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MICROWAVE HEATING AND SEPARATION OF WATER-IN-OIL EMULSIONS

C.S. Fang and P.M.C. Lai

Laboratory and field tests showed that viscous and stable water-in-oil emulsions can be demulsified and separated into oil and water layers by the combined process of microwave heating and gravity sedimentation. The process provides an opportunity for waste reduction and oil recovery from waterin-oil emulsions. The process was tested with bench-scale experiments using laboratory samples and sludge samples collected from a dump-site. The laboratory samples were 50-50% and 3070% water-in-oil emulsions. The results were encouraging and consistent with the observation in field tests. In some cases better than 80% of the water in emulsion samples was separated.

Key Words:

Microwave heating, Demulsification, Separation, Water-inoil emulsions.

ABOUT THE AUTHORS:

C.S. Fang is affiliated with Department of Chemical Engineering, University of Southwestern Louisiana, Lafayette, LA 70504-4130. Peter L.C. Lai is affiliated with CTCI Corporation, Taipei, Taiwan.

Manuscript received July 28, 1994. Accepted for publication November 30, 1994.

© International Microwave Power Institute

  • V iscous and stable water-in-oil emulsions are generated in various industrial operations, such as petroleum refining, oil and gas

production, and transportation of natural gas through pipelines. Since it is no longer permitted by law to discharge oil-containing emulsions to a dump site, the present practice is to use demulsifying chemicals to break the emulsion and separate water from oil. After separation, water is discharged to the river or lake. Examples of demulsifying chemicals are alkyl substituted benzene sulfonic acids and alkyl phenolic resins [Kermmer, 1988]. For water-in-oil emulsions which usually have high viscosity, the required mixing of these chemicals with the emulsion is dif- ficult. Also when a high dosage of chemicals is used to overcome the difficulty, it leads to a secondary pollutant, since the separated water may contain too much chemicals to be discharged to public water. As an alternative, microwave heating was studied. The concept of microwave heating of emulsions was first suggested by Klaila [ 1983] and Wolf [ 1986] in their patent applications. In recent years, active research and development work on microwave demulsification technology for applications in chemical plants was carried out by Samardzija [ 19911. Following his patent award, Klaila conducted several field tests, with a 50 kW microwave generator, which was equipped with wave guides and a microwave power monitor. One of the tests was in March 1984 in Coffeyville, Kansas [Fang et al, 1988; 1989] with approximately 120 bbls of slop oil in a large storage tank that was 10 ft in diameter and 10 ft high. The slop oil was an emulsion of 50% oil, 22.5% bottom sediment and 27.5% water. After 228 kWh of microwave energy was applied continuously at 20 kW, the temperature of the top portion of emulsion reached approximately 100°C and the emulsion was separated to oil and water layers. A similar result was obtained in the field test in Louisiana for 188 bbls of crude-oil/water emulsion left in a tank, which was 10 ft in diameter and 15 ft high. After 18.2 hours and 417.5 kWh of microwave radiation, the emulsion was separated to 146 bbls of dehydrated oil and 42 bbls of clear water. In parallel with the field tests, experimental tests

on the controlled emulsion samples was conducted. These samples of known compositions were prepared in the laboratory. The objective of the experiments was to produce quantitative information. Viscous samples of sludge collected from a dumpsite were also tested to demonstrate the effectiveness of mi- crowave demulsification technology. The results are presented

International Microwave Power Institute

47

here with equations to calculate approximate values of temMicrowave Oven

perature increase and the rate of heat generation of irradiated

TC Amplifier

9 Laboratory Study Thermocoupl es Experimental Apparatus A Kenmore domestic microwave oven (Sears Model 566.8878611) was
9
Laboratory Study
Thermocoupl
es
Experimental Apparatus
A Kenmore domestic microwave oven (Sears
Model 566.8878611) was used in heating emulsion
samples. Its rated power output is 700 watts at 2450
MHz, consuming approximately 1400 watts of
t
IBM PC-XT

electric power. A 800 ml cylindrical glass container was used as the sample holder. The top and bottom of the container were covered with aluminum foil, as shown in Figure 1, so that microwaves enter only on the side surface of samples. The diameter and height of emulsion sample in the container were, respectively, 88 mm and 132 mm, as shown in Figure

2.

Nine J-type subminiature thermocouples (OMEGA Model SICSS-020U-6) were inserted to different locations of the sample body to measure local temperatures of emulsion: three in the top layer, three in the middle layer and three in the bottom layer, as shown in Figure 2. The diameter of the thermocouples was 0.010 inch. These thermocouples were connected to thermocouple amplifiers (Cole- Parmer No. J8109-00, Model 20B) and a data acquisition analog/digital interface card (Cole-Parmer No. J-8109-27, Model 134) in a desktop personal computer. A data logging computer program, written in BASIC, was used to specify the interval of data sampling and calibration constants. The overall system accuracy in temperature measurements was ±1.5°C with 0.1°C resolution.

A/D In terf ac e

Computer

FIGURE 1: Experimental apparatus.

TOP

View

SIDE VIEW

here with equations to calculate approximate values of temMicrowave Oven perature increase and the rate of

Sample Preparation and Procedures

Samples of water-in-oil emulsion were prepared using Golden State SAE-30 motor oil and distilled water. This particular

800

ml JAR

motor oil was used because it contained the fewest additives. In many cases, emulsions in the oilfield are very stable. To assure the stability of emulsion samples prepared in the labo- ratory, 0.95 NaOH solution was added to distilled water used Er$.7ISION in preparation of samples. After oil had been poured into a domestic blender (Sears, Kenmore Power 10), the blender

~l

''

_

i_

 

LAYERS

TOP

°

MIDDLE

M

was turned on at the "3" position, which provided agitation

o

and shear of liquid at 12,400 rpm. The NaOH solution was "~ added slowly to oil during agitation. After all solution was added, agitation was continued until the mixture became too viscous for the blender to continue mixing. The pH values of

I

S B >30I~

samples were measured with a Chemcadet pH meter (Cole-

(DLMENSICN aI

mm) Parmer Model J-5986-60). The pH value of 50-50% emul sion samples was 12.6 to 12.8. The 50-50% water-in-oil FIGURE 2: Locations of Thermocouples.

emulsion was prepared initially by using the same volumes 40 of oil and aqueous NaOH solution, but the actual

  • 3

G 120s

   

volumetric composition when analyzed with a centrifuge was found to

1OOs

80s

  • 5 60S

 

Sample Size: 800 ml

Highest Power Setting, 700

W

30s

be 46.50% water and 53.5% oil by volume. The 30-70% wa-

 

0

 

a ----------------------------------120s

 

100s

30 ter-in-oil emulsion was prepared with 30% aqueous solution

0

I0

9-- 60s

 

.-- 30s

 

10

20

30

40

Distance from Center, mm

5

0

Experimental Results

FIGURE

3: Temperature

distributions of 50-50% water- in-oil emulsion (middle layer) at the end of microwave radiation.

100

Sample Size: 800 ml Highest Power Setting,

W

 

700

0

0

 

X

 

X

 
 

Radiation

 

o

+ 260s

 

X 240s

 

0

c ISOs

 

0

A 120s

 

1005

 

r

0 SOS

 

60

 

30s

40 15

1o

U

5

s o

d 60

U

50

30
CL

E

Q

20

10

0

 

w

-

0

-0

 
 

-

 

10

20

  • 0 30

Distance from Center, min

v

25

and 70% motor oil by volume, however the actual Composi- tion was 22.50% water and 77.50% oil. A drop of water

soluble ink (Pelikan brand) was added to a small amount of the emulsion sample, approximately 5 ml, in a test tube. No dispersion of the ink was observed. Clear water droplets were E observed when the samples were placed under a microscope. Therefore, the continuous phase of emulsion was oil and the sample was indeed a water-in-oil emulsion. Microscopic examination showed the diameter of water

droplets to be in the range of 1 to 100 µm. Most were in 10 to 40 tm range. The glass container containing 800 ml of emulsion sample was placed in the center of a Kenmore microwave oven and the microwave radiation was applied at the highest power setting. Radiation time varied from 30, 60, 80, to 120 sec- onds, or longer. After radiation, the sample was insulated with polyurethane form and removed from the oven. Nine ther- mocouples were inserted in the sample quickly, and the com- puter immediately recorded the temperatures. The amount of water separated and settled to the bottom of the container by gravity was monitored and measured every five or ten min- utes. Similar temperature measurements were conducted using distilled water. The results served as reference points for the emulsion experiments.

droplets to be in the range of 1 to 100 µm. Most were in 10 to

Experimental results from temperature and volume measurements include the following: (1) temperature distributions, (2) temperature histograms, (3) volume rates of microwave heat generation, and (4) separation of water from emulsion. The first three items are presented here, while the last item is presented in the next section.

(1) Temperature Distributions. Nine temperature readings were obtained for each run, showing temperature distributions for the top, middle and bottom layers. Figures 3 and 4 show rapid temperature rises at three locations of the middle layer of 50-50% and 30-70% water-in-oil emulsions, respectively, after 30, 60, 80, 100 and 120 seconds of radiation. Similar temperature distributions were obtained for the top and bottom layers of the same sample. For viscous water-in-oil emulsions, the motion of emulsions in the horizontal direction is slow. Therefore, horizontal-temperature distributions in Figures 3 and 4 show that water-in-oil emulsions were heated uniformly through the

FIGURE 4: Temperature distributions of 30-70% water-in-oil emulsion (middle layer) at the end of microwave radiation.

in-oil emulsions is plotted against time, showing temperature histograms of irradiated samples at the No. 2 location, which is 2.5 cm from the center of the glass container.

droplets to be in the range of 1 to 100 µm. Most were in 10 to

body of emulsion by microwaves. This was expected, since the dielectric loss of oil is small. The small decline of temperature near the container wall may be caused by the heat loss to the surrounding atmosphere.

(2) Temperature Histograms. In Figures 5 and 6 the temperature increase of 50-50% and 30-70% water-

The rates of increase in temperature of irradiated samples are shown in Table 1. These samples include distilled water, SAE motor oil, 50-50% and 30-70% water-in-oil emulsions. The bulk temperature of emulsions were obtained from the average values of nine local temperature readings. The rate of temperature increase was calculated from temperature increase divided by radiation time. It is interesting to observe that the rates of temperature increase of emulsions were not between the rates for water and oil. The average rates of temperature increase of 50-50% and 30-70% water-in-oil emulsions are 0.24 and 0.31 °C/sec, respectively. The rates appear to decrease at higher temperatures. This is believed to be the result of the decreasing dielectric loss of water. The heat loss to the

hA

eaA

,

q MW =

V (T-T~)+ V [(T+2 73 .1 6) -(Ta +2 73 .1 6)'] +PC B

\ d dt T

100 2-T 2 - M 2 - B 80 60 Calculated 40 (3) Rate of Heat
100
2-T 2
-
M
2
-
B
80
60
Calculated
40
(3) Rate of Heat Generation. The volume rate of
Sample size: 800
Location: No. 2
0
l
p /W /
0
50
100
150
200
250
300
Time of Radiation, t, sec
FIGURE 5: Temperature
increase of 50-50% water-in-
oil emulsion.
heat generation is of great interest, since it is not only
an important term in the energy balance equation, but
also a term connecting the temperature increase and
the dielectric property of irradiated emulsion. Based
on the assumption that the rate of heat transfer from
emulsified water droplets to the surrounding oil is so
fast that water and oil practically have the same
temperature, the lumped-capacity energy balance
10
produces the following energy-balance equation:
surrounding is
not
a strong
factor
for
this
phenomenon,
based
on
the
heat
convection
and
radiation calculations.
The first, second and third terms in the right-
hand side of Equation (1) represent, respectively,
the heat loss by convective heat transfer to the
surrounding air, radiative heat loss from the wall
surface, and heat accumulation in the emulsion. The
contributions of the first and second terms are much
smaller than that of the third term. The heat generated
by the glass container is assumed to be negligible,
because of its small mass and low dielectric constant.
In applying Equation (1) to the volume rate of heat
(1
0
generation, gMW, the density (p) and heat capacity (C P )
250
30
0
50
100
150
200
0
Time of Radiation, t, sec
of emulsions are calculated by the following simple
mixing rules:

FIGURE 6: Temperature increase of 30-70% water-in-

49

Pm =PWO+PO(l - 0)

(2)

C p,m -Cp,,o+Cp,O(1-0)

(3

The volume rate of microwave heat generation of water, motor oil and emulsions calculated from the temperature measurements and Equation (1) are shown in the fourth column of Table 1. They are considered as experimental values of the volume rate of heat generation.

Separation of Emulsion

Temperature

The objective of heating viscous water-in-oil emulsions with microwave radiation is to separate water from oil. The separation involves two processes: coalescence of emulsified water droplets and sedimentation of coalesced water drop- lets. Both processes are affected by temperature. The rate of water separation in sedimentation depends on the settling velocity of water droplets in the emulsion. If the concentration of water droplets is low, droplets move without interaction with others and their settling velocity is given by Stoke's law [Bird, et al., 19601. Otherwise, the hindered settling velocity is given by the Richardson-Zaki correlation

   

TABLE 1

 

Experimental Results of Microwave Heating

 
 

Radiation Time,

Temp

Rate of Temp.

Volume Rate of

 

t,sec

Increase

Increase

Heat Generation

AT, °C

dT/dt, °C/s

q MW , cal/s.cm'

Water

 

30

4.7

0.157

0.156

60

10.0

0.167

0.167

120

20.4

0.170

0.170

180

30.7

0.171

0.171

240

39.7

0.165

0.166

300

48.1

0.160

0.162

360

56.8

0.158

0.159

SAE Motor Oil

 

30

1.0

0.033

0.0136

60

2.6

0.060

0.0246

90

4.4

0.0489

0.0201

120

6.6

  • 0.055 0.0227

 

150

10.2

  • 0.068 0.0282

Water-in-Oil Emulsion (50% water, 50% oil)

  • 0.216 0.151

30

6.49

  • 0.261 0.183

  • 0.235 0.165

60

15.6

80

18.8

  • 0.265 0.186

100

26.5

  • 0.229 0.161

120

27.5

 
  • 0.364 0.212

 

Water-in-Oil Emulsion (30% water, 70% oil)

  • 0.320 0.186

30

10.9

  • 0.319 0.186

60

19.2

80

25.5

  • 0.307 0.180

 
 
  • 0.306 0.179

too

30.7

  • 0.293 0.173

120

36.7

180

52.7

  • 0.289 0.172

 
 
  • 0.287 0.171

240

69.5

  • 0.264 0.158

260

74.7

300

79.2

50

Journal of Microwave Power and Electromagnetic Energy

Vol. 30 No. 1,

 

1995

Properties

[Probstein, 1989]. In both cases the settling velocity is proportional to the density difference, square of droplet diameter, and the reciprocal of oil viscosity. The viscosity of oil is very sensitive to temperature, much more than density difference. Therefore, as temperature increases, viscosity decreases much faster than the density difference. The results are a higher settling velocity and faster separation of emulsified water from oil. According to Osipow [ 1977], the rate of

Rate = Ale-8, i

RT

coalescence is given by:

(4)

As temperature increases, the rate of coalescence increases. The diameter of water droplets plays an important role, since the settling velocity depends on the square of diameter, as indicated above.

Experimental Data of Separation

The results of separation of 50-50% and 30-70% water-in-oil emulsions are shown, respectively, in

Figures

7

and

8,

where

the

percent

of

water

separation is plotted against the time of sedimentation, i s . The water separation in percent was calculated from volume measurements as follows:

Water Separation, % = V x 100%

0

(5)

The rate of heat generated from microwave radiation depends upon physical and dielectric properties, and may be predicted from electromagnetic field theory [Johnk, 1975; Decareau, 1985; Osepchuk, 1984; Decareau and Peterson, 1986]. There are three dielectric properties involved in microwave heat

100.0 90.0 Radiation 80.0 n 120s o loos 70.0 w 80s 80.0 • 30s 50.0 40.0
100.0
90.0
Radiation
80.0
n 120s
o loos
70.0
w 80s
80.0
30s
50.0
40.0
30.0
a-------------------------------------------a
o'°
o
0
/
100.0
20.0
1
90.0
/
0
0
0.0
80.0
0
10
20
A
30
40
50
A
e0
70.0
Time of Sedimentation, t s , min.
60.0
FIGURE 7:
50.0
Separation
40.0 Radiation 30.0 20.0/ / 0300S A In~" 270s 10.0 0260S r • 250s 0.0 ∎
40.0
Radiation
30.0
20.0/ /
0300S
A
In~"
270s
10.0
0260S
r
• 250s
0.0
∎ 240s
0
5
100
150
0

In Figure 7, 120 seconds of microwave radiation provided a significant improvement in separation of 50-50% emulsion over that of 30 second radiation. It took a little more radiation for 30-70% emulsion to produce separation, according to the results shown in Figure 8. In both cases the separation was made possible by microwave radiation. The rate of separation increased when more microwave radiation was applied, as shown in Figures 7 and 8. However,

  • i too much radiation was found to cause turbulence in emulsion and reverse the separation process. Experiments shown in Figures 7 and 8 were discontinued at the onset of turbulence.

of water from 50- 50% water-in-oil emulsion after microwave radiation.

Properties [Probstein, 1989]. In both cases the settling velocity is proportional to the density difference, square

Time of Sedimentation, t s , min.

FIGURE 8: Separation of water from 30-70% water-in-oil emulsion after microwave radiation.

ing. They are dielectric constant, dielectric loss and loss tangent. Loss tangent is the ratio of dielectric

Theory of Microwave Heating Dielectric

= 85.215 - 0.33583T

= 320.658T-10268

(6)

(7)

constant to dielectric loss. Dielectric properties of

5

various liquids have been reported by von Hippel [1954], Weast [19681, Tinga and Nelson [1973], Singh and Sinha [1985], Singh et al. [1986], Ritzoulis et al. [1986], Smyth [ 1977], Mudgett et al. [ 1974], and Mudgett [1982]. Dielectric constant and dielectric loss of water used in this work are given by the following two equations:

which are the least-fit equations of the data given by von Hippel [ 1954]. Temperature T is in °C. Dielectric properties of various petroleum oils also were given by von Hippel. Based on his data, the dielectric constant and loss tangent of motor oil used in this work were estimated and expressed in the following equations:

c ° = 2.24 - 0.000727T

tan S ° = (0.527T + 4.82) x 10 -4

Attenuation Factor

(8)

(9)

The Beer-Lambert's equation [Atkins, 1986] in physical chemistry states that the loss of electromagnetic energy, including microwaves, is proportional to the energy intensity and pathlength. This equation will be used to calculate the rate of heat generation by microwave radiation. Considering that the lost microwave energy is converted to thermal energy (heat), the volume rate of heat generation is given by the following equation:

ta g

loss tangent of petroleum oils are in the ranges of 2.0 to 2.2 and 0.001 to .005, respectively. Therefore, the following equations were developed to include the case where microwaves may go through the entire thickness of emulsion sample. If microwaves go through the water-in-oil emulsion, they should reach the other side of microwave cavity, and be reflected back into the emulsion as shown in Figure 9. This process of microwave propagation is repeated many times until the radiation is discontinued. If the emulsion is in a cylindrical glass container with its top and bottom ends covered with aluminum foil and the container is placed in the center of the micro- wave oven, the volume rate of microwave heat generation can be developed as follows. As a first approximation, considering that microwaves propagate only in the radial direction, in the first forward pass of microwaves, the pathlength of microwaves before reaching the element under consideration is R-r (z=R-r). The volume rate of heat generation produced by this first forward pass of microwaves in the element is given by Equation (10) as follows:

gMw,z =

h

4.184 (z)

4.184

tag [P e

-

2 a F _ ( R

-

T)1

1R

where the local microwave flux, P( z ), is given by the integrated form of the Beer-Lambert's equation; that is:

P(z) = P( ° )e -2,,z

The combination of Equations (10) and (11) gives the local volume rate of heat generation in terms of incoming microwave flux P(o) and the attenuation factor of the emulsion. The attenuation factor can be calculated from the following equation given by the electromagnetic field theory [von Hippel, 1954]:

ing to von Hippel [ 1954], the dielectric constant and

2itf

\

1/2

ag= C°C (VI +tan2S-1I

(12)

where the pathlength z is equal to R-r, and the quantity inside the brackets is the local microwave flux at the location r. The remaining microwaves continue to propagate the

Inner Surface of Microwave Oven

The attenuation factor of water varies from 0.465 cm - I at 15°C to 0.085 cm -1 at 95°C. Therefore, under

FIGURE 9: Multiple pass propagation and absorption of microwaves within emulsion.

  • 52 Journal of Microwave Power and Electromagnetic

Energy

Vol. 30 No. 1,

1995

the same intensity of microwave power, water generates less heat at higher temperatures.

Volume Rate of Heat Generation

Since the continuous phase of water-in-oil emulsion is oil, which has a low dielectric constant and a low dielectric loss factor, it is relatively "transparent" to microwaves. Accord

pathlength of r + R inside the emulsion to reach the cavity wall. After the reflection by the wall, microwaves travel the additional pathlength of r + R to return to the element. Therefore, the returning microwave power reaching the element is attenuated by the pathlength of r + R + R + r. The volume rate of heat generated by the first backward pass of microwaves in the element is:

2 C CE { PRe -2a F (R-r) e -2a t (r+R+R+r) 4.18 4

which gives q Mw to be used in Equation (1). The volume rates of heat generation of water and motor oil were calculated from Equations (12) and (17), using the dielectric properties of water and oil given by Equations (4) through (7). The results of the calculations are shown in Table 2. The calculated volume rates of heat generation of water are 10.9% to 41.1 % lower than the corresponding experimental values. The literature values of dielectric properties of water

J

Similarly, the volume rates of heat generated by the subsequent forward and reflected passes of microwaves can be obtained. The combined volume rate of heat generated by the i-th forward and reflected passes is:

2a. E

-2aF[R+4(i-1)R-rj + PRe -2a F [3R+4(i-

1)R+r]

gMw,i = 4.184 j PRe

(15)

The microwave intensity decreases each time microwaves pass the element. The summation of g Mw.I given in Equation (15) over the total number of passes gives the volume rate of heat generation for the element at r.

The average volume rate of heat generation can be obtained from the integration of the local volume rate over the entire volume of emulsion. That is:

rR qMW = 1 nR2H J° 27trH~ gMW,idr

(17)

i+1

where itR 2 H is the volume of irradiated emulsion. After integration,

qMW = 2aE P R

2 2

________

  • 4.184 (2aER) i=1

{[l+e 2a,

..

R

(2a E R-1)Je- 2a,:[R+4(i-1)R]

+[1- (2(X E R+ 1)e-2a, Je-2a,,.[3R+4('-')R]l

..

R

5

at temperatures higher than the room temperature may be too low. Table 2 shows that values of dielectric properties of motor oil estimated from the information given in the literature are also too low.

Temperature Increase

The calculated volume rates of heat generation of

50-50% and 30-70% water-in-oil

emulsions

are

shown in the fourth column of Table 3. The

deviations of the calculated values from the corresponding experimental values vary from -5.96%

The ability to predict the temperature increase of irradiated emulsions is of great interest in the design and operation of microwave heating and separation processes. Equation (1) shows that it can be achieved if the volume rate of heat generation is known. After converting Equation (1) to a difference equation, the temperature rise at a given location per unit time is given as follows:

AT _ qMw hA

 

At

C PP

Pp

Pp V

(T; - T,

(18)

e (TA [(T 1 + 273.2)' - (T. + 273.2)' ]

vp

where AT is Ti J+I - T, ,j and AT/At is the approximate value of dT/dt, which is the rate of temperature increase in °C/s. From the rate of increase and the initial temperature, the temperature increase, AT, is calculated from Equation (18) and shown in Figures 5 and 6. Equation (18) appears to be able to predict the temperature increase of 50-50% water-in-oil emulsion reasonably well in the early stage of radiation. The deviations between the calculated and experimental values are in the range from -2.0% to -25.7%. For 30- 70% emulsion, the deviations vary from -27.7% to 39.9%. An alternative calculation using permittivity data [Mudgett et al., 1974] and the mixing rule suggested by Noguchi and Maeda [ 1973] was tried. The differences between the calculated and experimental values were larger than these values indicated above. Considering that emulsion is a heterogeneous mixture of water and oil, and heat is generated separately in the suspended phase (water droplets) and continuous phase (oil), Equation (17) is applied separately for water and oil with individual attenuation factors. The total volume rate of heat generation of emulsion to be used in Equation (1) is given by:

qMW = gMW,w`Y+gMW,o0 - 0)

TABLE 2 Volume rates of heat generation of water and motor oil by microwave radiation.

 

Vol. Rate of Heat Generation, gmw , ca 1 /s . cm'

Radiation

Ave. Temp.*

Experimental

Calculated

Deviation

Time

a

T ave ,

Values

Values

%

t, sec

Eq. (17)

Water

30

25.0

0.156

0.139

-10.9

60

27.5

0.167

0.132

-21.0

120

33.1

0.170

0.120

-29.4

180

38.9

0.171

0.110

-35.7

240

43.5

0.166

0.104

-37.3

300

47.6

0.162

0.0980

-39.5

360

51.8

0.159

0.0937

-41.1

Motor Oil

  • 30 20.6

0.0136

0.0522

284

  • 60 23.7

0.0246

0.0522

112

  • 90 19.4

0.0201

0.0521

159

  • 120 23.9

0.0227

0.0521

130

  • 150 31.1

0.0282

0.0521

84.8

(0.142 cal/s•cm 3 ) to -31.7% (0.127 cal/s•cm 3 ) for 50- 50% emulsion, and -31.6% (0.108 cal/s•cm 3 ) to -42.5% (0.122 cal/ s•cm 3 ) for 30-70% emulsion.

Dump-Site Sludge

Thick, viscous, brown water-in-oil emulsion was collected from a dump-site of a compressor station and tested with microwave radiation. This emulsion is referred to as "sludge" in the field, and its physical appearance and property are very similar to emulsion samples prepared in the laboratory. From an analysis using a bench-top centrifuge, the composition of this dump-site sludge was found to be 21.1% oil, 76.6% water and 2.3% solids by weight. Three experimental runs were made to separate

the emulsion from the dump-site into water, oil and solid by microwave heating. In each run, 300 grams of this emulsion in a glass beaker were placed in the microwave oven for 20, 30 and 80 minutes of radiation. The microwave power to the cavity was calibrated against the power level setting. Based on this calibration and the power levels used, microwave energy inputs to these three samples were calculated to be 58.3, 69.6 and 117.1 watt-hours, respectively. After radiation, samples were placed on a bench for gravity sedimentation. After a few minutes on the bench, three or more layers of fluid began to appear in the beaker. An oil layer on the top and a water layer on the bottom were observed. One or two layers of slop were found between water and oil layers. A portion of oil was believed to be evaporated during irradiation. The water layer was removed and weighed,

while other layers were fed to a filter to separate solids. The filtrate, after a few minutes of gravity settling, separated into two layers again: a water layer and slop layer. Table 4 shows the amounts and percents of each layer obtained in these experimental runs. The separation was accomplished without using any chemical demulsifier.

TABLE 3

Volume rates of heat generation of emulsions by microwave radiation.

 

Vol. Rate of Heat Generation, g MN „ca1/s . cm'

Radiation Time

 

Ave. Temp.*

Experimental

Calculated

t, sec

T~ Ve , °C

Values

Values

Water-in-Oil Emulsion (50% water, 50% oil)

 
 
  • 30 24.8

 

0.151

0.142

  • 60 29.4

0.183

0.134

  • 80 31.0

0.165

0.130

  • 100 34.9

0.186

0.127

  • 120 35.4

0.161

0.125

Water-in-Oil Emulsion (30% water, 70% oil)

 
 
  • 30 27.1

 

0.212

0.122

  • 60 31.2

0.186

0.117

  • 80 34.4

0.186

0.115

  • 100 36.9

0.180

0.113

  • 120 40.0

0.179

0.112

  • 180 47.9

0.173

0.110

  • 240 56.3

0.172

0.109

  • 260 59.0

0.171

0.108

  • 300 61.2

0.158

0.108

The

emulsion

with

20

minutes

microwave

radiation produced four layers: water layer (51.2%), liquid-solid mixture layer (12.8%), oil layer (8.9%) and slop layer (12.5%). From material balance, it is believed that 14.6%, mostly oil, is evaporated. The cases of 30 and 80 minute radiation appeared to have excessive energy inputs, causing turbulence and mixing of water and oil. The oil layer disappeared in these two cases.

and oil layers. This method can be important for separation of viscous and stable water-in-oil emulsions that are difficult to pump and mix with chemical demulsifiers. The microwave demulsification process was demonstrated by tests of laboratory samples and field samples. Laboratory experiments under better controlled conditions produced data that confirmed the field test findings.

Conclusion

 

Small temperature gradients through the body of irradiated emulsions prove that viscous water-in-oil emulsions are heated more quickly and uniformly by

Microwave heating provides a new option in breaking waterin-oil emulsions and enhances gravity sedimentation to separate the emulsions into water

microwaves than by conventional convective heating, providing a faster water-oil separation. The temperature rise and volume rate of heat generation of emulsions induced by microwave radiation can be calculated from basic dielectric

55

properties, considering water-inoil emulsion as a heterogeneous mixture of water and oil. The

calculated values using the data available in the

literature are approximately 30% experimental values.

lower than

 

TABLE 4

 
 

Separation of dump-site sludge by microwave heating.

 
 

Run 1

 

Run 2

 

Run 3

 

Microwave Radiation Time, min.

20

30

 

80

Energy Input, w-hr

 

58.3

 

69.6

117.1

Water Layer, grams

153.7

159.6

146.2

 

(51.2%)

(53.2%)

(48.7%)

 

Solid Layer, grams

 

38.5

 

20.6

24.9

 

(12.8%)

(6.9%)

(8.3%)

 

Oil Layer, grams

 

26.8

 

0

0

 

(8.9%)

 
 

Emulsion Layer, grams

37.5

 

65.8

 

71.1

 

(12.5%)

(21.9%)

(23.7%)

 

Evaporation, grams

 

43.5

 

54.0

57.8

 

(14.6%)

(18.0%)

(19.3%)

 

Emulsion before Radiation, grams

300

300

 

300

 

(100%)

 

(100%)

(100%)

n

increment in radiation time, t j+l - t j , sec. or min.

 

convective heat transfer area, cm 2 constant constant

pressure, cal/g•°C

 

tans

loss tangent time of settling, min.

i

s

volume of irradiated

 

heat capacity at constant

V

 

emulsion, Equation (1), cm 3

 

Vo

volume of water separated, cm 3

 

= initial volume of water in emulsion, cm 3

 

Greek

Letters

aE

= electromagnetic attenuation factor,

S

cm -1

E

loss angle

"

Er .

= emissivity of surface = relative permittivity (dielectric

E r

constant) = dielectric loss

P

= density of emulsion, g/cm 3

6

Notatio

A

A1

B

1

C

p

c

f o

H

h

P

(0)

P

(z)

PR

qM

gMW,r or z

R

r

T

T a

Tav

e

 

AT

speed of light, cm/s frequency of incident microwaves z height of container, cm convective heat transfer coefficient, cal/s•cm 2 •°C microwave power flux at z = 0, watts/cm 2 local time-average microwave power flux, watts/cm 2 time-average microwave power flux at the surface of container, watts/cm 2 average volume rate of heat generation induced by microwaves, cal/s•cm 3 local volume rate of heat generation, cal/s•cm 3 radius of sample container, cm

Stefan-Boltzmann constant = volume fraction of emulsified water

= the i-th step of computations in the

j= the radial j-th step of computation for radiation

time m = mixture or emulsion o w = water

= oil

Subscripts

gas constant in Equation (4) radial coordinate, cm i temperature of emulsion, °C ambient temperature, °C average temperature, °C temperature increase, °C time, sec. or min.

References

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and

dispersions

of

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