PARTITIONING OF HYDROGEN SULPHIDE IN WELLSTREAM FLUIDS

1. INTRODUCTION AND BASIC PRINCIPLES

Hydrogen sulphide (H2S) is a highly toxic and corrosive gas (1) exerting its effects in
wellstream fluids at the ‘part per million’ concentration. The conceptual background
and a detailed mathematical description of H2S partitioning behaviour is presented for
both two and three phase systems under defined down hole and topsides conditions,
thus allowing calculation of the concentrations and masses of hydrogen sulphide in
all wellstream fluid phases from hydrocarbon producing wells. Statistical function
fitting has been used to enable numerical implementation of these techniques.

The term ‘H2S’ in common usage is ambiguously applied to the gaseous phase, to
the undissociated dissolved gas and the aqueous sulphide ions derived from that gas
(HS- and S2-). Much confusion can be avoided if the strict chemical sense of the term
‘H2S’ is recognised, that relating to an undissociated molecule. In conversation, the
expression ‘H2S molecule’ serves to clarify any misunderstandings. The text of this
document uses ‘H2S’ throughout in its correct chemical sense of the undissociated
molecule.

H2S is a mobile species readily transferring between the hydrocarbon phases and the
water phase of produced fluids in a manner that is predictable under any given set of
conditions with respect to pressure, temperature, pH and salinity of associated water
and the mass ratios of the various fluids. An understanding of this partitioning
behaviour together with the means to calculate the equilibrium concentrations of H2S
in the different wellstream fluids is an essential precursor to adopting safe wellstream
handling and processing strategies.

The literature contains many references to the solubility and partial pressures of H2S,
in a wide variety of liquid organic compounds (see for example 2-5), water (see for
example 6, 7) and aqueous solutions of inorganic compounds (see for example 8, 9).
There are relatively few publications which deal with the solubility and partial
pressures of gases in produced crude oils (10, 11, 12) and formation waters.
Literature that is available indicates a distribution ratio in the range of 3-7:1 for H2S in
pure paraffin compounds and gives some data for H2S/CO2/CH4 in various
combinations in paraffin mixtures and other organic compounds.

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Solubility data for H2S and those for other organic compounds generally give rise to
a similar range of distribution ratios with water as the second liquid phase (13).
Generally, H2S is considerably more soluble in organic compounds than in aqueous
solutions, except at high pH, the solubility increasing with increase in aromatic nature
and decreasing with increase in paraffin and polar nature. The effect of the pH of
associated water is critical, as described in Section 3. The diversity of organic
compounds other than paraffin compounds present in various crude oils may
therefore markedly affect the solubility of H2S in the crude oil and its distribution
between crude oil and water. The variability of crude oil probably explains the wide
range of distribution ratios cited in the literature. Clearly, heavy, more aromatic,
crude has a higher H2S solvency than a lighter, predominantly paraffinic crude.
There is also a possibility that H2S may react chemically with certain compounds
which could be present in crude oil or even formation water and appear to affect,
artificially, the distribution ratios of H2S between crude oil and water.

The numerical work reported in this paper applies to typically light or medium density
crudes and should have reasonable applicability to most oil production systems.

The method of computation of H2S solubility in crude oil and formation waters and the
derivation of distribution ratios based on the respective partition coefficients could
use Henry’s Law or Gerrard’s Reference Line method (3,4,14) and various complex
cubic equations of state(10,11-14). Gerrard’s elegant and realistic method and the
cubic equations of state have been used to model real situations and make
corrections for the inherent non-ideal behaviour of H2S; and the use of Henry’s Law
has been criticised for this reason. Both of these methods are therefore applicable to
relatively high H2S partial pressures obtained where high H2S mole fractions and total
system pressures cause significant deviation from ideal gas behaviour assumed by
Henry’s Law. The methods require comprehensive compositional data for gas, oil
and water phases and, in order to use other cubic equations of state, moderately
high computational power.

Where the degree of souring is not expected to rise above a few hundred mg/kg
(ppmw) in the oil phase, even in the anticipated worse case, the use of Henry’s Law
is fully justified. This is because at these concentrations the partial pressure of H2S,
which is of paramount importance, is low at wellhead and even at reservoir
pressures; and total system pressures are well below the point where non-ideal gas
behaviour starts to become measurably significant. Furthermore, under down hole
conditions, at pressures above the bubble point, there is no separate gas phase, and
hence the question of applicability of Henry’s Law or not is irrelevant.

It is on the above basis, therefore, that the present determination and calculation
methodology were developed. The mathematical treatment in this paper details the
method of calculation of the full wellstream concentrations and mass of H2S and
derived sulphides for either two or three phase systems under defined down hole and
topsides conditions. Note that, although outside the scope of the current paper, this
treatment is applicable to the study of other components, such as carbon dioxide
(CO2).

A comprehensive list of literature references can be found in Chapter 7 of Reference

1.
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2. GLOSSARY OF TERMS

G = Pressure of system in mm Hg (abs).

H = Total wellstream mass of H2S, in kg/day.
HG = Mass of produced H2S in the gas phase, in kg/day.
H′O = Mass of H2S in the oil when above bubble point, in kg/day.
HO = Mass of produced H2S H2S in the oil phase, in kg/day.
HW = Mass of produced H2S in the water phase, in kg/day.
KG = Effective partition rate coefficient for gas.
KO = Partition rate coefficient for oil.
KOW = Concentration ratio of H2S, oil to water.
KW = Partition rate coefficient for water.
KWO = Concentration ratio of H2S, water to oil.
K *WO = Apparent KWO value not corrected for pH.
M = Total wellstream production mass, in kg/day.
MG = Mass of produced gas, in kg/day.
mG = Average molecular mass of partitioned gas (typical value = 20).
mH = Molecular mass of H2S = 34.
mO = Average molecular mass of wellstream hydrocarbon fluids.
M′O = Mass of oil above bubble point, in kg/day.
mN = Molecular mass of N2 = 28.
MO = Mass of produced oil, in kg/day.
MW = Mass of produced water, in kg/day.
p = Partial pressure of H2S in the gas phase in mm Hg (abs).
P = Pressure of system in atmospheres (abs).
QN = Mass, of purge nitrogen, in kg.
QO = Mass, of purged oil sample, in kg.
rG = Proportion by mass of produced gas.
rO′ = Proportion by mass of produced oil when above bubble point.
rO = Proportion by mass of produced oil.
rW = Proportion by mass of produced water.
STP = Standard Temperature and Pressure, 0o Centigrade and 1 atmospheres
(abs).
T = Temperature of system in degrees Centigrade.
V1 = Volume occupied by one mole of any gas at STP, namely 22.4 litres.
VN = Volume of purge nitrogen, measured at STP.
XG = Concentration of H2S in the gas phase, in mg/kg.
X ′O = Concentration of H2S in the oil phase when above bubble point, in mg/kg.
XO = Concentration of H2S in the oil phase in mg/kg.
XW = Concentration of sulphide species (H2S + HS- + S2-) in the water phase in
mg/kg.
XWE = Concentration of H2S as the undissociated molecule in the water phase at
specified pH, in mg/kg.
y = Mole fraction of H2S in gas phase.
Y = Concentration of H2S in gas phase in ppmv.
YN = Concentration of H2S in purge nitrogen measured at STP, in ppmv.
Z = Overall concentration of sulphide species (H2S + HS- + S2-) in wellstream in
mg/kg.
 4

ZE = Concentration of H2S as the undissociated molecule in production for

partitioning at actual pH, in mg/kg.
θ = Proportion of H2S in water retained for partitioning at given pH.

3. BASIC RELATIONSHIPS AND PH EFFECTS

Mass relationships:

M = MO + M G + M W , M′O = MO + MG (3.1)

rO = M O / M, rG = M G / M, rW = M W / M, rO′ = rO + rG (3.2)

H = HO + HG + H W , H′O = HO + HG (3.3)

10 6 HO = X OM O , 10 6 HG = X GM G , 10 6 H W = X W M W , 10 6 H = ZM (3.4)

Partition relationships:

K OW = K W / K O , K WO = K O / K W (3.5)

Z = rO X O + rG X G + rW X W (3.6)

[o r Z = r O′ X ′O + r W X W a b o ve th e b u b b le p o in t (3 .6 ′ ) ]

p = X OK O = X WEK W = X GK G , K G = 10 −6 Gm G / m H (3.7)

[or p = X ′OK O = X WEK W above the bubble po int (3.7 ′ )]

Water pH effects:

H2S exists as the undissociated H2S molecule, soluble in hydrocarbon phases and
water. As the pH of water increases above pH 5.0 so the concentration of the
undissociated H2S decreases in a predictable manner by dissociating to form the acid
- -
sulphide ion (HS ). This ionic species, and the further dissociated sulphide ion (S2 ),
which exists under alkaline conditions above pH 9.0, are completely unable to
partition from the water to either the liquid hydrocarbon or the gas phases. Indeed,
any H2S in the hydrocarbon phase coming into contact with an alkaline water will, in
addition to partitioning into the water, dissociate to the stable ionic species and
continue to do so until the partitioning and dissociation reactions reach an
equilibrium. This equilibrium state may or may not support the existence of H2S in
the gas phase.

On occasions, in a two phase system, the hydrocarbon phase will become less sour
below the bubble point pressure i.e. in a three phase mixture, when dissolved CO2
 5

outgasses, this raises the pH of the water which consequently ‘locks-up’ additional
-
H2S, in the water phase, as HS ions.

It is therefore most important to take account of the pH effect when using measured
amounts of H2S in a gas phase to deduce the corresponding concentration (s) in the
associated phase(s) or in determining the necessary ‘partition coefficients’.

From (6.1) we derive θ linking the ‘effective concentration’ of H2S as the

undissociated molecule in the water (available for partitioning) to the pH of the
system:

X WE = θX W (3.8)

Z E = rO X O + rG X G + rW X WE (3.9)

[ or Z E = rO′ X ′O + rW X WE above the bubble point ( 3.9 ′ )]

Conversion from atmospheres to mm Hg:

G = 760P (3.10)

4. THREE-PHASE PARTITIONING (BELOW BUBBLE POINT

PRESSURE)

Light or medium density crude oil bubble point pressures are generally within the
range 35 - 540 atmospheres over the operating temperatures of the wellstream. That
is to say, the particular bubble points for the various gas molecules typically present
in any quantity lie within this range. As pressures are lowered, so more gas
components partition out, raising the oilstream G.O.R. and the average molecular
weight of the produced gas. The bubble point pressure for a given molecule will not
vary much over the usual range of separator temperatures (T, ambient up to 120oC,
say), as can be seen from examining the standard relationship: P (bubble) = P∞ exp
[1/(T + 273)] with P∞ ≅ 70 atmospheres say, for a typical well head gas component.

(a) Gas Phase

Typically start with Y measured directly in ppmv. The common commercial detector
tube techniques are very quick and simple to apply on site at production wellheads or
gas separators. Also, they are qualitatively better than the usual techniques for
measuring concentration in the oil phase, although not so accurate as the titrimetric
methods for water. Titrimetric methods for water are not, however, amenable for use
on site at the production wellheads and the dissolved sulphides need to be
chemically ‘fixed’ to avoid loss by oxidation and degassing during transit to the
laboratory. Measurement of H2S concentrations in gas phase is, therefore, the most
commonly adopted practice.
 6

From the glossary above it can be seen that gas phase measurements may be
supplied as, or be needed to be expressed as: ppmv (Y), partial pressure in mm Hg
(p), mg/kg (XG ≡ ppmw) or mole fraction (y). The various relationships between
these units are summarised in the table of transformations given below:

Converting from

Y (ppmv) p (mm Hg) XG (ppmw) y (mole fraction)

Converting Y Y 106 p/G mG XG /mH 106 y
To
p 10-6 YG p 10-6 GXG mG /mH yG (4.1)

XG mHY/mG 106 mH p/(G mG) XG 106 mH y/mG

y 10-6 Y p/G 10-6 XG mG /mH y

We have,

XO = p / KO & X WE = p / K w (4.2)

Then (3.8) implies:

X W = X WE / θ (4.3)

and Z comes from (3.6) directly.

(b) Water Phase

One standard technique starts by 'fixing' the H2S in the water entirely as HS- or S2-,
by the addition of alkali to raise the pH. The implied total mg/kg of H2S that could
have been found in the water at a low enough pH (below 5.0) is then back-calculated.
This method therefore supplies a value for XW, rather than XWE, which must be
calculated from (3.8); which in turn supplies a value for XO via (3.7) and for p via
(4.2). Finally, observe that (4.1) and (4.2) together imply

XG = p / KG (4.4)

(c) Oil Phase

One standard technique is to purge a sample of oil with nitrogen gas so as to

(nominally, at least) remove all the H2S, and then to find the ppmv, YN say, at STP, of
this purged H2S in the nitrogen. This figure must be converted back to recover the oil
concentration via the mass balance equation:

X O Q O = X NQN (4.5)

which implies
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⎡m ⎤⎡ V m ⎤
X O = ⎢ N YN ⎥ ⎢ N N ⎥ (4.6)
⎣mG ⎦ ⎣ V1Q O ⎦

Then (4.2) followed by (4.4) and (4.1) recovers p, XWE, XG, y and Y in turn. These can
be applied to (4.3) then (3.6) for Xw and Z, if required.

(d) Overall Mixture

An alternative situation occurs when the overall figure for H2S production, H, is given
(in kg/day). This typically arises either as a design parameter for oilfield equipment or
from modelling of H2S production down hole by bacterial activity. Then (3.4) gives Z
immediately, whilst substituting for XG from (4.4) and for XO and XWE from (4.2) and
hence into (3.6) using (3.8), we find:

[
p = Z / rOK O−1 + rGK G−1 + rW K −WE
1
] (4.7)

Then

Y = p 106/G (4.8)

whilst (4.2) gives XO and XWE , (4.4) gives XG , (3.6) gives Z and finally (3.8)
recovers XW.

5. TWO-PHASE PARTITIONING (ABOVE BUBBLE POINT PRESSURE)

Here the two phases are oil and water in the proportions r'O and rW respectively. We
have

X ′O / X WE = K OW (5.1)

(a) Water Phase

Given XW as measured from a sample of water, (3.8) and (5.1) imply

X ′O = K OW θ X W (5.2)

with (3.6') for the overall concentration. Note that this water sample measurement will
produce an ‘apparent’ value for the partition coefficient equal to X'o/Xw . From (5.2)
we see that this is proportional to the fundamental diffusion ratio, KOW, coinciding with
it only when θ =1.

(b) Oil Phase

Given a direct measurement of X ′O , (5.1) and (5.2) give XWE and XW, then (3.6') gives
Z. When H2S is given as a mole% concentration in the wellstream downhole
hydrocarbon phase, this can be converted into mg/kg by
 8

⎡ mole% ⎤ ⎡ 10 m H ⎤
6

XO = ⎢ ⎢ ⎥
⎣ 100 ⎥⎦ ⎣ m O ⎦
(5.3)

(c) Overall Mixture

Given Z, perhaps derived from a top-side three phase analysis, we can substitute
both for X ′O from ( 3.7′ ) and for XW from (3.8), into ( 3.6′ ) to give

X WE = θ Z / (rO′ K OW θ + rW ) (5.4)

and hence Xw from (3.8), and X ′O from (5.1).

(d) apparent partition constant

For fixed pH the ratio

X ′O / X W = K *OW (5.5)

defines an 'apparent' partition constant, which is not however a true partition constant
since it is not a ratio of diffusion speeds and it depends on pH. From (3.8) and (5.1)
we see that

K *OW = θ K OW (5.6)

Also, solving for ZE, we find

Z E = θZ
[rO′ K OW + rW ] (5.7)
[θ rO′ K OW + rW ]
for (down-hole) two-phase mixtures, and

[r −1
OK O + rG K −G1 + r W K −W1 ]
Z E = θZ (5.8)
[ θ (r −1
OK O + rG K −G1 ) + r W K −W1 ]
for (top-side) three-phase mixtures.
 9

6. RESPONSE SURFACE FITS TO TABULATED VALUES

Plotting a standard table of retention proportions on a base 10 logistic scale, shows a

clear linear trend with unit slope, crossing the pH axis at 6.7, and therefore implying
the following relationship between θ and pH :

θ = (1 + 10 pH− 6.7 ) −1 (6.1)

The partition K constants depend on pressure, temperature and the precise chemical
composition of the various phases. They can be difficult to measure and various
values can be found in the literature.

Access to a table of partition coefficients for a typical light to medium density

petroleum production system has enabled another function fitting exercise to produce
the following formulae for the two necessary partition coefficients, KO and KW:

K O = α O + α1C + α 2 C2 + α 3 A 2 + α 4 CA + α 5 A 3 + α 6 C2 A + α 7 CA 2 + α 8 CA 3 + α 9 C2 A 2 (6.2)

K W = 0.86 + X exp[β o + β 1C] (6.3)

where C = T/100, A = P/100, X = |A - 0.75|, and the α & β values are given in the
table below:

α parameter value β parameter value

α0 0.0527417 β0 -0.395580
α1 0.1381160 β1 -0.681974
α2 0.1308090
α3 0.0431212
α4 -0.0898511
α5 -0.0151593
α6 -0.1232030
α7 0.1688330
α8 -0.0598966
α9 0.0371972

The tabulated values for both KO and KW covered the ranges 0≤P≤150 and 0≤T≤100.
A plot of the 4th order response surface, given below, as fitted to these supplied KO
values, can be seen in Figure 1. The corresponding plot for Kw can be seen in Figure
2, extended out to T ≈ 160 and P = 250. The extrapolated sections of this latter
graph appear to be consistent with the pattern of fit seen for the interpolated region
and hence this formula is perhaps usable out to the higher parameter values.
Although some extra, statistically significant, terms could have been included in the
model for KW , they were of little practical significance within the interpolated region,
and unfortunately became unstable for extrapolations. Hence the simplified model
given above was considered to be preferable.
 10

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(1) “Oilfield Reservoir Souring”, UK Health & Safety Executive OTH 92385
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(3) EAKIN, B. E. and DEVANEY, W. E. Aiche, Symp. Ser., 70, 80, (1974).

(4) GERRARD, W. J. Appl. Chem. Biotechnol, 22, 623, (1972).

(5) HSU, C. and LU, B.C.Y., J. Chem. Eng., 50, 144, (1972).

(6) REAMER, H. H., SAGE, R. H.. and LACEY, W. N. Ind. Eng. Chem., 43, 975,
(1951).

(7) ROBINSON, D.B., Proc. Ann. Conv. Gas Process Assoc., Tech. Pap., 54, 25,
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(8) ANDREWS, J. C. and KENDALL, J. JACS, 43, 1545, (1921).

(9) ANDO N., SADA, E. and KITU, S. J. Appl. Chem. Biotechnol., 22 1185,
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(10) ERBAR, J. H. and MAJEED, A.I., EFCE Publ. Ser., 27, C15/1-C15/7 (Int.
Conf. Inf. Genie Chim., 2) (1983).

(11) ERBAR, J. H. MOSHFEGIAN, M. and SHARIAT, A. ACS Symp. Ser., 133,

333, (1980).

(12) WAGNER, J. and MAJEED, A.I. ACS Symp Ber., 300, 452, (1986).

(13) RORSCHACH, R. P. and GARDINER, F. T. Ind. Eng. Chemical., 41, 1380,

(1949).

(14) GERRARD, W. “Solubility of gases and liquids”, Plenum Press, (1976).