Journal of Petroleum Science and Engineering 70 (2010) 140–144

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Journal of Petroleum Science and Engineering

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p e t r o l

Research paper

Desalting and dewatering of crude oil in ultrasonic standing wave field

Guoxiang Ye 1, Xiaoping Lu ⁎, Pingfang Han, Xuan Shen
Institute of Sonochemical Engineering, Nanjing University of Technology, Nanjing, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A standing wave field of ultrasound was established in the designed standing wave tube. The enhancement of
Received 28 May 2007 ultrasound irradiation on desalting and dewatering process of LU-NING pipeline oil was studied. The results
Accepted 11 November 2009 showed that the best conditions of the oil pretreatment was: adding 30 mg/L demulsifier, injecting 5% (v.)
wash water, irradiating the crude oil 5 min by 10 kHz ultrasound (intensity 0.38 W/cm2, standing wave field),
Keywords: settling for 90 min. The final results of salt and water contents were 3.851 mg/L and 0.37%, respectively. The
ultrasound
effect of standing wave field combined with demulsifier was better than that of the demulsifier only. High
crude oil
standing wave field
temperature (80 °C) in the process was better than low temperature. Salt balance study showed that the key of
desalting desalting was: the wash water and the oil should be mixed sufficiently to extract the salts into the water as
dewatering more as possible, the water added in should be provided to be separated out. If one stage of desalting process
could not achieve the norm, two stages of desalting process should be considered.
Crown Copyright © 2009 Published by Elsevier B.V. All rights reserved.

1. Introduction monodisperse (Shvetsov and Kabirov, 1992). Thus, chemical demul-

sifiers were used for desalting heavy crude oils (Elliott et al., 1995;
Removal of corrosive water soluble salts, particularly chlorides of Varadaraj et al., 2001). Pacifico V. Manalastas suggested that a
sodium and potassium from crude oil is an important processing chemical demulsifier added into the crude oil before adding the wash
operation in refining of crude oils. The process of desalting usually water could help desalting and save the amount of wash water
involves addition 1–20% (w.) of wash water to the crude oil, mixing to (Manalastas et al., 2001). Paul Eaton reported the injection of a
form a W/O emulsion and then subjecting the emulsion to pretreatment mix of water and a special ethoxylated polyol
electrostatic demulsification or hydrocyclone treatment (Goyal demulsifier with water targeting a removal rate of more than 95%
et al., 1993; Varadaraj, 2006). Under the influence of electrostatic or salts (Eaton, 2002).
centrifugal fields the dispersed water droplets coalesce and the W/O With the quality deteriorating of the crude oils, methods such as
emulsion is demulsified. Water and the water soluble salts are cross-flow membrane (MeKechnie and Thompson, 1987), multiple
separated from the crude oil and removed. Most crude oils that stage desalting processes (Martin, 1980; Robinson, 1983; Hargreaves
contain asphaltenes and naphthenic acids tend to form stable W/O and Hensley, 1983) were developed. But nowadays, even three stages
emulsions, which are complex scattered systems (Kumar et al., 2001). of electrostatic demulsification can't meet the norm of refining. New
Salts of chlorides in the oil may be hydrolyzed into HCl to erode the researches showed that, ultrasound irradiation is a good method to
instruments, reduce the efficiency of energy exchanging, and increase enhance the process of desalting and dewatering (Sun et al., 1999; Yu
the oil flow resistance and even obstruct the pipes. Moreover, over et al., 2001; Varadaraj et al., 2001; Combette et al., 2001; Han et al.,
amount of salts and water in the crude oil would poison the catalysts 2004; Cai et al., 2005). Most of the studies concerned on the influences
in refining. In order to mitigate the corrosion, it is advantageous to of reverberation ultrasonic field to desalting of the crude oils, few of
reduce the salt concentration to under 5.0 mg/L and water content to them mentioned on applying the standing wave field of ultrasound to
under 0.3% (v.) of the crude oil before refining. that.
The crude oils are necessary to desalting and dewatering before When the standing wave of the ultrasound spreads in a fluent
distillation (Dantas et al., 2001). Key to the desalting of the crude oil is medium which contains scattered drops, the “displacement effect”
to demulsification and dewatering. The efficiency of these processes happens, this phenomenon is named demulsification. When the
depend greatly on the degree of polydisperdity of the W/O emulsion drop's density differs from that of the medium, the ultrasound
that is formed. The highly efficiency is obtained if the emulsion is standing wave will push the drop moves to the wave nodes or
antinodes. Then the drops collapse and settle down, thus to obtain the
result of demulsification. When water droplets scattered in the oil,
⁎ Corresponding author. Tel.: + 86 25 8358 8072; fax: + 86 25 8358 7066.
E-mail addresses: [email protected] (G. Ye), [email protected] (X. Lu).
standing wave of the ultrasound will push the water particles to the
1
Present address: Institute of Environment Engineering, Zhejiang University, wave nodes because the density of water is bigger than that of the
Hangzhou, PR China. crude oil.

0920-4105/$ – see front matter. Crown Copyright © 2009 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.petrol.2009.11.005
 G. Ye et al. / Journal of Petroleum Science and Engineering 70 (2010) 140–144 141

This thesis studied the standing wave field of ultrasound used for
enhancement to the LU-NING Pipeline crude oil, Sinopec. The original
salt content of the crude oil and other characters were listed in
Table 1.

2. Establishment of the standing wave field

2.1. Theories and design of the standing wave tube

The crude oil was treated in a standing wave tube. One end of the
standing wave tube was blinded, the other end of which was fixed
with the ultrasound transducer (Fig. 1).
The tube provides a good condition to obtain plane wave. Plane wave
spreading in a tube with “hard” blinded end must get a total reflection at
the interface. The reflection wave which spreads at the opposite
direction of the incident wave has the same amplitude and frequency as
the incident one. These two waves will interfere to each other. Once the
standing wave field is established, an ultrasound field with high Fig. 1. Structure of the standing wave instrument. 1 ultrasound transducer, 2 thermo
standing wave ratio can be obtained by choosing a proper distance control instrument, 3 ultrasound generator, 4 thermometer, 5 insulation, 6 standing
between the acoustic radiation surface and the reflection surface. The wave tube, 7 osciliograph, 8 hydrophone, 9 bracket.
ultrasound intensity at wave nodes is very low and that at antinodes
may be 4 times as high as the incident wave (Abe et al., 2002). measurement points to the reflection surface of the tube. The Y-axis
The standing wave tube was made of steel, 5.6 cm of inner meant the ultrasound intensity measured at different points.
diameter, 34.8 cm long and 0.2 cm of wall thickness. One end of the The measured and the calculated wave node numbers were the
tube was blinded by a smooth steel circular flat-plate in order to get a same to each other, the sound intensity measured at the antinodes
reflecting wave. The thickness of the end plate was also 0.2 cm. were also in consonant with the calculated value (Fig. 2). There was a
The acoustic impedance Zs of the medium can be calculated as little attenuation at the end of reflection surface. The result was
Zs =ρ0 ×c0. Where, ρ0 and c0 are the density and sound velocity of the satisfactory for the steady standing wave field established in the tube.
medium. The acoustic impedance of the crude oil Zoil under 80 °C was The standing wave field formed by 20 kHz ultrasound in the tube
calculated by measurement of sound velocity and density of the crude was also studied (Fig. 3). The results showed that there also formed
oil, which was 1.045 × 106 kg/(cm2s). And Zsteel could be estimated as steady wave nodes and antinodes in the tube. The wave shape of
Zsteel = ρsteel × csteel = 7.8 × 103 × 6.1 × 10 3 = 47.58 × 106 kg/(cm2s). 20 kHz ultrasound was not as good as that of 10 kHz ultrasound.
The acoustic impedance of air could be estimated as Zair =ρair ×cair = Because the standing wave tube was designed for 10 kHz ultrasound
1.29 × 330 = 0.43 × 103 kg/(cm2s). The calculations showed when the and 80 °C crude oil (inner diameter ≤ 8.8 cm). 20 kHz ultrasound
tube was filled with the crude oil, and a sound wave incidences from the needed a tube with an inner diameter less than 4.4 cm to form a good
empty end, the wave would all transmit from the oil to the steel, for Zsteel standing wave field. It could not form good plane wave and excellent
is 10 times bigger than Zoil, and the thickness of the steel end (0.2 cm) standing wave in a tube with an inner diameter of 5.6 cm.
was much smaller than the ultrasound wave length in steel (30.5 cm of Nevertheless, we had also got a wave in the tube by 20 kHz ultrasound,
20 kHz ultrasound, 61.0 cm of 10 kHz ultrasound). However, at the which was not very regular and had low standing wave ratio.
surface between steel and air, the sound wave would be totally reflected The experiments showed that low frequency ultrasound could
into steel, for Zair is far smaller than Zsteel. Thus, the wave was totally form a better steady standing wave field in a suitable tube. It was hard
reflected back. to form a good standing wave field by experiments with high
frequency ultrasound, for which needed more accuracy both in size of
2.2. Checkup of the standing wave field standing wave tube and in adjustment of distance between the
acoustic radiation surface and the reflection surface. On the other
In order to check up the formation of standing wave field, an hand, the small tubes which match high frequency ultrasounds were
experiment was done using the degassed water. useless in industry application.
The tube was filled with pure water, which was kept at 80 °C for
2 h to get rid of the air. This step could avoid the sound attenuation
caused by gas bubbles. Then the water was cooled to 33 °C. Wave
length of 10 kHz ultrasound at 33 °C in water was 15.15 cm. Thus, the
distance from the acoustic radiation surface to the reflection surface
should be adjusted as 30.3 cm (2 times as the wave length). The sound
intensity in the tube was measured by hydrophone. The results were
shown in Fig. 2. The vertical axis meant the length between

Table 1
Characters of LU-NING Pipeline oil.a

Species Value Species Value

API° 22 Salt content (mg NaCl / L) 31.93

Density (20 °C) (g / cm2) 0.9199 Water content (% v.) 0.25
Kinematical viscosity 108.0 Carbon residue (% v.) 6.41
(50 °C) (mm2/s)
Pour point (°C) 19 Ash (% v.) 0.015
Acid value (mg KOH / g) 1.92 Characteristic factor (K value) 11.75
Fig. 2. Standing wave field measured by hydrophone. -□- measured value, — calculated
a
Provided by Yangzi Petrochemical Company, Sinopec (YPC). value; ultrasound frequency: 10 kHz, ultrasound power 10 W.
142 G. Ye et al. / Journal of Petroleum Science and Engineering 70 (2010) 140–144

Fig. 3. Standing wave field measured by hydrophone. Ultrasound frequency: 20 kHz,

ultrasound power 50 W. Fig. 4. Influences of demulsifier dosage to salt content and water content at different
temperature. Water injected 5%, without ultrasound irradiation; Salt content -▲-
60 °C,-■- 80 °C; water content -△-60 °C, -□-80 °C.
3. Analyzes
of the first antinode near the probe was measured to represent the
700 mL crude oil was heated to 80 °C. Then 5% (v.) wash water was ultrasound intensity of the field.
added in it. The mixture of the crude oil and the water was agitated at The optimal ultrasound intensity was 0.38 W / cm2 for the
400 rpm for 10 min and agitated for another 5 min after adding desalting and dewatering processes (Fig. 6). Below this intensity,
20 mg/L demulsifier. Then the crude oil was placed into the standing the ultrasound field did not have enough energy to push the tiny
wave tube, the distance of acoustic radiation surface and reflection water particles to accumulate. When the ultrasound intensity was
surface was adjusted to a proper distance to get a good standing wave higher than the cavitation threshold, it would cause cavitation effect
field. After 5 min of ultrasonic irradiation, the crude oil was poured to scatter the water particles in crude oil again. So it was very
into a beaker and settled at 75 °C for 90 min. Then the water content important to keep the ultrasound intensity below the cavitation
and salt content of the supernatant oil and the settled water were threshold when use it to demulsify.
measured. From the results, it could also be found that, higher temperature
Water content of the crude oil was analyzed by the method “GB/ benefited more for the process. At 80 °C, the final water content of oil
T8929-1998 measurement of water content in crude oil (distillation)”. was 0.39%, salt content was 4.15 mg/L, which could meet the norm of
Salt content was measured by ZWC-2001 salt content measuring refinery.
instrument (with microcomputer workstation).
4.4. Influences of ultrasound irradiation time
4. Results and discussion
In the standing wave field of ultrasound, tiny water particles were
4.1. Influences of demulsifier dosage pushed to collapse into bigger ones. When the water particles were
big enough to stop vibrating with the ultrasound, they would settle
The demulsifier was important during desalting and dewatering of down by gravity. With the increasing of irradiation time, more and
the crude oil. Different crude oils should choose different types and more tiny water particles collapsed into big ones. At the same time,
dosages of demulsifiers by experiments. The demulsifier used in this the number of water particles decreased. Thus the odds of collapsing
study was type NP-1, provided by YPC. Thus it should determine the decreased too. The desalting and dewatering results would not
optimal dosage of demulsifier firstly without ultrasound irradiation. increase as great as before. The suitable irradiation time was 5 min, as
Higher demulsifier dosage got better results both in desalting and shown in Fig. 7.
dewatering (Fig. 4). And when the dosage of demulsifier was higher When ultrasound irradiation time was less than 5 min, the desalting
than 30 mg/L, the results decrease very slowly. Considering the costs and dewatering results decreased quickly with the increasing of
of industry, 30 mg/L was preferred as the proper dosage. irradiation time. After 5 min, the desalting and dewatering results
improved little and even deteriorated. After 5 min irradiation at 80 °C,
4.2. Influences of water injected

The purpose of injecting water was to extract the salts out from the
crude oil. Thus the proper amount of water injection was also studied
before the ultrasonic experiments. The final salt content decreased
with the increasing of water injection (Fig. 5). When more than 5%
wash water was injected, the decreasing of salt content slowed down
and the final water content of the oil raised. Thus although adding
more wash water would help to extract more salts out, it would also
cause the raise of the final water content in the oil. It was not
preferable to add in too much wash water. The proper amount of wash
water is about 5% (v.).

4.3. Influences of ultrasound intensity

Ultrasound intensity was an important factor in the desalting and Fig. 5. Influences of water injected to salt content and water content. Demulsifier
dewatering process. In a standing wave field, the ultrasound intensity dosage: 30 mg/L, without ultrasound irradiation; -■- salt content; -□- water content.
 G. Ye et al. / Journal of Petroleum Science and Engineering 70 (2010) 140–144 143

Fig. 8. Influences of settling time to salt content and water content under different
Fig. 6. Influences of ultrasound intensity to salt content and water content. 10 kHz,
ultrasound intensity. 10 kHz, irradiation 5 min, demulsifier dosage 30 mg/L; water
irradiation 10 min, demulsifier dosage 30 mg/L; water injected 5%; salt content -▲-
injected 5%; ultrasound intensity: -●-, -○-0.13 W / cm2; -■-, -□- 0.33 W / cm2; -▲-, -△-
60 °C,-■- 80 °C; water content -△-60 °C, -□-80 °C.
0.94 W / cm2.

the final water and salt contents of the crude oil were 0.37% and content S0 (mg/L), the total salt amount Y0 (mg) contained in the
3.85 mg/L, respectively. The corresponding desalting and dewatering mixture was: Y0 = V0 × S0.
rates were 92% and 87.9%. When water was added to extract out the salts, the salt amount in
Although the temperature was much lower than that of refinery, it the oil after extraction was: Y1 = V0 × S1 the salt amount in the water
still got good results of desalting and dewatering by the united was: Y2 = V2 × S2. Where, Y1 (mg) was the salt amount in the oil, S1
treatment of ultrasound and demulsifier. Therefore, it could be (mg/L) was the salt content of the oil after extraction, Y2 was the salt
concluded that, if the ultrasonic treatment device was added into amount in water, V2 (L) was the water volume separated from the oil,
the electric desalting and dewatering processes, the burden of electric S2 (mg/L) was the salt content of the separated water.
treat process must be decreased. The total salt amount Y (mg) after desalting was: Y = Y1 + Y2. Note
that the small amount of original water content in oil was calculated
4.5. Influences of oil settling time into oil during the calculation.
The error of salt measuring before and after the desalting process
After ultrasound irradiation, the oil should be settled for a long should be: ΔY = (Y − Y0) / Y0 × 100%. A series of experiments had been
time under some determined temperature to let the water particles done to value the errors. The conditions of each experiment were
down. listed in Table 2. Errors of the experiments were shown in Table 3.
As shown in Fig. 8, the influence of settling time to the final results From Table 3, we got such results:
was also studied. The experiments were done under three different
ultrasound intensities: 0.13 W / cm2, 0.33 W / cm2 and 0.94 W / cm2. (1) Bad desalting results were because of insufficient mixing of
The water and salt contents both decreased quickly during 0–60 min water and crude oil. Salts in the oil were commonly of chloride
settling time, and which slowed down when settling time was more salts (NaCl, KCl, and CaCl2), final salt content calculated it as the
than 90 min. Thus the suitable settling time was 90 min. equivalent of NaCl. The solubility of NaCl in water was 7 mol/kg
H2O (409.5 g/L). And the solubility of KCl and CaCl2 were all
4.6. Salt balance bigger than that of NaCl. The salt content in the settled water
was 1.476 g/L calculated as NaCl, which was far below the
In order to study the measurement errors in the desalting process, solubility of these three salts. Thus, when the amount of wash
the salt balance of the experiments was calculated. When ever in the water was not enough or the mixing of crude oil and wash
oil phase or in the water phase, the total amount of salts was constant water were insufficient, the desalting results must be bad. The
to the original amount. If there was V0 (L) volume of the oil with salt step of water injection to wash out the salts was very important
in the desalting process.
(2) All errors of the experiments were below 15%, which was
according with the measurement error of the instruments.
(3) All errors of the experiments were positive. That is to say, the
calculated salt amount after desalting is always bigger than that
before desalting. The reason is that, when water content and

Table 2
Conditions of experiments.

No. Oil Water Ultrasound intensity I Ultrasound Settling

volume injection (W/cm2) irradiation time time t2
Voil (mL) Vwater (mL) t1 (min) (min)

1 620 43.4 70 5 90
2 680 47.6 70 7 90
3 620 31 50 5 90
4 600 30 50 5 120
Fig. 7. Influences of ultrasound irradiation time to salt content and water content at
5 630 12.6 50 5 90
different temperatures. 10 kHz, ultrasound intensity 0.38 W/cm2, demulsifier dosage
6 620 12.4 50 5 120
30 mg/L, water injected 5%; salt content -▲- 60 °C, -■- 80 °C; water content -△-60 °C,
7 620 49.6 50 5 120
-□-80 °C.
144 G. Ye et al. / Journal of Petroleum Science and Engineering 70 (2010) 140–144

Table 3
Errors of the salt balance.

No. 1 2 3 4 5 6 7

Errors (%) 0.28 9.23 4.51 5.41 5.94 4.59 13.3

salt content of the crude oil were analyzed, the upper layer of
crude oil was always taken as a sample. Actually, the water
content and salt content of the upper layer oil were always
smaller than that of the bottom layer.

4.7. Two stages of desalting experiments

To the crude oil which contains high degree of salts, one stage of
desalting may not meet the demand of refinery. Thus this thesis also
discussed two stages desalting process. The flow of secondary stage Fig. 10. Influences of two stage desalting process to salt content and water contents
desalting was the same to the first stage of desalting. The results of under different irradiation times. 10 kHz, ultrasound intensity 0.38 W/cm2, water
two stages of desalting and dewatering under different ultrasound injected 5%, demulsifier dosage 30 mg/L. Salt content -▲- first stage desalting, -■-
irradiation times and intensities are shown in Figs. 9 and 10. secondary stage desalting. Water content -△- first stage desalting, -□- secondary stage
desalting.
Two stages of desalting process improved desalting results and
influenced little of the final water content of the crude oil under
optimal ultrasonic conditions. Thus, when you want to achieve good Salt balance study showed that the difficulty of desalting was: the
desalting results to some kind of crude oil, the best method was not to water and oil should be mixed sufficiently to extract the salts into the
add a big amount of water. Because over amount of water may cause water as much as it can, the water added in should be provided to
high final water content in the oil. The proper way was to use the separate them out.
multiple stages desalting process with ultrasonic standing wave field. If one stage of desalting could not meet the norm, the two stages of
desalting process should be introduced in. The standing wave field of
5. Conclusions ultrasound should be merged in an electric desalting and dewatering
process to study the enhancement of ultrasound.
A good standing wave field was established in a designed standing
wave tube by 10 kHz ultrasound. And serials of experiments had been References
done in such a standing wave field to study the desalting and
Abe, Y., Kawaji, M., Watanabe, T., 2002. Study on the bubble motion control by
dewatering of the LU-NING pipeline crude oil. ultrasonic wave. Exp. Thermal Fluid Sci. 26, 817–826.
The results showed that the best condition to treat the crude oil Cai, Y.W., Xie, W., LU, X.P., et al., 2005. Demulsification and dehydration of water-in-
was: ultrasound intensity 0.38 W/cm2 (standing wave field), 10 kHz, crude oil emulsions in ultrasonic standing wave field. Pet. Process. Petrochem. 36
(5), 13–17 (Chinese).
irradiating the crude oil for 5 min, adding 30 mg/L demulsifier, 5% (v.) Combette, P., Roudil, D., Despaux, G., 2001. Emulsion characterization by focused
of water injection, and settling for 90 min. The final results of salt and ultrasonic waves. Ultrasonics 39, 329–334.
water contents were 3.851 mg/L and 0.37%. Dantas, T.N.de C., Neto, A.A.D., Moura, E.F., 2001. Micoremulsion systems applied to
breakdown petroleum emulsions. J. Pet. Sci. Eng. 32, 145–149.
Standing wave field united with demulsifier was better than using Eaton, P., 2002. Method for pretreatment of refinery feed desalting the feedstock, and
the demulsifier only. The desalting rate and dewatering rate of the related additive. US 6,383,368 B1.
former were 11.5% and 4.3% higher than the latter. Elliott, P.L., Braden, M.L., Newman, D.J., 1995. Desalter wash water additive. US
5,449,463.
High temperature (80 °C) in the process was better than low
Goyal, S.K., Mosby, J.F., Treadman, II, J.E., 1993. Removal of metals and water-insoluble
temperature. materials from desalter emulsions. US 5,219,471.
Desalting results increased with the increasing of injection water. Han, P.F., Qi, G.M., LU, X.P., 2004. Study of crude oil emulsion breaking via ultrasound.
But when injection water was more than 5% (v.), it would be difficult Chem. Eng. (China) 32 (1), 42–46.
Hargreaves, J.T., Hensley, A. L., 1983. Multiple stage desalting and dedusting process. US
to dewater for the following process. Considering such a condition, 4,415,434.
the proper amount of injection water was 5%. Kumar, K., Nikolon, A.D., Wasan, D.T., 2001. Mechanisms of stabilization of water-in-
crude-oil emulsion. Ind. Eng. Chem. Res. 40, 3009–3014.
Manalastas, P.V., Varadaraj, R., Savage, D. W., et al., 2001. Crude oil desalting method. US
6, 228, 239 B1.
Martin, R. B., 1980. Plural parallel stage desalting and dehydration. US 4,209,374.
MeKechnie, M. T., Thompson D. G., 1987. Method for desalting crude oil. US 4,684,457.
Robinson, J. R. 1983. Plural stage desalting/dehydrating apparatus. US 4,374,724.
Shvetsov, V. N., Kabirov. I. I., 1992. Crude oil desalting with electric polverization of
washwater. Kazan' state Pedagogical Insititute. Translated from Khimiya i
Tekhnologiya Topiv i Masel. (6), 16–18.
Sun, B.J., Yan, D.C., Qiao, W.X., 1999. The study of demulsification with ultrasonic
irradiation on oil emulsion. Acta Acustica 24 (3), 327–331 (Chinese).
Varadaraj, R., 2006. Oil desalting by forming unstable water-in-oil emulsions.
US7,108,780 B2.
Varadaraj, R., Savage, D. W., Brons, C. H., 2001. Chemical demulsifier for desalting heavy
crude. US 6,168,702 B1.
Yu, J.Y., Yuan, P., Yu, L., 2001. Experiment study on the sound-field parameters for
crude-oil dehydration by ultrasonic demulsification. Appl. Acouct. 20 (3), 27–30
(Chinese).

Fig. 9. Influences of two stage desalting process to salt content and water content under
different ultrasound intensity. 10 kHz, irradiation 5 min, water injected 5%, demulsifier
dosage 30 mg/L; salt content -▲- first stage desalting, -■- secondary stage desalting;
water content -△- first stage desalting, -□- secondary stage desalting.