Demulsifier formulations optimize crude oil emulsion separation

1
Demulsifiers: Water-in oil emulsion separation results
Chandran Udumbasseri, Technical Consultant
cudumbasseri@yahoo.co.in; chandran.udumbasseri#@gmail.com
Introduction
Crude oil emulsion breaking is one of the hardest operations in oil separation
from entrapped saline water. The oil coming out of a crude oil drilling well is
composed of dissolved natural gas, water trapped as free and emulsified,
and solid materials like sand, mud, insoluble inorganics, sludge, and other
rock sediments from the bottom of the well. The water is usually salty and
varies from well to well. The composition of each well is different. It
necessitates different types of processing chemistry for each well. There is
only a general outline of processing for all types of crude emulsion
separation but needs specific processing chemistry well.
The crude oil coming out of a well is sent to separating plant where
demulsifier is injected in the incoming pipeline. Due to turbulent flow the
demulsifier gets mixed up evenly in the crude oil and initiates emulsion
breaking. The crude then goes to high pressure separating tank (horizontal,
slanted, spherical, hemispherical or vertical) where freed natural gas moves
to collecting compressors, water separates at the bottom while oil float as
top layer.
The water is drained from the tank as the oil is allowed to move to low
pressure separator where remaining gas is removed from the crude oil. The
crude which is wet coming out of this second separator is sometimes heated
to facilitate emulsion breaking or allowed to go to dehydrator unit for
removing residual water electro statically. After complete water removal by
dehydrator the oil is dry in nature with some crystals of salt remaining in the
suspended state in the oil. So the oil is again washed with water by mixing
wash water. Outgoing oil is tested to ensure dryness and salt level.
Some test results are given below for different oils
Saudi oil
Flow diagram
HPPT
HPPT
LPPT
DehydratorDesalter
Shipment line
Production
Header
Sample Point
Wash water injection

2
1. Plant 1
Process Data
Process Information
Total production rate 233000BD
Total crude oil rate 145000BD
Percentage water cut 38-42%
Temperature at production header 130F
Oil level in separators & dryers 50%
Salt in crude, average 5 PTB
Water cut
Free Water 20-40%
Total water 52-58%
Emulsion 12-38%
After bottle testing the best performing demulsifier bases are given below
Demulsifier
Bases
Conc Water
dropping
mls/minutes
W
Q
IQ
Salt
content
Chemistry RSN
ppm 10 20 40 PTB
DG270 20 12 20 32 F F- 17.85 Modified ester 6.7
DI938 20 6 9 12 F F 48.8 Polymeric polyol 7.7
Croda-D3501X 20 9 16 18 F F 24.6 Alkoxylated phenolic resin 15
D311 20 9 12 18 P F 27.9 Oxylate phenolic resin 18
D309 20 8 9 10 G F 46.6 Oxylate phenolic resin 29
DB5951 20 7 12 24 P F + 27.9 Tetrol 11
DI945 20 10 11 18 F F 44.9 Amine alkoxylate 16
D3575X 20 13 19 24 G G 19.38 Mixed resin ethoxylate 17
DB9393 20 0 0 Tr - - 3.4 Amine ethoxylate 6.7
D3422X 20 0 3 12 F F- 3.56 Imine alkoxylate 8
D510 20 4 6 12 P P 7.28 Imine alkoxylate 11
DB9947 20 4 16 18 F G 9.17 Resin EO/PO alkoxylate 13
DB9429 20 5 18 22 G F+ 35.4 Resin alkoxylate 10-14
D304 20 5 12 14 G G 13.17 Resin alkoxylate 21
DRA21 20 9 14 16 P P 8.25 Oxy phenolic resin 21
DRI9030 20 0 5 16 F G 11.68 Esterified phenolic polymer 7-8
DRI9037 20 0 10 16 F F 7.68 Polyol 7-8
RDM9510 20 0 5 8 P P 9.24 Blend 7-9
13190 20 9 18 20 G F 7.3 Epoxy resin 7.6
PG1.5 20 0 0 5 P P 5.15 Polyglycol 14.1
PG2.5 20 1 5 16 F F- 9.5 Poly glycol 17.3
DRC232 20 8 10 14 G G 53.9 Oxylated resin 14.3
DEE5 20 0 0 0 - - 1.48 Polyethylene amine mixture 6
RS19 20 10 24 30 G G 17.82 Alkoxylated resin 12
RS15 20 5 14 24 F F 29.2 Alkoxylated resin 13
CB361 20 9 16 18 G F 27.8 NPF-EO/PO
DB9392 20 0 9 22 G P 2.49 PEI alkoxylated 8.3
Basorol-P17R2 20 2 2 6 G P 5.5
Syn PEL101 20 5 9 14 G G 35.4
Syn T1301 20 14 20 20 G F 30.2
W033 20 3 10 13 G G 29.2 Polyol 16
W0801 20 3 5 10 G G 24
3073 20 4 6 15 F P 37.1

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The following formulations were found better performers
Selected Formulations
Formulation Ratio Grading Average activity
DB9947/DB9392/DB9393 2/2/1 1 42%
W033/DB9392/DB9393 2/2/1 2 42%
DB9947/DG270/DB9393 2/2/1 3 42%
DB9958/DG270/DB9393 1/1/1 4 42%
DRI9037/DB9392/DB9393 2/2/1 5 50%
DG270/DB5951/DB9393 1/2/1 6 50%
Conclusion-Final Formulation
Formulation
Conc Water dropping
mls/minutes WQ IQ
Top oil water cut,
%
Salt
content
ppm 10 20 40 W1 W2 ∆ PTB
incumbent
20 Tr 4 18 F2+
F 5.2 5.2 0 24.9
30 5 18 50 F-
P 2.0 2.15 0.15 5.67
(F1)DB9947/DB9392/DB9393
2/2/1
20 4 6 42 VG G 0 0 0 2.04
30 14 48 54 VG G 0 0 0 2.08
(F2)W033/DB9392/DB9393
2/2/1
20 5 12 36 G F+
0.05 0.05 0 1.29
30 20 36 52 F-
G 0 0 0 0.84
Evaluation
Evaluation of results: The final demulsifier is based on DB9947, DB9392,
DB9393, DB 5951, DB9958 (all BASF bases), DG270 (Marchem) and W033
(Deshi)
The table of bases screening is giving the following data for using
formulations
Formulation
Conc Water dropping
mls/minutes
WQ IQ
Salt
conte
nt
Chemistry
ppm 10 20 40 PTB
DG270 20 12 20 32 F F- 17.85 Ester
DB5951 20 7 12 24 P F + 27.9 Tetrol
DB9392 20 0 9 22 G P 2.49 PEI alkoxylate
DB9947 20 4 16 18 F G 9.17 ResinEO/PO alkoxylate
DRI9037 20 0 10 16 F F 7.68 Polyol
W033 20 3 10 13 G G 29.2 Polyol
DB9393 20 0 0 Tr - - 3.4 Imine ethoxylate
Highest water dropper is DG270. The efficiency reduces down the line. Low
salt content is present in DB9393 without any water dropping while DB9392
shows both low salt (2.49) and comparatively higher water dropping (22).
W033 is poor water dropper and high salt, but with good water quality.
DB9947 and DRI 9037 show similar behavior in water dropping and salt.
The formulator used DB9947/DB9392/DB9393 (resin alkoxylate /PEI
alkoxylate / amine alkoxylate), W033/DB9392/DB9393 (polyols /PEI
alkoxylate / amine alkoxylate), W033/DB9392/DB9392 (polyols /PEI

4
alkoxylate /amine ethoxylate) and DB9947/DG270/DB9393 (resin
alkoxylate/ester/amine ethoxylate) as the first four formulations
For the final approved selection the following two formulations were
selected.
Formulation
Conc Water dropping
mls/minutes WQ IQ
Top oil water
cut, %
Salt
content
ppm 10 20 40 W1 W2 ∆ PTB
(F1)DB9947/DB9392/DB9393
2/2/1
20 4 6 42 VG G 0 0 0 2.04
(F2)W033/DB9392/DB9393
2/2/1
20 5 12 36 G F+
0.05 0.05 0 1.29
In formulation F1, water dropping was 42ml, salt content 2.04PTB; top oil
water cut 0%, very good water quality and good interface quality.
How was the quantity of dropped water increased to 42? This is the
synergistic effect that helped the formulation to drop more water.
The salt content considerably reduced to 2.04PTB, which is due to the
removal of most of the water from the organic layer. The top oil BS&W was
0% which supported the low salt content in the oil layer. In F1 the interface
quality was reported as good which supported the very low BS&W (0%).
Coming to F2 water dropping is a little less (36) but salt content was
reported as low as 1.29PTB. This shows that F2 needed more time for
flocculating the remaining water which was already separated and hangs in
the oil layer. It was evident from the quality of interface which says Fair plus
that means some more time is required for the clearing of interface.
It appears a little bit complicated to come out with constructive formulations
that can perform well in bulk trials. Mostly the formulators’ knowledge and
experience matters a lot in the conclusion.
Criteria for better performing demulsifier formulation:
1.1. Competent formulator with outstanding chemical knowledge and
experience is a plus point for a formulation. Such formulator can
bring out best performing formulation even if the demulsifier bases
are not up to the requirements.
1.2. Well performing demulsifier bases can give very good performing
formulations.
Below are given more results from bottle testing which can be evaluated and
understood.

5
2. Plant 2
Process Data
Process Information
Total water cut 68000BD
Temperature at production header 130F
Oil level in separators & dryers 50%
BS&W
Free water 3-5%
Total water 40-45%
Emulsion 35-42%
Demulsifier bases performed with this crude
Demulsifier
Bases
Conc Water dropping
mls/minutes WQ IQ
Salt
content Chemistry RSN
ppm 10 20 40 PTB
DI937 50 1.5 1.3 5 F F 82.3 Polymeric polyol 7.7
DG270 50 2 2.5 9 F G 76 Modified ester 6.7
D311 50 0.2 7 9 P F 93 Oxylate phenolic resin 18
D3575X 50 4 6.5 8 F F 68.8 Resin ethoxylate 17
D510 50 0 0 0 - - 76 Imine alkoxylate 11
DRI9030 50 0 2 4 F F 70 Ester of phenolic polymer 7-8
DB9429 50 0 2.5 5 G F+ 77.8 Resin alkoxylate 10-14
RS15 50 0 0.5 3 G G 77.8 Alkoxylated resin 12-14
RS19 50 Tr 1 4 F F+ 75 Alkoxylated resin 12
3501X 50 1.8 4 6 F F 75 -
T1301 50 0 4 8 G G 75 - -
W-033 50 0.4 2.5 6 G G 75 Polyol -
DB9955 50 0 2 7 F+ G 75 EO/PO alkoxylate 13-15
Basorol L62 50 0 0.1 1.2 F+ F+ 71 - -
Kemelix-D310 50 0 2 4 F G 72 - -
CB MC238A 50 0.3 0.4 1.0 F F 33 - -
Croda-D300 50 0 0 0.6 F F+ 73 Blend 7-9
DG4283 60 9 10 12 F+ F+ 70.6 Rsin alkoxylate 10.6
D3627X 60 3 7 9 F+ F+ 73 Resin alkoxylate 21
DB9946 60 1.3 9 10 VG G 67 Resin alkoxylate 10-12
SynPE25R2 60 0 2 3 F F+ 56 Polyol alkoxylate 13
DI224 60 0 0.4 1 F F+ 44 - -
DI936 60 4 7 9 F F+ 61 Polyol 8.4
W33/DP188/DB9393 4/1/1 1 42%
DB9947/DG270/DB9393 2/2/1 2 42%
DB9947/DB9392/DB9393 2/2/1 3 42%
DRI9030/D510/DB9393 2/2/1 4 42%

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Formulation
Conc Water dropping
mls/minutes WQ IQ
Top oil water cut,
%
Salt
content
ppm 10 20 30 40 W1 W2 ∆ PTB
Incumbent
60 12 18 20 21 F F 13 15 2 44.8
70 16 23 23 24 F F 8 10 2 32.5
W033/DP188/DB9393;
4/1/1
60 16 20 24 26 VG VG 5 5 0 4.37
DB9947/DG270/DB9393;
2/2/1
60 23 24 28 36 G G 0.4 0.4 0 8.26
Evaluation:
In the Plant 2, efficient emulsion breakers are DB9947, DB9393, DB9392 (all
from BASF), DP188 (Majorchem), DG270 (Marchem), D510 (Croda),
DRI9030 (Akzo) and W033 (Deshi)
Demulsifier
Bases
Conc Water dropping
mls/minutes WQ IQ
Salt
conte
nt
Chemistry RSN
DG270 50 2 2.5 9 F G 76 Modified ester 6.7
DRI9030 50 0 2 4 F F 70 Ester of phenolic polymer 7-8
W-033 50 0.4 2.5 6 G G 75 Polyol -
The formulator has included the formulation from Plant 1 to see their
performance. So he has taken corresponding bases from those formulations.
This definitely reduces the time of scanning and formulations.
As the salts were found high (in the range of 60-75 PTB) it appears that
more time was required for individual bases to drop more water. The water
cut was 45% but maximum water dropped was 12 and formulator did not
consider particular base for formulation. Also the dosage concentration
needed was more than 50ppm.
The selected formulations
Formulation
Conc Water dropping
mls/minutes WQ IQ
Top oil
water cut, %
Salt
content
ppm 10 20 30 40 W1 W2 ∆ PTB
W033/DP188/DB9393; 4/1/1 60 16 20 24 26 VG VG 5 5 0 4.37
DB9947/DG270/DB9393; 2/2/1 60 23 24 28 36 G G 0.4 0.4 0 8.26
First formulation showed lower water dropping (26ml) while second
formulation showed (36ml) higher dropping. But the formulator did not
consider water dropping as the best criteria. First formulation showed very
low salt content, 0% top oil BS&W, very good water and interface quality.
Low salt content and 0% BS&W ensure that the emulsion has completely
broken; good water quality and interface quality ensure that there is no
over-treat and all the emulsion has broken.
This justifies formulator’s selection considering first formula as best
performer.

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It explains that more water dropping is not the criteria for selection.
Ensuring complete emulsion breaking is the criteria for selection of a
formula.
3. Plant 3
Process Data
Process Information
Temperature at production header 110F(Winter);
150F(summer)
BS&W
Free water 4-16%
Total water 20-34%
Emulsion 4-30%
Demulsifier bases performed better with this crude
Demulsifier
Bases
Conc Water dropping
mls/minutes WQ IQ
Salt
ppm 10 20 40 PTB
DI937 25 1.2 4 5 F F 40.7 Polymeric polyol 7.7
DG270 25 2 7 8 F F 66 Modified ester 6.7
D311 25 2.5 4 5 F F+ 73 Oxylate phenolic resin 18
D3575X 25 4 5 5 G F 62 Resin ethoxylate 17
DB9393 25 Tr Tr Tr - - 40 PEI ethoxylated 6.5
DB9392 25 Tr 1 4 F F+ 73 PIE ethoxylated 8.3
DB9947 25 1 1.8 4 F+ F2+ 69 Resin EO/Po ethoxylate 13
DRI9030 25 3 7 7 F F+ 62 Ester of phenolic polymer 7-8
PG1.5 25 1.2 1.5 4 VG F+ 90 Polyglycol 14
RS15 25 1.6 4 7 F F+ 68 Alkoxylated resin 12-
14
D3501X 25 2 3 4 F F 83 -
W-033 25 6 8 9 G G 70 Polyol -
DI936 25 3.5 5 8 F+ F 65 Acrylate polyol 8.4
Basorol K2090 25 Tr 3 5 F+ F+ 68 - -
CB DI910 25 0 0 0 - - 50 - -
DG4283 25 4 5 6 G F+ 68 Resin alkoxylate 10.6
RDM9510 25 4 8 9 F F+ 54 Blend 7-9

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DB9947/DB9392/DB9393 2/2/1 1 37.5%
W033/ DB9392/DB9393 2/2/1 2 37.5%
W033/DG270/DB9393 2/2/1 3 37.5%
Formulation
Conc Water dropping
mls/minutes WQ IQ
Top oil water cut,
%
Salt
content
ppm 10 20 30 40 W1 W2 ∆ uS/cm
Incumbent
30 6.5 9.5 12 18 F+ F 0 0.4 0.4 19.84
35 9 14 18 24 G F 0 0.4 0.4 19.45
40 12 17 20 26 F F 0 0.3 0.3 11.29
DB9947/DB9392/DB9393
2/2/1
35 9.5 18 24 30 G G 0 0 0 5.54
W033/ DB9392/DB9393
2/2/1
35 10 14 18 31 VG VG 0.05 0.05 0 5.92
Evaluation:
This plant (3) crude oil is similar to Plant 1 crude oil. So most of the
demulsifiers performed in 1 also performed in Plant 3. So the final selected
formulation is the same.
4. Plant 4
Process Data
Process Information
Percentage water cut 22%
Water separation in HPPT 10-15 mbd
Temperature at production header 95-115F(W); 135F(S)
Oil level in separators 35%
Oil level dehydrator 50%
Oil level desalter 50%
Salt in crude, average 5-6 PTB
BS&W
Free water 0 – 2%
Total water 24-26%
Emulsion 24-26%
Demulsifier bases performing with this crude
Demulsifier
Bases
Conc Water dropping
mls/minutes
WQ IQ
Salt
conte
nt
Chemistry RSN
ppm 10 20 40 PTB
DI938 30 2 2.5 3 F F 48.9 Polymeric polyol 7.7
DI937 30 1 3 4 F+ F 48 Polymeric polyol 7.6
DG4283 30 2 3 3 F+ F+ 46 Resin alkoxylate 10.6
DB9946 30 0 1 2 G F+ 50 Resin alkoxylate 11

9
D3627X 30 Tr 3 4 F+ F+ 46 Resin alkoxylate 21
D311 30 2 3 4 F F 44.6 Oxylate phenolic resin 18
D3575X 30 3 4 4 F+ F 48.9 Mixed resin ethoxylate 17
DB9393 30 0 0 Tr - - 50 Amine ethoxylate 6.7
DB9947 30 1 1.1 2 F+ F+ 50 Resin EO/PO alkoxylate 13
DRI9037 40 2 4 4 F+ F+ 51 Polyol 7-8
RDM9510 40 2 4 4 F+ F+ 49 Blend 7-9
RS15 40 Tr 1.8 4 F+ F+ 46 Alkoxylated resin 13
DB9392 40 0 0 0 - - 56 PEI alkoxylated 8.3
W033 40 1 3 4 G G 52
3073 40 0.7 1.8 3 F+ F++ 48
DI936 40 1 2 4 F F 55 Acrylic polyol 8.4
DB9904 40 Tr - - - - 44 Tetrol block polymer 11.5
W033/DB9392/DB9393 2/2/1 1 35%
W033/RS15/ DB9393 2/2/1 2 35%
W033/DRI9037/ DB9393 2/2/1 3 35%
Formulation
Conc Water dropping
mls/minutes WQ IQ
Top oil water cut,
%
Salt
content
ppm 10 20 30 40 W1 W2 ∆ PTB
Incumbent 60 9 10 12 16 F F 4 4.5 0.5 24.9
W033/DB9392/DB9393;2/2/1 40 9 16 22 22 VG VG 0.05 0.05 0 4.74
W033/RS15/ DB9393;2/2/1 40 10 18 22 22 VG VG 0.1 0.1 0 4.79
W033/DRI9037/ DB9393;2/2/1 40 10 14 17 22 VG VG 0.1 0.15 0.05 6.71
Evaluation: The plant 4 crude oil appears similar to that of 1, 2 and 3. So
the final formulation is similar to that of previous formulations.
5. Plant 5
Process Data
Process Information
Temperature at production header 95-115F(W);
135F(S)
Oil level dehydrator 50%
Oil level desalter 50%

10
BS&W
Free water 0 – 3%
Total water 14-17%
Emulsion 14-16%
Demulsifier
Bases
Con
c
Water dropping
mls/minutes
WQ IQ
Salt
conte
nt
Chemistry RSN
ppm 10 20 40 PTB
D501 25 0 0.5 1 F+ F 42.7 Polyol 22
D400 25 2 3 3 G F+ 36.7 Ethoxylate phenolic resin 18
PE10100 30 3 4 4 F+ F 48.9 EO/PO Block polymer 20.1
W033 40 0 Tr 2.4 G G - Polyol 10
RS15 40 Tr Tr 0.5 F+ F+ 42.7 Alkoxylated resin 13
L62 40 0 Tr 0.3 G G 42 -
CB-AP954 40 0 0.1 1.0 G G 40 -
D401 40 0 0.1 0.4 F+ F+ 43 -
D3424X 40 0 0.2 0.5 F+ F+ 42 -
DB9954A 50 0 1 1 F+ F+ 47 Resin alkoxylate 11
DRI9037 30 Tr Tr 0.2 F+ F+ 40 Polymeric Polyol 7-8
Formulation
Conc Water dropping
mls/minutes
WQ IQ
Top oil water cut, % Salt
conten
t
ppm 10 20 30 40 W1 W2 ∆ PTB
Incumbent
70 3 4.5 5 6 F+ F+ 12 12 0 43.5
75 3.1 4.8 5 6 F+ F+ 12 12 0 45
W033/D501/DRI9037
(1/2/1) with 10% (H
Acid)
60 2 4.8 7 8 VG G 11 11 0 33.8
Evaluation
The demulsifier bases that worked in this crude oil were very limited; a
maximum of 57% water was dropped with the formulation. All the three
bases in this formulation were polyols from different suppliers - D501 (polyol
RSN 22), W033 (polyol RSN 10), DRI9037 (polyol RSN 7-8). As the RSN
differs each of them works at different solvent conditions. Most of the time
polyols appear as assisting demulsification rather than actual main emulsion
breaker. So there is a lack of competent emulsion breaker in the list of
demulsifiers that were used for screening this crude oil emulsion. The H-acid
was used here to clarify both water quality and improve interface quality.
Need of a highly branched flocculant demulsifier is lacking in this testing

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6. Plant 6
Process Data
Process Information
Temperature at production header 110-120F(W); 135F(S)
Oil level in dehydrator/desalter 50%
Water cut
Free water 2– 4%
Total water 16-18%
Emulsion 12-16%
Demulsifier
Bases
Con
c
Water dropping
mls/minutes
WQ IQ
Salt
conte
nt
Chemistry RSN
ppm 10 20 40 uS/cm
D501 35 Tr 1.8 2 F+ F 29.2 Polyol 22
DB9393 35 Tr 1 2 F F 24.2 Amine ethoxylate 6.5
D311 35 0 0 0 - - 37 Oxylated phenolic resin 18
W033 35 1 2.5 3 F G 32 Polyol 16
RS15 35 3 Tr 0.5 F+ F+ 42.7 Alkoxylated resin 13
DRI9037 35 Tr Tr 1 F F 30 Polymeric Polyol 7-8
CBDI950 35 0 1 2 P P 33 Polyol 8
DI937 35 0 0.1 0.4 F+ F+ 34.6 Polymerized polyol 7.6
CB 461 35 Tr 1 1.5 F+ F+ 32 NPR rsin alkoxylate 12.5
CBRO510 35 0.6 1.8 2 P F 33.7 Resin alkoxylate 20
DI945 35 0 1 2 F F 30.7 Amine oxyalkylate 16
DG4283 35 0.5 3 3 G F 32.7 Resin alkoxylate 10.6
D3575X 35 1 2 3 G F 29.4 Modified resin ethoxylate 17
D3627X 35 1 1.5 1.5 F F 30 Resin alkoxylate 21
D3535X 35 1 2 3 F F 32 APF resin ethoxylate 17
DB9946 35 1.5 1.8 2.5 F F 28.2 Resin alkoxylate 11
DB9947 35 1 2 2 F F 29 Resin (EO/PO) alkoxylate 13
DB9955 35 1.5 3 3 F F 28 Resin alkoxylate EO/PO 14
PE6400 35 1 1.5 1.8 F F 29 EO/PO block 20.1
DP-188 35 0.8 1 2 F F 26 Polyol 16
DB9942 35 Tr 2 3 F F 44 Resin alkoxylate 8-9
DRC232 35 0.5 1 4 F F 40 Resin alkoxylate 14.3
DPG482 35 0.5 1 2.8 F F 44 Polyglycol 18.8
DB9429 35 Tr 1 2.8 F F - Resin alkoxylate 10-14
DE-E5 35 Tr 1 1.2 F F 26 Amine alkoxylated 6
DRI9045 35 1.2 1.8 2 F F 40 -
CB361 35 1 2 2 F F 42 NPF EO/PO -
DRC168 35 0 2 2 F F 44 -
RS11 35 Tr 1.8 2 F F 40 Alkoxylated resin 17
L101 35 0 1 1.6 F F 39 -

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Formulation
Conc Water dropping
mls/minutes WQ IQ
Top oil water cut,
%
Salt
content
ppm 10 20 30 40 W1 W2 ∆ PTB
Incumbent 50 7 9 9 10 F+ F- 3 3.5 0.5 14.71
W033/DP188/DB939
(2/1/1)
40 7 10 13 15.5 G G 0.6 0.6 0 9.73
RS15/DEE5/DB9393
(2/1/1)
40 4 10 13 14 G G 0.2 0.2 0 8.97
Evaluation: The crude oil feed for this plant different in its behavior
compared to 1, 2, 3, and 5. The water cut in this crude oil emulsion is 16-
18% so the expected water dropping was around 11-12 ml from 100ml
sample, taking in to account of an average dropping of 70% emulsion
breaking. But the highest amount of water dropped is just free water.
The screen test did not support the formulator with good information. The
salt test also did not support with good information.
So the formulator depended on synergism.
The final formulations selected were W033/DP188/DB9393 and
RS15/DEE5/DB9393. The formulator reached at these formulations after a
number of tests.
W033 and DP188 are polyols, DB9393 and DEE5 are imine alkoxylates and
RS15 is a resin alkoxylate.
Polyol with imine alkoxylate synergism (F1) dropped almost 92% water in
the emulsion. Salt content reduced to 9PTB and top oil BS&W 0% with a
0.6% suspended water.
Resin with imine alkoxylates synergism dropped 85% water, salt content
reduced to 9PTB and top oil BS&W 0% with suspended water of 0.2%
The study of synergism was explained in the following article shown in
Linkedin slideshare:” Review of demulsifier bottle testing procedure” by
the same author.
7. Plant 7
Process Data
Process Information
Percentage water cut 46%
Temperature at production header 108F(W);
150F(S)
BS&W

13
Free water 50– 56%
Total water 50-56%
Emulsion 0-2%
Demulsifier
Bases
Conc Water dropping
mls/minutes WQ IQ
Salt
ppm 10 20 40 PTB
DG270 15 24 32 34 G G 51.4 Modified ester 6.7
DB9393 15 Tr 0.2 7 G F+ 4.32 Amine ethoxylate 6.7
DI945 15 11 12 20 VG G 81.2 Amine oxyalkylate 16
D3575X 15 12 18 19 F+ F+ 120 Modified resin ethoxylate 17
DE E5 15 0 6 33 F F+ 6.32 Polyethylene amine alkoxy 6
D3422X 15 1.5 5 36 F+ F+ 3.86 Polyimine alkoxylate 8
DEPA10 15 8 12 22 F+ F+ 5.78 Polyethylene imine alkoxy 9-10
DB9390 15 7 14 27 VG G 5.88 PEI alkoxylate
DB9360 15 3 6 10 VG G 17 PEI alkoxylate -
DRI9037 15 4 10 18 F+ F + 22 Polymeric Polyol 7-8
DI936 15 3 10 20 F F 32 Acrylic polyol 8.4
DB9904 15 10 20 26 G F 73 Tetrol 11-12
DP188 15 1 18 42 VG F+ 3.78 Polyol 16
DG4283 15 10 14 15 F+ F 98 Resin alkoxylate 10.6
DB9947 15 13 16 24 VG G 95 Resin EO/PO alkoxylate 13
RDI3124 15 8 12 16 F G 123 Resin oxyalkylate 13.9
DR19030 15 2 8 19 F+ F 5.85 Ester phenolic polymer 7-8
DRM9510 15 3 9 14 F+ F+ 40 Blend 7.9
DRC232 15 12 18 21 F G 88 Oxylated resin 14.3
CB361 15 4 10 15 F+ F 104 NPF EO/PO -
Formulation
Conc Water dropping
mls/minutes WQ IQ
Top oil water
cut, %
Salt
content
ppm 5 10 20 30 40 60 W1 W2 ∆ uS/cm
Incumbent 11 22 28 36 43 48 52 VG F 0.3 0.4 0.1 28.1
DI945/D3422X/CB9393
(2/2/1), F1
15 20 28 39 48 51 54 VG G 0.1 0.2 0.1 7.95
D3575X/DRM9510/DB9393
(2/1/1), F2
15 20 28 35 43 50 52 F G 0.15 0.2 0.05 9.55
D3575X/DI936/DB9393
(1/2/1), F3
15 20 36 48 50 50 52 F G 0.1 0.2 0.1 9.79
Evaluation:
The water cut in this plant is 50-56%.better performers are:
Demulsifier
Bases
Conc Water dropping
mls/minutes WQ IQ
Salt
ppm 10 20 40 PTB
DG270 15 24 32 34 G G 51.4 Modified ester 6.7
D3422X 15 1.5 5 36 F+ F+ 3.86 Polyimine alkoxylate 8
DP188 15 1 18 42 VG F+ 3.78 Polyol 16
DE E5 15 0 6 33 F F+ 6.32 Polyethylene amine alkoxy 6

14
Evaluation:
In the final formulation the bases used were much different, may be the
reproducibility of performance lost or not found in the subsequent tests,
which were not presented here by the formulator.
The final formulations show good water dropping, low salt content, low top
oil BS&W, good water quality (F1) and interface quality.
DI945 (amine alkoxylate), D3422X (amine alkoxylate), CB9393 (resin
alkoxylate), D3475X (resin alkoxylate), DRM9510 (blend formulation),
DI936( polyol) and DB9393 (amine alkoxylate) are the selected bases for
the final formulation
Here amine alkoxyalte and resin alkoxylate are the blend of formulation, F1
ad F2, and polyol and amine alkoxylate are the blends of F3 formulation.
Formulation
Conc Water dropping
mls/minutes WQ IQ
Top oil water
cut, %
Salt
content
ppm 5 10 20 30 40 60 W1 W2 ∆ uS/cm
DI945/D3422X/CB9393
(2/2/1), F1
15 20 28 39 48 51 54 VG G 0.1 0.2 0.1 7.95
Plant crude oils and selected demulsifier blends
Plant crude oil Slected demulsifier blends
1 2 3
Plant1 Resin alkoxylate/amine
alkoxylate
Polyol/amine alkoxylate
Plant 2 Resin alkoxylate/amine
alkoxylate
Polyol/ester/amine
alkoxylate
alkoxylate
Polyol alkoxylate/amine
alkoxylate
Plant 4 Resin alkoxylate/ amine
alkoxylate
Polyol/resin
alkoxylate/amine
alkoxylate
Plant 5 Polyol (RSN22)/polyol
(RSN 10)/polyol (RSN
7.5) with sulfonate acid
Plant 6 Polyol/amine alkoxylate Resin alkoxylate/amine
alkoxylate
alkoxylate
From above data for all gas oil separating plants the demulsifier formulations
that performed well in bottle tests (also in subsequent field trials) are blends
of resin alkoxylates/amine alkoxylate and polyol/amine alkoxylates. In some
cases resin alkoxylate/polyol/amine alkoxylate blend was also working.
Esters give added advantage to the blends.
Polyols are usually EO/PO co-polymers with multiple hydroxyl end groups.
The hydroxyl end groups usually extend to water droplets of medium sized

15
emulsions. Esters are also hydroxyl containing polymers which associate
with water by hydrogen bonding.
Amine/imine alkoxylates with their extended network functions as treaters
that can break even small micro emulsions. The nitrogen in amines like
oxygen in polyols can develop different types of association with water
molecules using Vander Waals forces.
The general concept is that nitrogen and oxygen containing polymers with
net work character can break the water-in oil emulsion and flocculate.
Giants in fossil fuels

16
Iranian oil
The demulsifier formulations were developed for GOSPs having crude oils
with API gravity in the range 16-25. The crude oil appeared to contain more
asphaltene and very viscous and sticky in nature. The total retention time
was 16-24 hours which shows bottle test result conclusion may be time
consuming if replicated plant retention time. So the tests were restricted
with 1 hour retention time for bottle testing. As the incumbent samples were
also tested along with that of vendor’s demulsifiers, the results can be
comparable. The dry crude oil specification was - salt content < 10PTB, and
water (BS&W) <0.5%. As the crude oil was sticky the demulsifiers were
dosed at 60o
C to have good mixing and distribution.
1. Plant 1
Process Data:
Process Information
Quantity Unit
Production Rate 73000bd MBD
Wash Water 3650bd BD
Salt inlet 5120 ppm
Free Water inlet 0.8 %
Specification
Salt Outlet 33 ppm
Water Outlet 0.025 %
Screening
S No Formula Ratio
Conc.
(ppm)
Water
dropping
Quality Top oil
water
cut, %
Salt
content
PTBW IF
1 Incumbent -1 --- 100 0 --- --- 2.2 18.1
2 Incumbent-2 --- 100 Tr --- --- 2.0 22.2
3 Incumbent- --- 100 0 --- --- 2.1 21.6
4 Vender 1 --- 100 Tr --- --- 2.1 21.5
5 D309 --- 100 6.5 G G 1.0 8.0
6 DB2903 --- 100 Tr --- --- 3.6 14.0
7 DB9955 --- 100 1 G F 3.4 13.8
8 DB9955/D510 1:1 100 1.5 G G 0.2 9.4
9 DB9955:DB2903:D510 1:1:1 100 1.3 VG G 1.7 12.8
10 D309:DB5914:D510 1:2:1 50 3 G F 1.4 12.0
11 D309:DB5914:D510 2:1:1 50 2 G F 1.5 12.5
12 D309:DB5914:DB9393 1:1:1 50 1 VG F 1.9 14.2
13 D309:DB5914:DI938 2:1:1 50 2 VG P 1.4 12.5
Final selection
S
No
Formula Ratio
Conc.
(ppm)
Water
dropping
WQ IQ
Top oil
water cut,
%
Salt content
PTB
1 D309:DB5914:DI938 2:1:1 50 6 G F 1.0 6.53
2 D309:DB5914:DI938 1:2:1 50 8 G F 1.0 4.0
3 Incumbent -1 --- 150 4 G F 1.4 9.9

17
Evaluation:
The better performed demulsifier bases are given the table with final
formulations. D309 was found good water dropper for this crude emulsion.
The final formulations were with D309, DB5914 and DI938
Demulsifier base-supplier Chemistry RSN
D309-Croda Ethoxylated phenolic resin 21
DB5914-BASF Tetrol EO/PO 39
DI938-Marchem Polymeric polyol 7.7
In this formulation, the demulsifier with RSN7.7 can remain in the organic
layer, while demulsifiers with RSN 21 and 39 can quickly move towards
emulsion and thus to water. But dosing demulsifier with higher RSN is a
negative mark for this formulation which may result in the poor performance
of demulsifier while the needed dosage injection can go up during the
emulsion breaking process.
This shows that bottle test conclusion was not complete with the given
timings and available demulsifier bases.
In the laboratory the vendor’s formulation did better performance than
incumbent even at low dosage with high water dropping, salt content and
water quality. The interface was not sharp as required. The top oil WS&W
was above requirement even though much better than incumbent.
2. Plant 2
Process Data
Process information
Quantity Unit
Production Rate 112000 BD
Wash Water 4480 BD
Salt inlet 12690 ppm
Specification
Salt Outlet 28 ppm
Demulsifiers and formulation that performed well
S
No
Formula Ratio
Conc.
(ppm)
Water
dropping
Quality Top oil
water
cut,%
Salt
content
PTB
w IF
1 Incumbent --- 100 0.8 F F 0.07 3.1
2 Vendor 1 --- 100 0.5 G F 0.1 3.5
3 Vendor 2 --- 100 0.5 G F 0.15 3.6
4 Vendor 3 --- 100 0.5 G F 0.05 2.2

18
5 D309 --- 100 2.8 G F 0 4.7
6 DI938:D309:DB9393 3:0.25:1 100 2.2 F P 0.1 6.7
7 DB9955: D510 1:1 50 1.2 G G 0 1.6
8 DB9955:D309:D510 1:1:1 50 1.2 VG G 0 0.7
9 DB9955:D309:DB9393 1:1:1 50 1.6 VG F 0 0.7
Final selection
S
No
Formula Ratio
Conc.
(ppm)
Water
dropping
WQ IQ
Top oil
water
cut,%
Salt
content
PTB
1 Incumbent 150 38 G G 0 6.7
2 Vendor 1 250 36 G G 0 7.0
3 DB9955:D309:DB9393 1:1:1 100 38 G F 0 2.5
Evaluation:
The final formulation in Plant 2 is a blend of DB9955 D309 and DB9393
DB9955-BASF Resin alkoxylate 13.5-15.5
DB9393-BASF Amine alkoxylate 6.7
Two resin alkoxylates were blended with amine alkoxylate. RSN range shows
a complete distribution from oil to emulsion to water level.
Water dropping by this formulation at a lower dosage was better with very
good low salt content and top oil BS&W. Water quality for this formulation
was good while interface quality was satisfactory.
3. Plant 3
Process data
Process Information
Quantity Unit
Production Rate 112 MBD
Wash Water 4480 BD
Salt inlet 12690 ppm
Salt Outlet 28 ppm
Demulsifier formulations:
S No Formula Ratio
Conc.
(ppm)
Water
dropping
Quality Top oil
water
cut
Salt
content
(µS/cm)W IF
1 Incumbent --- 200 0.5 P F 0.8 15.1
2 Vendor 1 --- 200 1.2 P G 0.8 17.6
3 D309 --- 100 0.8 P G 0.8 16.8
4 DB9955 : D510 1:1 100 1.2 P G 0.6 18.9
5 DB9955:DB2903:D510 1:1:1 100 1.2 F G 0.8 18.7
6 DB9955:D309:DB9393 1:1:1 100 0.6 P G 0.8 14.9

19
Final selection
S
No
Formula Ratio
Conc.
(ppm)
Water
dropping
Quality Top oil
water
cut
Salt
content
(µS/cm)W IF
1 Incumbent -1 --- 150 0.8 F G 0.4 10.3
2 DB9955:DB2903:D510,F1 1:1:1 75 1.2 F G 0.3 8.4
1 Incumbent -2 --- 150 1.0 F G 0.1 2.5
2 DB9955:DB2903:D510,F2 1:1:1 75 1.0 F G 0.4 10.5
1 Incumbent -3 --- 150 3.0 F G 0.2 1.9
2 D309:DB5914:DB9393,F3 2:1:1 75 2.1 F G 0.4 6.6
3 D309:DB5914:DB9393 1:2:1 75 2.0 F G 0.3 5.5
Evaluation:
There were three flows to be evaluated for the different incumbent
formulations. The selected demulsifier bases have the following chemistry.
DB9955-BASF Resin alkoxylate 13.5-15.5
DB9393-BASF Amine alkoxylate 6.7
DB2903-BASF EO/PO block polymer 23
DB5914-BASF Tetrol 39-45
D510-Croda APF resin alkoxyate 8
F1&F2: DB9955(RSN:14)/DB2903(RSN:23)/D510(RSN:8):resin alkoylate/
EO-PO polymer/Resin alkoxylate
This formulation is more weighed towards water soluble area. But presence
of D510 in the oil layer can support more emulsion breaking
F3: D309 (RSN: 21) /DB5914 (RSN: 40) /DB9393 (RSN: 6.7) phenolic
resin/tetrol/amine alkoxylate
This formulation has amine alkoxylate which can break small emulsions.
Crude oils and demulsifier formulations
Plant
Selected formulations
Plant1 Resin alkoxylate/tetrol/polyol
Plant 2 Resin alkoxylate/resin alkoxylate/amine alkoxylate
Plant3-1&2 Resin alkoxylate/block polymer
Plant 3 -3 Resin alkoxylate/tetrol/amine alkoxylate
The general formulation for all these crude oil can be considered as resin
alkoxylate and polyol (tetrol and EO/PO polymers are polyols by nature).
Second formulation is resin alkoxylate with amine alkoxylate. Third one is
resin alkoxylate, polyol and amine alkoxylate.

20
Comparison of demulsifier formulations: Saudi oil & Iranian oil
Type Saudi oil Iran oil
1 Resin alkoxylate/amine alkoxylate Resin alkoxylate/amine alkoxylate
2 Resin alkoxylate/polyol Resin alkoxylate /polyol
3 Resin alkoxylate/polyol/amine
alkoxylate
Resin alkoxylate/polyol/amine alkoxylate
4 Polyol/amine alkoxylate NA
5 Polyol/ester/amine alkoxylate NA
6 Polyols with RSN ranging from oil
solubility to water solubility
NA
As concluded above combination of resin alkoxylate with amine alkoxylate,
resin alkoxylate with polyols and combination of all three types are the
general formulation that works in both oils.
The above conclusions are based on the available data. There are other
types of demulsifiers with different chemistry (diepoxides, PU demulsifiers,
ether polyols, vegetable oil based demulsifiers, sorbitan and starch based
demulsifiers, silicone based demulsifiers, etc...). Further testing and
screening with all types of demulsifiers may give more specific and high
performing formulations.

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