., SPE 122109, Characterization of Microemulsion in Water Emulsions by Acoustic
Spectroscopy, to be presented at the SPE European Formation Damage Conference, Scheveningen,
The Netherlands, 27-29, May 2009.