Demulsifier Chemistry and Relative Solubility Number

Chandran Udumbasseri, Technical Consultant

cudumbasseri@yahoo.co.in; chandran.udumbasseri@gmail.com

Definition
RSN value is an empirical measure of relative solubility of the demulsifier polymer in
organic solvent and water. Polar polymer is soluble in polar solvent and less polar one in
solvent with less polarity. So polymers with polarity distribute itself evenly in a polar
solvent. Polymer with less polar character can distribute evenly in the less polar
solvent. So the availability of polymer molecule for their function is even in that
polymer solvent mixture.
If RSN increases the hydrophilic nature of the polymer also increases. Such polymer
tends to move towards more polar solvent. So a demulsifier with high RSN value moves
towards water layer causing emulsion breaking. This causes fast and more water
separation.
Polymer with low RSN value means that it is more soluble in organic layer. Such
polymers distribute evenly in organic layer available through out for small water-in-oil
emulsion droplets. This enhances more emulsion breaking even though freed small
water droplet aggregation is not supported by polymer structure (water droplet
flocculating polymers will be having network structure with different types of branching
and additional water attracting groups).

This note is giving some information on the relationship between RSN values of
demulsifier bases with same chemistry and their water dropping character or emulsion
breaking ability.
Tests were conducted on bases with similar chemistry from the same supplier
(manufacturer)
Figure1 shows demulsifier bases from BASF, EO/PO block polymers (PLURONIC Series)

The plots for bases 6100, 6200, L44, show increase of water dropping (%). But for
bases 9400 and 10500 the water dropping rate decreases.
The order is given below

L44 (RSN 21.9) 9400 (RSN 28.5)

6200 (RSN 16.1) 10500 (RSN 31.5)
6100 (RSN 11.7)
Water dropping Water dropping
 Figure 1

So the rate of water drooping increases up to RSN value 21.9 and then decreases with
increase of RSN value. This is for BASF Pluronic series

Below is given the water dropping (%) for bases from CRODA with demulsifier
chemistry, Alkoxylated ethylene diamine
Figure 2

In the above Figure 2 the rate of water dropping increased as RSN value of the bases
increased from 12 to 22
Below figure (3) is the same plot of water dropping against the value RSN for each time
plot The plots explain a RSN range where maximum water dropping is possible.
Maximum water dropping is in the RSN range 11 to 22.
 Figure 3

Chemistry of demulsifiers that work better with Saudi Crude oil

The figure 4 shows probable demulsifiers with their chemistry that find application in
Saudi Crude oil in Gawar area. The chemistry is as given by the product suppliers. The
main applicable demulsifiers are polyols, amine (PEI) ethoxylate and NPF ethoxylates as
shown in the chart.
The above histogram shows most probable demulsifier with their chemistry. Their
respective RSN value are given below

S/N Chemistry RSN

1 Polymeric polyol 7-8
2 Polyester 6.7
3 Polyol 12-16
4 Oxylated phenolic resins 18-22
5 Amine ethoxylate 6.6
6 BPF alkoxylate 7-8
7 EO/PO alkoxylate 6-11
8 NPF ethoxylate 6-7
9 Diepoxide 6.7
10 PEI alkoxylate 6-8
11 Block polymer 7-10
12 Resin alkoxylate 6-12
13 EO/PO block polymer 7-9
The table shows that except serial numbers 3& 4 the rest are all having RSN below 12. That
means the demulsifiers can work efficiently if RSN is below 13
Nos 3& 4 are special case demulsifiers that can be used at lower temperature.
A typical demulsifier formulation is shown below for all GOSPs

GOSP# Demulsifier bases in formulation RSN values

A B C D A B C D E
U8 Polyglycol PGAlkoxylate - - 7 10 - - -
U9 Resin alkoxylate Polyurethane - - 8.3 9.6 - - -
U12 Polyglycol Resin - - 7 12 - - -
U13 Resin Oxyalkylate Ethoxy alcohol - - 8 18 - - -
H1 Resin Oxyalkyalte Polyurethane - - 8 9.6 - - -
H2 PG oxyalkylate Phenol oxyalkylate Polyurethane - 10 12 9.6 - -
A2 PG oxyalkylate Resin alkoxylate P olyurethane - 10 12 9.6 - -
A3 Polyglycol Resin oxyalkylate Poly Urethane Alc ethoxylate 7 12 9.6 18 -
S1 PG alkoxylate Polyurethane Resin oxylate Alc ethoxylate NPF resin 12.5 9.6 12 18 6.4
S3 PG alkoxylate Polyurethane Resin oxylate Alc ethoxylate NPF resin 12.5 9.6 12 18 6.4
U4 Oxyalkylate Ethoxy alcohol - - 8 18 - - -
U7 Polyglycol PGAlkoxylate - - 7 10 - - -
U10 Oxyalkylate Ethoxy alcohol - - 8 18 - - -
U11 PGalkoxylate Polyurethane NPF resin - 7 9.6 6.4 - -
Hw2 NPF resin Resin oxyalkylate polyglycol - 6.4 12 7 - -
Hw3 NPF resin Resin oxyalkylate polyglycol - 6.4 12 7 - -
Hw4 PG alkoxylate Polyurethane Resin oxyakylate Polyglycol 12.5 9.6 12 7
A4 PG alkoxylate Resin oxyalkylate Polyglycol - - 12.5 12 7 - -
A6 Phenol oxyalkylate Polyurethane Polyglycol - 12 9.6 7 - -
S4 Polyurethane Polyglycol Resin alkoxylate - 9.6 7 8.3 - -
S5 Polyurethane Polyglycol Resin alkoxylate - 9.6 7 8.3 - -
S6 Polyurethane Polyglycol Resin alkoxylate - 9.6 7 8.3 - -

Demulsifier formulations using suppliers (BASF, Croda, Majorchem, Marchem) bases are
shown below
 GOSP# Demulsifier bases in formulat ion RSN values
A B C A B C
U8 DI938 DI937 - 7.6 7.7 -
U9 DI938 - - 7.6 - -
U12 DI938 D309 DB9393 7.6 21 6.7
U13 DI938 DI937 - 7.6 7.7 -
H1 DI938 RO238 DB9393 7.6 8.7 6.7
H2 DI938 RO238 DB9393 7.6 8.7 6.7
A2 DI938 DB9393 - 7.6 6.7 -
A3 DI938 DB9393 - 7.6 6.7 -
S1 C461 DP188 - 12.5 16 -
S3 D3575X - - 17 - -
U4 DI938 D309 DB9393 7.6 21 6.7
U7 D311 DI937 - 18 7.7 -
U10 DP188 - - 16 - -
U11 DI938 D309 DB9393 7.6 21 6.7
Hw2 DP188 D311 DB9393 16 18 6.7
Hw3 DP188 D311 DB9393 16 18 6.7
Hw4 DP188 D311 DB9393 16 18 6.7
A4 C461 DI938 - 12.5 7.6 -
A6 D311 - - 18 - -
S4 DP188 DI938 - 16 7.6 -
S5 DG270 DI938 - 6.7 7.6 -
S6 D309 DI937 DB9393 21 7.6 6.7

RSN value and desalting efficiency of demulsifier bases with same

chemistry
The results summarized below are from the actual bottle test results at site conducted at
Saudi Aramco GOSPs. In the given table, RSN value for each chemical is given in the
last column.
Results
Plant-1: Bases with numbers 1, 2, 3 are alkoxylated phenolic resins from Croda while
bases 4 and 5 are imine alkoxylate from Croda. 6 & 7 are polyglycol bases from
Marchem and 8 & 9 are alkoxylated resin bases from KAO (Danox). In each group the
salt content increases with increase of RSN value.
Plant 2-10
Pairs of bases given in each table show the above effect of ‘increase of salt in crude oil
content with increase of RSN value”.
Plant 1
S Product ID pp Water W IQ salt Chemical name RSN
N m dropping, ml Q
10 20 30
1 Croda- D3501X 20 9 16 18 F F 24.6 Alkoxylated phenolic 15
resin
2 Croda- D311 20 9 12 18 P F 27.9 Oxylate phenolic resin 18
3 Croda- D309 20 8 9 10 G F 46.6 Oxylate phenolic resin 29
4 Croda- D3422X 20 0 3 12 F F- 3.56 Imine alkoxylate 8
5 Croda- D510 20 4 6 12 P P 7.28 Imine alkoxylate 11
6 Marchem-PG1.5 20 0 0 5 P P 5.15 Polyglycol 14.1
7 Marchem-PG2.5 20 1 5 16 F F- 9.5 Poly glycol 17.3
 8 KAO-RS19 20 10 24 30 G G 17.82 Alkoxylated resin 12
9 KAO-RS15 20 5 14 24 F F 29.2 Alkoxylated resin 13

Plant 2
1 DG4283 60 9 10 12 F+ F+ 70.6 Rsin alkoxylate 10.6
2 D3627X 60 3 7 9 F+ F+ 73 Resin alkoxylate 21

Plant 3
1 BASF-DB9393 25 Tr Tr Tr - - 40 PEI ethoxylated 6.5
2 BASF-DB9392 25 Tr 1 4 F F+ 73 PIE ethoxylated 8.3

Plant 4
1 DG4283 30 2 3 3 F+ F+ 46 Resin alkoxylate 10.6
2 DB9946 30 0 1 2 G F+ 50 Resin alkoxylate 11

Plant 5
1 DB9393 15 Tr 0. 7 G F+ 4.32 Amine ethoxylate 6.7
2
2 DI945 15 11 12 20 VG G 81.2 Amine oxyalkylate 16
3 D3422X 15 1. 5 36 F+ F+ 3.86 Polyimine alkoxylate 8
5
4 DEPA10 15 8 12 22 F+ F+ 5.78 Polyethylene imine 9-10
alkoxylate
5 DRI9037 15 4 10 18 F+ F + 22 Polymeric Polyol 7-8
6 DI936 15 3 10 20 F F 32 Acrylic polyol 8.4

Observation
1. As the RSN increases to 22 the water dropping ability of the demulsifiers
increases. Increase in RSN shows more affinity towards water. So the demulsifier
moves towards the water in oil emulsion and try to dissolve in water using
hydrogen bonding. This causes the breaking of emulsion. But as more and more
water separates more demulsifier dissolves in water based on their partition
coefficient between oil and water phases. This ultimately reduces the performance
of demulsifier due to unavailability in the oil layer.
2. As the RSN increases above 22, the demulsifier tends to dissolve in water layer
instead of functioning as emulsion breaker
3. When RSN is below 11 the demulsifier distributes evenly in the organic layer
making available for all types of emulsion macro and micro sized
4. The breaking is both types of emulsions causes the reduction in the BS&W and salt
gets removed from the oil layer. This helps to remove most of the salt from the oil
layer. So decrease in RSN favors removal of salt from the oil layer.