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OIL INDUSTRY I
Chemicals in the Oil Industry
22 23 March 1983
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INSTITUTION
r t u
Special Publication No 45
Industry
Edited by
P. H. Ogden
Akzo Chemie U K Ltd.
Copyright 1983
The Royal Society of Chemistry
ISBN 0-85186-885-1
Printed in Great Britain by Henry Ling Ltd., at the Dorset Press, Dorchester, Dorset
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Introduction
The volume of chemical additives used may be rather small when compared with
the total quantity of oil produced, the proportion usually being expressed
as parts per million; however, it represents a considerable quantity of
chemical, frequently specialty and often expensive.
On the other hand, because the use of chemicals is relatively small compared
with the volume of crude oil, production operatives, with a few exceptions,
have been unaware of the fundamental aspects of their chemical additives.
The term specialty chemical is frequently used as a misnomer for a formulated
product, such as a corrosion inhibitor ,or scale dissolver, which might be a
mixture of several active ingredients with selected solvents or surfactants
in order to allow easy application and effective transportation to the site
of operation.
If a technology gap exists between the oil producer and the chemical manufacturer,
this has been filled by the chemical service company. Such organisations combine
a kpowledge of the chemistry involved with a good understanding of oil production
technology. Their role has been extremely important but their interests
would not be served by widespread dissemination of their knowledge and it could
be argued that they sell service and expertise rather than a chemical product.
The objective of the symposium of which the proceedings follow was to draw
together representatives of the oil producing industry, the chemical service
companies, and the general chemical industry in order to describe some of the
problems associated with oil production; to define those problems which can be
solved through the use of chemical additives; the type of chemical currently
111
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favoured; the level of service required to supply such chemicals effectively
to the oil industry; the volume of chemicals used; and the financial outlay
required of the oil producer. As such, the sympOSiU1D was to be technically
informative and also to enable participants to gauge the level at which their
respective organisations might reasonably participate in the future of this
growth business.
The-North West Region of the Royal Society of Chemistry wishes to record its
gratitude to all of the contributors to these proceedings through which we
have been able to cover many of the chemical aspects of drilling, stimulation,
production and transportation. Enhanced Oil RecoverY,which is an extremely
important aspect of future oil production and is a subject which possibly
holds the highest promise for future chemical sales to the industry, will be
described in a future symposium.
Paul H. Ogden
IV
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Contents
v
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Quaternary Ammonium Compounds: Evaluation and
Application in the Control of Sulphate-reducing
Bacteria 159
By E. Bessems and A.F. CZemmit
vi
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Application of Chemistry to the Drilling Operation
By G. H. Smith
BP RESEARCH CENTRE, SUNBURY-ON-THAMES, MIDDLESEX TW16 7LN, U.K.
50'
1000'
~~~
~
I I
~ll~
I~
30"
18%"
Cement
O~
4000' l3~"
8000' 9%"
10000' 7"
ACKNOWLEDGEMENT
REFERENCES
4. Smith, Dwight K.
Cementing. SPE Monograph Volume 4
Second printing. Society of Petroleum Engineers of AIME.
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By M. E. Hille
HOECHST AG., D-6230 FRANKFURT-AM-MAIN, WEST GERMANY
Efficient drilling muds have been developed in the past for many
different geological formations through which wells had to be
drilled. l ,2
The high HT/HP water loss often leads to formation damage which
decreases ~he production rates. High gelled muds are frequently
the cause of deficient cementation. Particularly at high mud
densities, the cement sludges will not completely displace the
mud and the cement will build preferential flow channels in the
highly viscous mud of the annulus. By this means the hydrocarbon-
bearing formations will not be entirely sealed and, especially
at high formation pressures and differential pressure, the gas
will flow to other porous layers through the annulus.
The largest gap in drilling mud technology until now has been
the lack of highly effective additives for conditioning saltwater-
containing drilling muds which are exposed to high temperatures
during drilling at great depths. 5
H H H H H H H H
I I I I H2 0 I f I ,
(-c - c-) (-C - C-) ( - c - c-) (-c-c-)
I I n I I m I f n I I m
H C=O H C=O H C=O H C=O
I
6-Na+ NH
2
o,- Na + b-NH+
4
Table 1
r
15 h at 200C
I 11 III I II III
t
10 g CaS0 4 100 g caC1
2
10 g Additive 20 g Additive
u
Additive Water losses according to API in cm
P
~'
Viny1su1fonate/viny1- 8.5 9.0 4.8 8.8 10.4 5.5 ~
r;;--
amide
5'
mg approx. 0.8-1.0 x 10 6 So
~
~
~
~
~
~
V:J
~
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Chemicals for Water-based Drilling Fluids 17
For the stated reasons these products have only found limited
acceptance as additives in drilling mud systems for deep wells.
They inhibit swelling clays very well and are therefore used in
the formulation of drilling muds in which the calcium concentration
has to be kept low.
Table 4 shows the means of the slightly saline drilling mud (NaCl
7-8%, ca++ 2000 to 6000 ppm) of a deep bore-hole with a final
depth of about 5600 m and a temperature of 195 c at the bottom.
At a depth of about 4900 m this drilling mud has been changed from
a CMC conditioning to polymer. The planned final depth was
safely reached after unproblematical drilling, with only small
drilling mud replenishments being required.
Registered trademark
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20 Chemicals in the Oil Industry
Table 2
3 4.8
API water loss (cm ) 3.8
3 62.0
HT/HP water loss (cm ) 44.4
35 bar/150C
Field mud: 3
Chalk, approx, 200 g KCl/l, density 1.40 g/cm
conditioned with CMC and CMHEC and plus 1% polymer
VS/VA
Table 3
Density 3
g/cm 1.46
Marsh 59/48
WV API 2.4
Filter cake 0.5
WV HT/HP 22.0
pH 7
at 50C at 90C
SV cp 28.5 20
PV cp 26 18
2
FL Ibs/lOO ft 5 4
10" gel 1.5 2.5
10' gel 1.5 3
3
Drilling mud: per 1 m water: 30 kg bentonite, 338 kg NaCl, 640
kg chalk, 35 kg polymer, 0.8 kg defoamer
HT/HP water 10ss/35 bar/150c
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Chemicals for Water-based Drilling Fluids 21
Density g/cm 3 1. 6 - 1. 66
Marsh sec 45 - 50
3
WV API cm 5 - 8
WV HT/HP 3
cm approx. 20
0
25 bar, 160 C
Filter cake mm 0.5 - 0.6
pH 9 - 10
SV cp 40 - 50
PV cp 30 - 40
Yield point 2
lbs/100 ft 5 - 15
10" gel 6 - 10
10' gel 18 - 30
Drilling mud: Bentonite heavy spar, NaCl 7-8%, Ca++ 2000 - 6000
ppm, approx. 1% VS/VA polymer plus a little CMC
References
1
G.R. Gray, H.C.H. Darley, and W.F. Rogers, 'Composition and
Properties of Oil Well Drilling Fluids', Fourth Edition, Gulf
Publishing Co., Houston, Texas, 1980.
2
K.H. Grodde, 'Bohrspulung und Zementschlamme in der Tiefbohr-
technik', Verlag Otto Vieth, Hamburg, 1963.
3
W.G. Chesser, and D.P. Enright, J. Petrol. Technol., June,
1980, 950 - 956.
4
C.E. Chadwick, Oil and Gas J. Oct. 1981, 251 - 257.
5 P. Simpson, World Oil, April 1967, 135 - 139.
6
D.E. O'Brien and M.E. Chenevert, J. Petrol Technol., Sept.
1973," 1089 - 1100.
7
R.K. Clark, R.F. Scheuermann, H. Rath, and H. van Laar,
J. Petrol. Technol., June 1976, 719 - 727.
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The Development and Application of Oil- base Muds
Introduction
it was found that water based muds were often not performing
fluid used.
following components:
cellulose) .
(a) Clays
Swelling clays entering the mud system can
give excessive viscosities and high fluid
losses (permeable filter cake and wrong
polymer/clay ratio) which ultimately leads
to hole erosion and collapse.
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24 Chemicals in the Oil Industry
base muds.
salinity in the water phase (by adding CaCl 2 ), oil muds not only
(1) Cost
Theoretically possible.
(d) Burial
consideration.
into muds with a water content of greater than 50% whilst main-
the molecule.
Anionic
Sodium stearate - +
CH 3 (CH 2 ) 16 COO Na
Sodium oleate CH 3 (CH 2 ) 7CH = CH (CH 2 ) 7
COO-Na+
- +
Sodium dodecyl sulphate CH3(CH2)11S04 Na
- +
Sodium dodecyl benzene sulphonate CH 3 (CH 2 ) 11C6H4S0sNa
Cationic
Dodecylamine hydrochloride
+
CH 3 (CH 2 ) 11 NH 3 Cl
Hexadecyltrimethylammonium bromide
+
CH3(CH2)15N(CH3)3Br
Trimethyl dodecyl ammonium chloride
+
C12H25N(CH3)3Cl
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The Development and Application of Oil-base Muds 29
H H H H H
2+
I I I I I
R N C C C N -H Cl Cl -
I I I I I
H
H H H H
Non-ionic
Polyethylene oxides
C6 HS 0 -- (CH 2 -- CH 2 -- O)30H
Amphoteric
+ (CH ) 2
3
Dodecyl betaine C H N
12 25 ----- CH CO-
2 2
together with a mineral, fused and then ground up. The particles
14
replacing the alkali metal cations with an onium salt , e.g.
16
(C14H29NH3)+Cl-. White claims that better results are obtained
dispersing.
of oil muds.
these are slow drilling rate and pollution. These problems have
been partial-Iy solved with relaxed fluid loss muds and "clean
oil" muds.
base mud with bentone for gels gave a much improved drilling
invert oil base mud using a rock bit. It was found that,
hydration.
24
According to O'Brien et aI, relaxing filtration
more the filtrate from the HT/HP for an oil mud gives a
Anguilla Anguilla
Littorima Littorea
Mythilus Edulis
Scrubicularia Plana
Palaemon SP
Artemia Salina
Phaeodacrylum Tricornutum
Dunaliella Tertiolacta.
period of time.
oil muds the cuttings may be discharged directly into the sea.
than from the diesel oil base mud (being less polar, clean oil
gives less adhesion).
r t u P
36 Chemicals in the Oil Industry
that of a normal oil base mud and where lost circulation occurs
The other chemicals in the " c l ean " oil mud are
~.. ~CH2CH20H
C12H25~S - N~
CH CH 0H
2 2
The emulsifier should also be non-toxic and
biodegradable.
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38 Chemicals in the Oil Industry
(2) Testing
REFERENCES
1. G. Miller, 3rd World Pet. Congress, Sect 11, The Hague, 1951.
APPENDIX
Molecular Formulae
Oils
Lecithin
Choline is:
H COOCR
2 , Lecithin
H COOCR'
I ~o
H2CO - p,---O-CH2CH2~(CH3) 30H -
OH
Amide Wax
H" /HSA
N- (CH) - N
/ 2n '"
R H
n is from 2 - 18
R is hydrogen or HSA.
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Chemical Aspects of Oilwell Cementing
Abstract
The USSR Standard defines two basic grades of oilwell cement, one
for "cold" wells and the other for "hot" wells. The tests on cement must
be made at 22 2C and 75 3C. For improving the properties of oilwell
cements for both "cold" and "hot" wells, GOST 1581-78 permits up to 15%
active and up to 10% inert mineral additives provided that they be
ground. In addition some special oilwell cements are produced under
various technical specifications, e.g. sulphate-
resistant types. Initial set for the "cold" well cements must be not
less than 2 hours and for the "hot" well cements not less than 1.75
hours. The retardation of the setting times of the "hot" well cements is
effected largely by the use of clinker low in alumina. The "hot" well
c~ment is designed for utilising at a temperature of about 75C. Oilwell
cements with 3-4% tricalcium aluminate content are produced both for
"hot" and "cold" wells.
TABLE 1
The normal raw materials and processes are used to make both the
Class A (ordinary type) or other classes of moderate or high sulphate
resisting clinkers of Portland cement which form the basis of oilwell
cements, and which comply, with the chemical requirements. The compound
composition will of course vary within the set limits depending on the
targets set by the manufacturer bearing in mind the materials and plant
available to him, and also the route which gives him the best control of
his quality. Oilwell cements are used in geothermal wells for both oil
and gas extraction.
Cement slurries
TABLE 2
REQUIRED WATER/CEMENT RATIOS
Thickening time
100
Thickening
Time
Time
Figure 1
TYPICAL CURVE SHAPE FOR THICKENING TIME
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Chemical Aspects ofOi/well Cementing 47
Operating conditions
Additives
a) Accelerators
b) Retarders
c) Friction reducers
d) Lightweight additives
e) Densifying additives
General
Hydration Behaviour
These reactions are not of the dissolution and precipitation type, but
occur topochemica11y at the silicate surfaces. The equations are only
approximate, because the calcium silicate hydrate formed, known as
C-S-H(I), is in reality a very poorly crystalline non-stoichiometric
material consisting principally of dimeric units at first, but
subsequently slowly polYmerising after a few days to give higher linear
units like pentamer and thence octamer with the passing of time.
Mechanism of Retardation
a) Background
b) Experimental Part
90
80
70
u 60
CO
~ 50
Vl
0
u
Vl
> 40
30
20
10
+ 1\ H20
The presence of some calcium hydroxide was due to the
moisturisation of some of the free lime content of the clinker:
Ca6[(A1,Fe)(OH)6]2(S04)326H20
Because of the impure nature of the phases and the fact that
Al(II1) readily enters into solid solution with Fe(III), it is
not possible in practice to apportion how much ettringite arises
from the ferrite phase and how much arises from the a1uminate
phase. Small amounts of calcium hydroxide, as present in the
unhydrated cement, were also observed here. No calcium silicate
r t u P
56 Chemicals in the Oil Industry
ricu re ,
Infrared Spectra ot (1) tJ~ratecl Cl... G Oil..11 C...Il't, (2) Ceaent
B7d.ratecl UDretard" to !hick.aiae Tt. of 10' JIIillut , (3) Ce.ent Hyd-
rated with 0 Retarder to Thick.Bin '1'i_ ot 222 JIIillutell
0....::
w
u
z
~
~
z
<C(
i
4000 3500 3000 2700 1800 1600 1400 1200 1000 800 600 LOO 200
WAVENUMBER Icm- 1 )
2
.~
~
z
~
~
<C(
i i i i i i i i I
4000 3500 3000 2700 1800 1600 1400 1200 1000 800 600 LOO 200
WAVENUMBER (cm-I)
3
~
i i i I , i
4000 3500 3000 2700 1800 1600 1400 1200 1000 800
WAVENUMBER (cm -1 )
r t u P
Chemical Aspects ofOilwell Cementing 57
d) Conclusion
Acknowledgement
TABLE 3
!PI Limit
~ !
CS 64.7 48 min - 65 max
3
Cs 7.0
2
CA 2.1 3
3
C AF
4 14.0
C4 AF + 2 x C A 18.2 24
3
K0 0.25
2
Na 0 0.16
2
Na 0 equivalent 0.32 0.75
2
MgO 0.7 6.0
53 1.9
Loss on Ignition 0 9
0
By E. J. Vase
SHELL U.K. EXPLORATION AND PRODUCTION, 1 ALTENS FARM ROAD, ABERDEEN, U.K.
Introduction
A production platform in the North sea will have some or all of the
following, depeming whether it is producing gas as most are in the
southern North Sea, or producing crude oil as in the northern
operations area:-
SHELL Operated
and Associated
Oil and Gas
SuJtom
Systems
N.North Sea
Orkney
~~
~O
c===J Oil
c===J Gas
DD Proposed
"' Mossmorran Gas
~raefoot Bay
Figure 1
r t u P
The Role ofChemicals in Oil and Gas Production 63
Platform Processes
DESIGN CAPACITY
GAS LlQUIOS
r t u P
64 Chemicals in the Oil Industry
160,000 barrels per day will provide adequate daily feedstock for an
average sized refinery.
62.6 Mega Watt would light a small town. '!he four Brent Platforms
produce and use electrical power equivalent to the needs of a city the
size of Aberdeen.
285 million standard cubic feet is sufficient gas per day to provide
2,800 houses with gas for one year.
(a) Produce a low vapour pressure (safe for handling) crooe oil.
(b) Provide gas for energy used on the platform, if required.
(c) Provide gas for gas injection or gas sales, if required.
In most North Sea oil bearing formations the oil is in contact with
large reservoirs of water (known as formation water) and as the oil is
produced it is replaced in the oil bearing zone by this formation
water. Eventually this water is produced with the crude oil: therefore
all producing platforms are provided with the means to separate this
water fran the crude.
r
6,OOOlbs/m.2
~
FUEL SYSTEM r;;--
5'
~
~
;:::
~
Cl
t
~
V:J
~
~
~
:;::
~
cs'
;:::
u
150,000
bbl/D
~CRUDE
P
+ NGL
Figure 2
0'1
VI
r t u P
66 Chemicals in the Oil Industry
On the Brent platfonns, water will drop out in the storage cells prior
to export to the Sullom Voe Oil Terminal, but on most other platforms
water is separated in the various stages of separation at the same time
as gas stabilisation takes place. This is called three phase
sepa~ation. (See Figure 3). f.t:>st producing platfonns in the Brent
System are able to export "dead" 8-11 lbs vap:>ur pressure crude or add
natural gas liquids to the crude before export to produce a gas rich
crude with vap:>ur pressures of between 40 to 150 psi. On the Shell
platfonns this is achieved by contacting snaIl portions of "decrl" crlrle
with natural gas liquids and reinjecting this rich crude into the main
crude stream leaving the platfonn. '1b obtain these natural gas liquids
the gases from the separator train are canpressed contacted with the
crude oil sidestream, cooled and allowed to separate again into rich
crude and the more volatile gas fraction. '!he gas separated at this
stage is contacted with Glycol to ranove water and then is either
reinjected into the producing reservoir or exported to shore. Other
North sea operators control vapour pressure by pressure control of the
last stage separator. Other operators inject NGLs directly into the
exported crude oil.
r------------ ------~--.-----
~~ ~i
o~
~!
~~
~3
",Cl:
...
~~
~
"'""a; 2~
0'1
00
OIATOYACE~
EARni
r
HOPPER
OVEReOARO
PUMP
t
SEA WATER
PUMPS
u
SEA
WATER
INTAKES
OXVGEN
SCAVENGING
F"LOWLlNES
TO WEu..5
Q
~
PUMP & TANI(
3
P
OVERBOARD
DUMP INJEC TION PUt.lPS (:;"
~
c;;--
s"
S-
~
OEAERATOR (~ANSFER) PUMPS
g
SEA WATER INTAKE DEAE RATION TRANSFER FIL TRATION INJECTION ~
~
~
~
Figure 4 ~
r t u P
The Role ofChemicals in Oil and Gas Production 69
Water produced with crude can be separated whilst stored in the storage
cells, but same installations separate water in the separation train.
In either case oil- contaminated water (100 to 1,000 ppn) has to be
processed to reduce any oil contamination to the level required by law
(about 40 to 50 ppm). Two systems are used, parallel plate
interceptors and gas flotation uni ts. In both these systems
polyelectrolytes can be used to improve performance.
The line used to transfer crude oil fran the Brent field to the
Shetlands is 160 kilanetres long and the gas pipeline to the St Fergus
gas plant is 450 kilanetres in length. Studies are being performed to
evaluate if corrosion is a problem in the oil line and at present it is
not yet being treated except two sections of line (Brent Alpha to Brent
Bravo and Brent Delta to Brent Charlie) which have corrosion inhibitor
continuously injected. Consideration is being made how best to treat
the very long gas line against sweet (carbon dioxide) corrosion, and we
are also prepar ing a procedure should sour (hydrogen sulphide)
corrosion manifest itself. Continuous injection of inihibitors could
be very, very expensive; therefore we are exper imenting with viscous
slugs, or gels impregnated with inhibitor. How effective such a
technique will be remains to be established.
Biocide Treatment
1- ---.------------,---------1---------1---------.------, , , , ,- 1
1 1 1 1 1 1 1 1 1 1 1 1
:Field : AUK : BRENr : BRENr : FORrIES :INDEFATIGABLE: LEMAN : LEMAN : 'lliISTLE : SPA : SPA :
1 I I I I I I I I I I I
1 1 1 1 I 1 1 1 1 1 1 1
r
: Formation :RCYI'LIEGEND : MIDDLE : IiliER :PALEOCENE : RCJrLIEGEND : RCTLIEGEND: ZECHSTElli : MIDDLE : WATER : WATER :
: : :JURASSIC :JURASSIC : : : : :JURASSIC: AUK : BRENr :
:Well : 30/16-3 :211/29-3 :211/29-3 : 21/10-5 : 48/18-3 I 49/26-4 : 49/26-5 :211/19-1: : :
I I I 1 I I I I I I I
~
1
:
1
:
1
:
1
::
1 1
::
1 1
:-"--:---:
1 1 1
:pH : 6.3 : 6.6 : 6.6 : 7.2 : 6.8 4. 7 : 4.4 : 7.0 : 7.9: 8.1:
I I I 1 I I I I I I I
1 1 1 1 1 1 1 1 1 I I
:Ion concns(mg/l) : : : : : : : : : :
t
1 1 I 1 1 I I I I I I
1 + 1 1 1 1 I I 1 1 1 I
:Na : 40,500: 9,600: 8,100: 33,000: : : 8,290: 11,000: 12,000:
: : : : : : )77,940 )75,250: )35,270: : : :
:K+ : 580: 170 : 180: 2, 700 : ) ) :) : 240: 400: 450:
I 1 I I I 1 I I I I I I
1 ++ 1 I I I 1 1 1 1 1 1 I
:Ca : 5,700 I 260 : 480: 3,950: 11,822: 12,770: 57,740: 292: 495: 346:
u
I I I I I I I I I I I
1 ++ I 1 1 I 1 1 1 I 1
:M3
I
:
I
900 65 55 :
I
500 :
1
4,093:
I
2,910:
I
41,290:
I
59 : 1,335:
I I
13.6:
I
:Ba+
I
I
:
I
I
N.A. 39
1
39 :
I
1
210 :
I
N.A.:
I
I
N.A.
1
:
I
N.A.:
1
I
I
54 :
I
1
- :
I
- :
1
I
1 ++ I 1 1 1 I 1 1 1 1
:Fe
I
:
I
69 73 6. 0 :
1
170 :
I
N. A.:
I
N. A. :
I
N. A.:
I
O. 2:
I
O. 05:
I
O. 02 :
I
Q
~
P
1 _ I 1 I 1 1 1 1 1 1
~
:Cl : 74,000 14,400 13,472: 58,500: 146,763: 146,830: 276,900: 12,800: 20,000: 20,500: ;::;.
I I I I I I I I I I I $:::l
1 _ 1 1 1 1 1 1 1 1 1 1
~
:HC03 : 150: 1,400 433 : 450 : 43 : 21: N.A.: 1,190: 95: 73:
I 1 I I I I I I I I I 5
1 _ 1 1 1 1 I 1 1 1 1 1
:00
I 3 :
I
Nil:
I
Nil Nil:
I
Nil:
I
Nil:
I
Nil :
I
Nil :
I
N.A.:
I
Nil:
I
17:
I
So
~
~
1 _ 1 1 1 1 1 1 1 1 1 1
:s04
I I
: 650 :
I
33 21 :
I
<10 :
I
461 :
I
570 :
I
80 :
I
11 : 2,760 : 2,820 :
I I I ~
1 _I 1 1 1 I 1 1 1 1_1 ~
~
V:l
~
r t u P
The Role ofChemicals in Oil and Gas Production 71
anaerobic. However our main concern has been the possibility of these
microbes becaning active in the oil bearing rocks by being injected
wi th the injection water. Q.lr microbiologists have advised against
attempting to treat the injection water and we have accepted their
advice. Biocides are used but in small dosage for particular
applications, such as a well closed in for several weeks at a time.
The policy of whether to use biocide to protect a reservoir when
pressure maintenance is through water injection varies widely in the
North Sea fron nil use through batch treatment to possibly continuous
injection.
Proouction will continue well into the next century even if no more
fields are discovered. As plant ages corrosion problems certainly are
not reduced. Seawater breakthrough will steadily increase with
sulphate scaling problems increasing in proportion. Carbonate scaling
and wax deposition will certainly continue during the lifetime of these
fields and hydrogen sulphide generation downhole is a possibility
lurking in the background. As larger quantities of water are produced
as fields age descaling chemicals consumption will increase in
proportion.
The whole area of enhanced oil recovery other than gas and water
injection is an uncharted area. Enhanced oil recovery with respect to
the North Sea is still very firmly with the E & P research laboratories
and any likely applications are a long way away.
(1) Demulsification.
(2) Carbonate scale inhibition.
(3) Sulphate scale inhibition.
(4) Sweet and sour corrosion inhibition.
(5) Defoamers.
(6) Oxygen scaveng ing .
r t u P
72 Chemicals in the Oil Industry
(7) Biocide treating.
(8) Wax inhibition.
(9) Wax solvents.
(10) Sulphate scale removers.
(11) Deoiling chemicals.
r t u P
Chemical Demulsification of Produced Crude Oil Emulsions
Abstract
water droplets.
r t u P
74 Chemicals in the Oil Industry
Introduction
Materials
Methods
100 MICRON ~
100
80
60
~
s-
O)
-+->
ItS
3
-0
40
0)
-+->
ItS
s-
ItS
c-
O)
(/)
20
100 --
80
CtQ. 60
~
Q)
+J
to
3:
-0
"CV 40
+J
's"..
tU
0-
Q)
I---
V>
20
~ -
o
80R 80S 80R 80S 80R
FIGURE 2 THE INFLUENCE OF CONSECUTIVE CRUDE OIL THERMAL PRETREATMENTS
ON THE WATER SEPARATION AFTER 24 HOURS FROM A 20% WATER-
IN-NORTH SEA CRUDE OIL EMULSION
r t u P
Chemical Demulsification ofProduced Crude Oil Emulsions 85
16
12 ,,
,
-1
'\
1r/mN m
8
o
o 0.2 0.4 0.6 0.8 1.0
A/A
o
FIGURE 3 CRUDE OIL-DISTILLED WATER RELATIVE COMPRESSION CURVES IN
ABSENCE (-----) AND PRESENCE OF DEMULSIFIER B DILUTED AS
1% SOLUTION IN PROPANOL( .... ) METHANOL (-----) AND
XYLENE ( - - -) AND ADDED TO THE OIL AT 0.2 ppm
The n-A curve observed for the specific North Sea crude
oil is similar to those curves obtained for a range of
other North Sea and Middle East crude oils as provided
elsewhere 3 ; subtle differences do exist which can be
related to relaxation rates within the adsorbed interfacial
film and the relative speed of compression. Addition of
demulsifier B to the crude oil interfacial film prior to
compression generally results in a reduction of the change
in n for a given compression but the reduction is clearly
r t u P
88 Chemicals in the Oil Industry
Conclusions
There are two important findings fro~ this and other related
studies.
Acknowledgements
References
43.
By G. E. Jackson
PETROLITE LIMITED, BIRCHILL ROAD, KIRKBY INDUSTRIAL ESTATE, LIVERPOOL L33 7TD,
U.K.
polyacrylamide
e-g.
-7-(CH 1
H N-'CH 'NH
)n- N
H
-r H
tCH1 )n-.l.-
H N-(CHJ- NH ____
2 \ ~n n
R,+
"N - Hl.
RI
amine amine salt
These polyamines may be further reacted to form quaternary
ammonium ~alts which are permanently charged,i~. in a
quaternised polymer the charge density is independent of pH.
e.g.
R
1
R2 -
'+
N-
I
R3 Cl
R
4
These polymers are available in a number of physical forms,
the low to medium molecular weight usually as solutions, but
as the molecular weight is increased the viscosity of the
polymer solution increases and for these it is normal to
use an emulsion or dispersion polymer. Solid polymers are
available commercially but not widely used in the oil-field.
Effect of Charge Density on Polymer Performance
In an effort better to understand the mechanism of emulsion
destabilisation, a study was made of the effect of charge
density on the performance of polyelectrolytes in a number
of wastewater treatment processes.
The polymers used were a series of polyquaternary
ammonium compounds (C23,C35,C55 and C ) quaternised to
76
varying degrees in order to vary the charge density on the
polymers. The charge density or mole % quaternised was 23,
35, 55, and 76 mole % respectively and the molecular weight
was essentially constant at rV10 6
1
100mgl- dispersion of 1 .11J.m particles in deionised water
buffered at pH 8 with ammonium chloride. Measurements were
made as a function of polyelectrolyte dose for each of the
four polymers.
60
A-
t 40
C7~ C
S8
/& EJ--
zeta
20 ;JJ ~
Potent al
- &. G
I-~//~'----,'/-----'--,--,../-...-..-.-....,----"-
. (iJr J!
mv
o
0
0.3
--+
-40 11 ~ 0/
- 60
~ Figure
I
90
CV
1 80
70
Residual
60
Oil
and
Grease 50
ppm
40
30
20
10
10 20 30 40
60
r 50 C
33
Turbidity
NTU
40
C,23
30
20
S 10 lS 20 2S
-1
g
/16.0m l
100
10.6mgl- 1
f 80
/
EJ/ ..J
~
Turbidity
NTU
60
Px10psi
40
10.6mgl- 1
20
2 3 4 s
Time hours -..
r t u P
Oily Wastewater Treatment in the Production ofCrude Oil 105
The criteria used to evaluate filter performance were:-
a) Rapid reduction of effluent turbidity to 1NTU, and
maintenance of this quality for the length of the filter
cycle.
b) The differen tial pressure across the bed, /::;. P, should
not increase rapidly i~. maximise filter cycle time.
Without chemical addition the turbidity removal was
maximum 10-20%. Addition of 10ppm of C gave good performance
76
for about 2 hours at which point 'breakthrough' occurred.
Increasing the dose to 16ppm gave good quality water for almost
six hours at which time the ~P limit of 6psig was reached and
the run terminated.
The other polymers were all tested under the same conditions
and at the same dose of 16mgl- 1 .
-1
47mgl
100
16mgl- 1
t 80
16mgl- 1
Turbidity
NTU
60
Px10psi
40
0
20 0 ~~
/,O~ ~O 0
~ooo-
1 2 345 6 7 8
References
Introduction
(a) Dilution with low wax content crude stock or light distillates.
Types of Wax. The waxes occurring in crude oils are very complex
mixtures of normal paraffins, branched or isoparaffins and cylcoparaffins
or naphthenes. These are simply illustrated in Figure 1. Although of
little practical relevance to the oil production situation where
precipitation and crystallisation is complex, it helps in the general
understanding if the basic characteristics of the two main categories of
wax extracted from crude oils are compared. These are listed in Table 1
and Figure 2 shows crystallisation exotherms measured by differential
scanning calorimetry (DSC) on some typical commercially available refined
paraffin and microcrystalline waxes. The individual base lines of these
curves, in this and all other similar figures showing DSC exotherms in
this paper, have, been staggered to minimise confusion of one curve with
another. Similar crystallisation exotherms on waxy crude oil samples
where, at the commencement of the test, the waxes are in solution show
that crystallisation is delayed to a lower temperature and the
temperature range over which crystallisation occurs is very much broader.
This is of course to be expected. In practice the crystallisation
process is considerably influenced by many factors including shear and
thermal history and although observation of these exotherms provides some
information it is of limited practical use.
\/\/\/\/\/\/\/\/\/
C~ C~ C~ C~ C~ C~ C~ C~ c~
NORMAL PARAFFIN
c~ c~ c~ c~ c~ c~ ,~ c~ c~
/\/\/\/\/\/\/\/\/\
c~ c~ c~ c~ c~ c~ c~ c~ ~ c~
\
CHz
ISOPARAFFIN /
CHJ
CYCLOPARAFFIN
Table 1
PARAFFIN WAX(M.PNTapprox.6SC)
PARAFFIN WAX
(M.PNT approx. SOC)
MICROCRYSTALLINE WAX
(M.PNT approx. 5SC)
MICROCRYSTALLINE WAX
(M.PNT approx. 8S-C)
t
dH
dt
1
Scale [- 2 m cal sec
Coating
80 60 40 20 o -20
Temperature (OCl
, I
I CH, CHz CH, CH, C:i z CHz C~
i l \ / \ 1 \ / \/\1\/1\
,CHz CHz CH, CH, CH, CHz CH, I
I I
I I
C~ C~ C~ C~ C~ C~ C~ C~ c~ C~ C~ c~ c~
/ \ / \ 1 ) / \ / '-I \./ \ / \ / \ / ~ / \ / \ / \
CH CKz iCH, CH, CHz CHz CH, CH, CHz I CH, CH, CH
/ I I /
o'
C~ C~ C~ C~ C~ C~ C~
I
C~ 0
\ C=1 /\/\/\/\/\/\/\/~
: CH, c~ CH, CH, CH, CH, C~ I
\
C:0
/
C~
J
I
I /
C~
I I
AMORPHOUS: CRYSTALLINE REGIONS : AMORPHOUS
REGION , J REGION
The exact way in which crystal modifiers operate is not absolutely clear
but it is a~most certainly a combination of different mechanisms
involving both nucleation and either co-crystallisation or absorption.
In order to achieve any effect the additive must be in solution in the
crude oil at a temperature at which at least some proportion and
preferably the major part of the offending waxes are also in solution.
As the oil cools the waxes and the additives crystallise out within the
same temperature range. Nucleation of crystals by crystallisable
polymethylene segments of the polymer is believed to lead, to the
formation of a large number of wax crystals. The growth of these
crystals is then subsequently arrested by the incorporation into the
lattice of further polymethylene segments of the additive whose bulky
substituent groups prevent further incorporation of molecules of the
paraffin. It also seems likely that the polymethy1ene segments of the
additive actually build onto the wax crystal as a result of nucleation by
the wax crystal itself. In order to achieve the maximum affect on wax
crystal growth it is desirable that molecules of the modifying additive
continue to precipitate from the crude oil throughout the whole period
during which the wax is also precipitating. To achieve this it is
sometimes useful to use blends of additives having slightly different
r t u P
The Use ofEthylene- Vinyl Acetate Copolymers 113
POLY METHACRYLATE
dHt
dt
Scale L
[
1m cal sec
-1
Cooling
Ba 60 40 20. 0 -20
Temperature ee)
Figure 4 Commercial pour point depressants- crystallisation exotherrns
r t u P
114 Chemicals in the Oil Industry
Comonomer Ratio or Vinyl Acetate Content. This is one of the two most
important factors which control all the properties of ethylene-vinyl
acetate copolymers, the other being average molecular weight which is,
of course, discussed below. As vinyl acetate content increases, three
important trends can be identified. Firstly degree of crystallinity is
reduced, secondly polarity of the polymer increases and thirdly, at very
high levels of vinyl acetate, chain stiffness is increased by steric
hindrance. However, as far as crude oil treatment is concerned, it is
the first of these that is of most importance. The relationship between
crystallinity and vinyl acetate content of EVA copolymers is shown in
Figure 5. Crystallisation exotherms measured by differential scanning
ca10rimetry on EVA copolymers having different vinyl acetate contents are
shown in Figure 6. It is interesting to note that the peaks of these
exotherms span the range for petroleum waxes. From the foregoing
discussions on wax control it follows that this ability to control
polymer crystallinity, and indirectly the temperature range over which
crystallisation occurs, by altering vinyl acetate content is of
considerable significance. It is of equal importance that this reduction
in crystallinity is, not surprisingly, accompanied by a corresponding
increase in solubility due to the increased amorphous content of the
r t u P
The Use ofEthylene- Vinyl Acetate Copolymers 115
o 10 20 30 40 50
VINYL ACETATE CONTENT~)
Figure Relationship between vinyl acetate content and degree of
crystallinity for EVA copolymers
Table 2
Pour Point
Vinyl Acetate MFI Hydrocarbon Branches per (OC)
Content 1000 Carbon Atoms
(% by weight)
24 20 7 7
33 25 6 2
28 6 6 9
28 400 9 2
28 400 9 2
28 400 19 -5
r t u P
116 Chemicals in the Oil Industry
18%VA
12.S%VA
dHl
dt
-1
Scale - 1 m cat sec
[
Cooling
80 60 40 20 0 -20
Temperature C
EVA copolymers containing less than about 15% of vinyl acetate by weight
tend to be comparatively insoluble unless their molecular weight is also
very low and these latter products are comparatively costly. For this
reason EVA copolymers containing from about 18-40% vinyl acetate are of
most interest in crude oil treatment and in fact products containing from
25-40% VA are the most commonly used.
r t u P
The Use ofEthylene- Vinyl Acetate Copolymers 117
Figures for molecular weight are in fact rarely quoted for polymeric
materials and for EVA copolymers it is standard international practice
to follow the melt flow rate or melt flow index (MFI) procedure of
classification using International Standards Organisation Test Method
ISO R292. This is a ram extrusion viscosity measurement carried out
under standardised conditions which gives a value which is inversely
related to molecular weight. This method of describing the molecular
weight of EVA copolymers will be adopted in this paper. Table 3 shows
the approximate relationship between MFI and number average molecular
weight.
Table 3
2 32,000
20 24,000
200 19,000
400 13,000
19 Chain Branches
9 Chain Branches
dHt
dt
Scale [= 1 m cal. sec'
VA Content 28 %
MFI 400
80 60 40 20 0 -20
Temoerature (OC)
Viscosity and Yield Stress. The viscosity of the crude oil during its
passage through a pipeline for example is clearly important. In
particular, throughput rates and energy consumption, and therefore
production costs, are obviously directly related to it. Laboratory
dynamic viscosity measurements give valuable information on this.
However, in many situations, arguably it is the yield stress of the oil
in the event of solidification (or gelation) which is of most
importance, since it is this which governs the ability to restart flow
after a production stoppage. For the purposes of. this paper emphasis has
therefore been placed on this aspect.
There are several techniques available for determining yield stress using
rotational viscometers or miniature pipelines but these tend to suffer
from certain disadvantages. In particular, the equipment is usually
comparatively expensive. There is also a risk of obtaining false
readings due to unseen contraction of the oil away from a critical
surface and further the time required to obtain statistically sound
results can be very lengthy.
r t u P
120 Chemicals in the Oil Industry
A very simple test which overcomes these limitations involves the use
of glass tubes say 100-200 mm long by 10 mm internal diameter. In this
test several samples, usually not less than 10, of each crude oil are
conditioned, cooled and sheared as appropriate above the pour point. The
glass tubes, sealed with a cork at one end, are then filled to a length
of approximately 100 mm with the crude oil. Cooling and conditioning is
then continued, obviously without shear, as required. Typically this may
involve cooling from about 35C to 4C over a period of several hours
followed by storage for 72 hours at this temperature before conducting
the test. The yield stress is simply measured by applying air pressure
to one end of the tube and recording on a manometer the pressure at which
the gelled slug of oil starts to flow. By testing a large number of
samples it is possible to eliminate obviously erroneous results. Ouite
clearly this test is far removed from actual operational conditions but
nevertheless it has again proved of value in the initial screening of EVA
copolymers as oil flow improvers.
OilFlow-'
Oil
Reservoir
Coolant Flow
Thermostatically
Controlled Bath +- Drain Cock
Peristaltic
Pump
W - W
% Reduction = __u t x 100
Wu
Simple laboratory tests of the type described in this paper are very
useful for initial screening of EVA copolymers for use as crude oil
flow improvers or wax deposition inhibitors.
Field Experience
The oilfield in question is located in Eastern Europe and the crude oil
has a pour point of l8-20C. This oil is required to be pumped through
a subterranean pipeline 70 kilometres in length. Winter soil
temperatures are 4c and the operator specifies a maximum pour point of
OC during winter to give a reasonable margin of safety. Laboratory pour
point tests showed that the addition of 100 ppm of EVA copolymer
containing 28% of vinyl acetate and having an MFI of 400 readily met this
requirement. In this case copolymers with a high level of chain
branching were selected since the copolymer solution, in a mixed aromatic
solvent, is pumped through a small diameter pipe 2.5 kilometres in length
and it therefore also needs to exhibit a low pour point. This solution
is added to the crude oil in a mixing tank which collects the output from
several wells. In practice the dosage rate of the active ingredient is
varied depending on the climatic conditions and is typically 20 ppm
during the summer and 100 ppm in winter. Throughout several years
operation no flow problems have been encountered either during rer.ular
production or on re-starting after stoppages.
r t u P
122 Chemicals in the 0 it Industry
Table 4 Effect of Different EVA Copolymers on the Pour Point of
Various Crude Oils
1 J 1
1 EVA Copolymer Characteristics 1 1
1 1 Addition 1 Pour Point
1 1 Rate of 1 (OC)
1 VA Content MFI Hydrocarbon 1 EVA to 1
1 % branches per 1 oil (ppm) I
1 1000 carbon 1 1
1 atoms 1 1
1 1 I
I 1
I Untreated Crude Oil 1 30
I 1
I 24 20 7 I 100 8
1,- 24 20 11 1 100 14
1 1
1 24 400 10 1 100 12
1 24 400 16 1 100 18
1 24 400 24 1 100 20
1 I
1 1
I 28 400 9 1 100 9
1 28 400 19 1 100 20
1 1
1 1
1 Untreated Crude Oil 1 8
1 1
1 24 20 7 1 25 1
I 28 400 9 1 25 -18
1 28 5 6 1 25 below -25
1 1
I 33 25 4.5 1 25 -23
1 33 45 8.5 1 25 -13
1 1
1 1
1 Untreated Crude Oil 1 -1
1 I
1 28 400 9 I 25 -26
1 28 400 19 1 25 -16
I 1
I 24 400 10 1 25 -22
1 24 400 16 1 25 -10
1 1
I I
1 Untreated Crude Oil I 21
I I
I 18 2 6 I 200 11
I 18 25 8 1 200 22
1 I
I 28 400 9 I 200 25
1 I
Table 5 Effect of Different EVA Copolymers on Pour Point, Yield Stress and Wax Deposition ~
of Various Crude Oils. ~
s:
~
r
% 1 I branches per I Rate I I I (%) I 7
1000 carbon I (ppm) I I I I :s;::
atoms I 1 I I I ~
~
~
~
Untreated Crude Oil I - I 30 I 250 I - I E;-
I I I I I ~
24 20 I 7 100 I 8 35 40 I (J
t
I 1 1 1
.g
\:)
28 1 5 I 6 1 100 1 11 I 30 I 55 I ~
~
28 I 400 I 9 I 100 I 9 I 25 I 50 I ~
"""'I:
~
28 I 400 I 19 I 100 I 20 I 55 I 25
28 I 400 1 21 I 100 I 21 I 70 1 20
u
I I I I I I
33 I 25 I 5 I 100 I 15 I 45 1 -
I I I I I I
40 I 50 I 6 I 100 I 26 I 85 I 35
I 1
1 1
- -
P
Untreated Crude Oil 1 I 8 I
I 1 1 1
28 I 400 1 9 I 100 1 Below -25 I - I 80
I 1 I I
1 I
Untreated Crude Oil I - 1 -1
I I I 1
28 I 5 1 6 I 100 1 Below -25 1 - I 75
I 1 I I I
28 I 400 I 9 I 100 I Below -25 1 - 1 85
N
w
r t u P
124 Chemicals in the Oil Industry
Future Development
Acknowledg_ement
References
6 P B Smith and R M J Ramsden, Proc Eur Offshore Pet Conf, London 1978,
283.
By K. S. Johnson
OILFIELD CHEMICAL SERVICES, 430 CLIFTON ROAD, ABERDEEN AB2 2EJ, U.K.
TABLE
---------1
!y~!~~~_~~~Q~_~Q~~Q~~~I~_~~~tj!~~h_~~~~Y~!~_E.QB-~Q~I~_~~~
~~g_~8~~!~~_~kE_~~I~8
North... Sea
---_.~ --- ~r~,~!~,!2_ ~l f
TABLE 2
----------
2 3 4
TABU:
---------3
Stoichiometric
Ratio Ba: S04
(theoreti ca1=
1:0.7) 1:0.04 1:0.61 1: 1.24 1: 1.95 1:2.7 1:3.64 -
Excess S04 2-
after reacti on
with Barium (i.e.
available for Sr) NIL NIL 123 268 403 537 -
Stoichiometric
Ratio Sr:S04
(theoreti ca1 =
1: 1.09) - - 1:0.24 1:0.55 1:0.87 1: 1.24 -
-
NOTES:
1. There is sufficient sulphate ion for complete barium precipitation at 6%
seawater breakthrough.
2. There is sufficient sulphate ion to satisfy the stoichiometry of barium and
strontium at approx. 20% seawater breakthrough.
3. The ionic strength of the formation water is 1.56. Hence solubilities of
both barium and strontium will be higher than theoretical for a given
tempera ture.
r t u P
130 Chemicals in the Oil Industry
Scaling Index by !
Stiff Davis Extr
of Langalier
method +1.65 +1.80 +1.83 +2.13 + 1.88 +1.86 +1.68
Temp above
which SI +VE 30 0 C 23 0 C 23 C 23 0 C 20 0 C 20 0 C 280 C
r t u P
Water Scaling Problems in the Oil Production Industry 131
!
+-----+----+----+---+-----t------;.--.,...-O+-----+--
I ~ I i
: ~: 1 I'
I ' cfil (;\3'-
I o:~ I i
~. -_.:- -~._~ -.-- ~_.. ---1-- -------I J -- -,- ",f
i 5 ~JS:! I I I
I
I ''ll 9 2.lI
\'
\
I
I I'
!
i' I
I
"'I
I
"
~-----l-}----- -'-.~ '\ t-_' 'r--~-t--:---l-/!--+--'------'---4'-'--
l---.~-l--::--: 1-~--1~1 .1;/
', Jji 2~ I "i \}-l-/j
I \
~---+----i------+----+-'
----t----+------1o-~--!---
i ,! I I.
I 1,0 ~c."> ~ ,p 411' 50 -'P ..~ ~c
i l l !
~ 10
,-----1---'--
I
r t u P
132 Chemicals in the Oil Industry
0
From the scaling index calculated at 85 C is also determined the
temperature at wh~ch the waters first become scaling. The minimum
temperature is 28 C, that of seawater alone. It may be deduced
therefore that 3n a downhole situation where the temperature rgnge
will be from 85 C (bottom hole temperature) reducing to say 60 C
as the surface separation equipment scaling could be expected
throughout the system.
It is also in~eresting to note that,since seawater has a positive
index from 28 C,for seawater used in water injection systems
there is the possibility of carbonate scale ~mere water is used,
for heat exchange/cooling purposes, prior to injection into the
formation.
TABLE 5 lists the common scaling species and the physical conditions
that influence scale formation.
TABLE
---------5
~~~Q~_~~~~!~_~~~~!~~_!~_Q!~E!~~g_~Y~I~~~_~!I~_!~Eh~~~~!~
E~Y~!~~~_E~~IQ~~
GRAPH
---------2
EFFECT OF COz PARTIAL P(~ESSURE ON THE
SOLUBILITY Of CALCIUM CA.ROONATF.
120
100 -
00-
(,0
c~
PHESSURE
(BAR) 40-
20
--~i ----y----.,.------.-,-...---,-.~
1000 I~OO 2000 2~OO 3000 3500
SOLUBILITY OF CoCO~
(mo ILlTHE)
r t u P
134 Chemicals in the Oil Industry
----------l
SOLUBILITY OF CaC03 AT I BAR
COl PARTIAL PRESSURE IN PURE WATER
1250
1000
750
SO~~~~1TY
(m~/I )
500
250
O~--"I--,--r-i
-'-~---r----.--~_--.
20 40 C:O 80 100
TEMPERATURE. QC
8000
LEGEND
TEMP C
o 05
5
p 10
6 25
35
50
70
90
o~----..----r- i I
50 100 ,~o 200 250 300
NoCI CONCENTRATION
'--
(om/l) -1
,..-.------------_._--_._---_ _---- ..
OOS04
SOLUBILITY
(moll)
o ----or-----_.,-.
L - ...
10
-------r.30
20
----~i-
40
IONIC STRENGTH
It can be seen that for say a mixed water containing barium and sulphate
ions that scaling may occur if the separate ionic concentrations are
above the values as defined by the key physical conditions. Hence
if barium is known to be present in the formation water and seawater
breakthrough has taken place then the probability of scale deposition
somewhere in the system should not be ignored. Failure to find
barium in the analysis of a produced water sample taken at the surface
facility in a water known to contain some barium must suggest that
precipitation has already taken place and the scale has already been
deposited downhole.
-------------------------_._---_._---
SOLUBILITY OF SrSO" IN No Cl SOLUTIONS t~T 25C
500
SrSO" 400
SOLUBILITY
(mQ/I) 300
200
100
------,-------,------T--- , -r
05 10 15 2-0 2-5
L- . . ...
IONIC STRENGTH . _ . . _ . _ . _ _. _ -
g~~~!'!!1i!}~~iQ!}_Qf_~rQ~~~i!l~~_Qf_~~l~_EQr'E~~iQ~_~~_~~l~~!~~iQ!}_
~~!bQ~~
pCa = log
Mols Ca++/litre
pAl k log
Equivalents total alkalinity/litre
The details of the calculation procedure a~e not given here but are
presented fully in the literature.3,4
A positive SI value indicates that scaling is likely i.e. pH>pHs:
water is supersaturated with respect to calcium carbonate.
At SI = 0 the water is on its saturation point with respect to
calcium carbonate.
A negative SI value indicates that scaling is unlikely t.e. pH(pHs:
water is not saturated with respect to calcium carbonate.
It must be appreciated that the method is not absolute. A calculated
low order positive index water (say up to + 0.5) may not under some
conditions deposit carbonate scale; however the posibi.lity should not
be overlooked. For waters of higher positive SI value it would be
unwise to assume no scaling will occur and to take some form of
scale control measure.
S = 1000[(X 2+4K)O.5_ X]
Er~~!i~~!_h~~2r~~2!:~_~~~b2~_2f_~~~!i~9_!~~~~~~t_E!:~~i~!!Q~_~~9
~~~!~_!~~i~i~2r_~~~!~~~12~
There are two basic methods in general use by oil and chemical service
companies.
Static Scale Precipitation method and the dynamic "Tube Blocking ll
technique.
The static precipitation method was developed by BP Research~ Sunbury;
the dynamic test method was originated by Shell Petroleum but has been
modified and improved by others.
Variously modified testing units have been made to the initial concept
by workers in the field of oilfield water scaling problems.
The basic principle, however, is essentially the same. The method
depends on the rate at which the pressure drop increases through a
standard length of capillary tubing. The tubing bore diameter is
normally of the order 1.Omm; length is dependent on individual
preference but should be no less than 1 metre. Generally stainless
steel tubing wound into a coil is used; care must be taken to ensure
the tubing configuration is the same for each comparative test since
change in bend radius will significantly alter the results.
The apparatus is shown diagrammatically in FIG 1 set up for calcium
carbonate scaling work.
It consists of a water storage reservoir for the water under test and
a second reservoir containing either a solution of the scale inhibitor
to be evaluated or the second water with or without added scale inhibitor.
Flow from the two reservoirs ;s accurately ratioed to give the required
values by two variable speed peristaltic pumps.
The two flows are mixed in the magnetically stirred mixing unit from
where the mixed waters (or water minus scaling ion + water with scaling
ion and scale inhibitor) are transferred to the test coil. The coil
is inrnersed in a constant temperature bath at the test temperature.
Flow from the coil is to waste or may be collected in an automatic
sampler for ions analysis. The pressure change across the system
(really the change across the capillary tube since the volume of the
rest of the system is a constant) is measured by a pressure transducer,
the signal from which is amplified and displayed on a moving chart
recorder.
L, I ,~,. C.01\_
i
r
\,1'\
WATER. FEEl)
PUMP w(-\~T
~F:NSwc...e:tt
t
\JRTER. ~
~c.ALE .. -rE,.t\'. c.oN~RoL.
INHH~rrOI<
PUNP
u
WfllER
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r t u P
Water Scaling Problems in the Oil Production Industry 143
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r t u P
Water Scaling Problems in the Oil Production Industry 147
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r t u P
Water Scaling Problems in the Oil Production Industry 149
References
----------
By J. A. Kelley
TRETOLITE DIVISION, PETROLITE CORPORATION, ST. LOUIS, MISSOURI 63119, U.S.A.
INTRODUCTION
Corrosion inhibitors are r-outinely used in oil production at rates varying from a few
parts per million (mg/I) to thousands of parts per million. Many of the commercial
corrosion inhibitors are unique mixtures that may contain surfactants, film enhancers,
demulsifiers, or an oxygen scavenger in addition to the inhibitor moiety. The purpose of
this paper is to provide a brief discussion of the chemistry of t!le inhibitor moieties and
provide a few illustrative examples of formulation considerations. This paper does not
attempt to describe all of the commerically available formulations, but rather the broad
chemistries within which they fall.
1) Amides/lmidazolines
2) Salts of nitrogenous molecules with carboxylic acids
3) Nitrogen Quaternaries
4) Polyoxyalkylated amines, amides, and imidazolines
5) Nitrogen heterocyclics
There are other, non-nitrogenous inhibitors that contain phosphorus, sulfur, or oxygen
atoms but they are used less frequently.
AMIDES/lMIDAZOLINES
Many of the common oil and water soluble corrosion inhibitors contain amides
and/or imidazolines which are produced by condensing a carboxylic acid with a primary
amine. The carboxylic group is often derived from low cost natural sources such as crude
or refined tall oil. 2 The typical fatty acid derived from tall oil is composed primarly of
C18 linear saturated and unsaturated chains with minor amounts of C16 linear chains and
some rosin acids. 3,4 Naphthenic acid mixtures derived from petroleum are also used. 5
r t u P
The Chemistry ofCorrosion Inhibitors Used in Oil Production 151
The amine frequently used in the reaction is a polyamine having the structure H2N(-
R-NH)x H where R is an alkylene group containing 2 to 6 carbon atoms and x is a
small whole number greater than 1. A frequently used polyamine is diethylene
triamine (R=CH2CH2 and x=2). Mixtures of higher homologs (x=4 etc.) can also be used. 2
where R is derived from the previously mentioned tall oil fatty acids. A water soluble or
water dispersible inhibitor blend is often made from such an imidazoline by adding a low
molecular weight organic acid and a mixture of solvents and perhaps a surfactant. 6,7
There are numerous references that discuss salts formed by the neutralization of the
basic nitrogen by tall oil fatty acids, polymerized fatty acids, naphthenic acids, or simple
organic acids. 8,9,10,11,12,13,14 A recent example utilizes a high molecular weight
polymerized carboxylic acid neutralized with a tallow amine.l S The use of polymerized
fatty acids in inhibitor formulations is estimated to be in the millioM of pounds per
year. 16 In general, any unreacted basic amine or the imidazoline itself can be fully or
partially neutralized with wide variety of acids.
QUATERNARY NITROGEN
The term quaternary nitrogen applies to compounds in which all of the hydrogens of
the ammonium ion have been replaced by linkages to carbon. These are often referred to
as cationics as shown:
+
R'
I
R~N -R X-
R
1",
r t u P
152 Chemicals in the Oil Industry
The quaternary nitrogen compounds are excellent cationic surfactants and may
possess biocidal, demulsifying, or corrosion inhibiting properties.l 7,18 In the fatty
amine quaternaries, at least one of the R groups consists of a long alkyl chain and
may have more than one cationic nitrogen atom.l 9 Other nitrogen containing
compounds that are quaternized include imidazolines,20 polymerized amines,21,22
and pyridines. 8
NITROGEN HETEROCYCLICS
INHIBITOR FORMULATION
A low cost water soluble inhibitor can be made using the imidazoline depicted
earlier by simply adding acetic acid and a suitable solvent. In an oilfield water system
where solid deposition such as iron sulfide is a problem, a suitable amount of a nonionic or
cationic surfactant has to be added to reduce the tendency for solids to deposit on metal
surfaces. A buildUp of iron sulfide often leads to a pitting type of corrosion under the
deposits. If the oilfield water contains low levels of oxygen, a small amount of a suitable
r t u P
The Chemistry ofCorrosion Inhibitors Used in Oil Production 153
A laboratory test called the C02 sparge test is often used to screen water
soluble/water dispersible inhibitors. The results correlate well with field experience. The
test is based on the linear polarization principle. There are numerous multichannel
instruments that allows ten or more inhibitors to be evaluated in a twenty-four hour
period. The test can be run as a sweet or sour system, in straight brine or a
brine/hydrocarbon ,mixture, and up to a temperature of 150 0 F. See Appendix 1 for more
details.
An effective oil soluble inhibitor can also be made from the same imidazoline by
simply replacing the acetic acid with a high molecular weight acid and using an aromatic
based solvent. To aid in uniform distribution of the inhibitor and ease of application, a
suitable nonionic or cationic surfactant is often added to make the oil soluble inhibitor
somewhat dispersible in the water. Secondly, a small amount of surfactant usua.lly
increases the effectiveness of the inhibitor. The table below illustrates the effect of the
addition of a surfactant and polymerized fatty acid to an amine based inhibitor. The
corrosion data was obtained from a dynamic corrosion test commonly known as a wheel
test, the details of which are given in Appendix 2.
Table 1 31
To minimize or avoid creating stable emulsions, a small amount of demulsifier may also
be added.
There are additional problems to consider when formulating an inhibitor for gas
wells. Care must be taken to devise a formulation that provides a uniform dispersion of
the inhibitor on the tubular goods for the selected application method. The inhibitor must
also possess good thermal and chemical stability in well fluids under production
conditions. Two of the inhibitor removal processes that exist in gas wells are washing by
r t u P
154 Chemicals in the Oil Industry
produced fluids and evaporation. Thus, the inhibitor moiety and any additives should have
a very low vapor pressure under production conditions and be as insoluble as possible in
well fluids, depending on the treatment method. 33
Inhibitors for use in gas wells are usually evaluated under higher pressures and
temperatures than are obtainable in the wheel test. Special test cells are often used to
simulate the acid gas partial pressure in these wells (u~ to 200 psi Pco2 or PH2 S).
Alternately, high pressure autoclaves capable of accomodating field fluids under the
conditions encountered in deep gas wells are often used. A typical autoclave test may run
for several weeks.
Most oil companies use a variety of laboratory tests to qualify inhibitors for field
use. These tests determine the need to add or delete components to achieve the desired
properties for a given application. Emulsion tendencies, solubility, partitioning
coefficient, and effectiveness in a variety of corrosion tests are among the qUalification
tests.,34,35,36
Considering all of the blend components and their possible combination, including
hundreds of surfactants and other additives, it is easy to understand the great number of
commercially available corrosion inhibitors.
The test relies on the linear polarization technique and utilizes the three electrode
system. One of the electrodes is called the reference electrode; the second the test
electrode; and the third the auxiliary electrode. The corrosion rate value (mpy) obtained
with the meter is the corrosion rate of the test electrode.
CURRENT SOURCE
t
CORROSION
METER [
~CO 2
-OIL
-BRINE
STANDARD BRINE
ION Mg/L
Na + 20,000
Mg ++ 2,000
Ca ++ 400
Cl - 32,500
SO - 590
4
r t u P
156 Chemicals in the Oil Industry
The wheel test is a dynamic corrosion test for evaluation of corL"osion inhibitors.
There are basically two versions of the test, both of which rely on determining the weight
loss of a steel coupon to calculate the corrosion rate. The first version (constant contact)
simulates treatment by continuous chemical application. The second (film peristency)
test corresponds to the conditions experienced during slug or batch type application of
chemicals. The procedure involves placing preweighed coupons into test cells with either
hydrocarbon (e.g. kerosene) and synthetic brine or actual produced fluids that have been
saturated with carbon dioxide, hydrogen sulfide or a combination of both. The chemical is
introduced into the cells at actual use concentration which may be in the fifty to one
hundred parts per million level for the constant contact version or thousands of parts per
million for the film persistency version. The coupons are added to the cells (care being
taken to exclude oxygen) and the cells loaded on a wheel that rotates inside a heated
cabinet. In the film persistency version the coupons are removed after a short period of
time (e.g. one hour), placed in fresh uninhibited fluids, and the test continued.
The total test period varies but is usually from twenty-four to seventy-two hours.
At the end of the specified time the coupons are removed, cleaned, and reweighed and a
percent protection for each inhibitor calculated as below:
REFERENCES
2. G.D. Chappell and J.R. Stanford, Corrosion Inhibitor Used in Brines Containing
Oxygen, U.S. 4,010,111, Mar. 1, 1977.
3. J. Drew and M. Propst, ''Tall Oil", Pulp Chemical Association, New York, 1981,
p.98.
4. L. Zachary, H. Bajak, and S. Eveline, "Tall Oil and Its Uses" Pulp Chemical
Asociation, New York, 1965, pp. 25-26.
5. C.L. Howle, Corrosion Inhibition with Oil Soluble Diamides, U.S. 3,997,469,
Dec. 14, 1976.
r t u P
The Chemistry ofCorrosion Inhibitors Used in Oil Production 157
8. M.D. Coffey, Corrosion Inhibitor for Aqueous Brines, G.B. 2,027,686 A, Feb.
27, 1980.
10. L. W. Jones, Water Dispersible Corrosion Inhibitor, U.S. 2,839,465, June 17,
1958.
12. G.D. Chappell and J.R. Stanford, Corrosion Inhibitor Used in Brines Containing
Oxygen, Canadian 1,019,554, Sept. 25, 1977.
13. J. Maddox, Jr. and W. Schoen, Composition and Process for Inhibiting
Corrosion in Oil Wells, Canadian 856,824, Nov. 24, 1970.
15. J.R. Stanford and G.D. Chappell, High Temperature Corrosion Inhibitor for
Gas and Oil Wells, U.S. 3,959,158, May 25, 1976.
16. E.C. Leonard, Polymerization-Dimer Acid, J. Am. Oil Chemists' Soc., 1979,
~ 782A.
18. T.J. Bellos, Method of Protecting Metal Surfaces Against Abrasive Wear in
Submersible Pumps, U.S. 3,661,784, May 9, 1972.
19. E.H. Pryde, "Fatty Acids", American Oil Chemists' Society, Champaign,
Illinois, 1979.
22. T.J. Bellos, Method of Protecting Metal Surfaces Against Abrasive Wear in
Pumps with Polyquaternaries, U.S. 3,751,364, Aug. 7, 1973.
23. J.L. Walker and T.E. Cornelius, Filming Amine Emulsions, U.S. 3,931,043, Jan.
6, 1976.
24. W.B. Hughes, Composition for and Method of Inhibiting Corrosion of Metals,
U.S. 2,940,927, June 14, 1960.
25. P. Merchant, Jr., C.O. Ohaji and F.L. Powell, Water Soluble Waterflood
Corrosion Inhibitor, U.S. 3,989,460, Nov. 2, 1976.
r t u P
158 Chemicals in the Oil Industry
27. S.P. Sharp, Inhibiting Corrosion in High Temperature, High Pressure Gas Wells,
WO 80/02700, Dec. 11, 1980.
30. D. Redmore, B.T. Outlaw, and R.L. Martin, Pyrophosphates, U.S. 4,075,291,
Feb. 21, 1978.
32. J. Stanford, Inhibition of Corrosion of Metals, U.S. 3,412,024, Nov. 19, 1958.
33. R.R. Annand, 28th Annual Southwestern Petroleum Short Course, April 1981,
Texas Tech. Unv., Lubbock, Texas, pp. 8,9,
34. A.C. Nestle, Materials Performance, Jan. 1968, Vol. 7, No. 1, p. 3l.
36. NACE Publication ID 182, Material Performance, Dec. 1982, Vol. 21 No. 12,
p.9.
r t u P
Quaternary Ammonium Compounds: Evaluation and
Application in the Control of Sulphate- reducing Bacteria
By E. Bessems
AKZO CHEMIE, DUREN, WEST GERMANY
A. F. Clemmit
AKZO CHEMIE U.K. LTD., HOLLINGWORTH ROAD, LITTLEBOROUGH,
GREATER MANCHESTER OL15 OBA, U.K.
1. Introduction
Fe +
2. Chemical Types
Disadvantages
oxidation of system
potentially corrosive
reaction with organic material
( ii) Phenolics
e. g. dichloroxylenol, benzyl cresol
Advftntages
long time of activity.
Disadvantages
Too toxic and environmentally unacceptable.
( iii) Organometallics
Mainly compounds of copper, tin and mercury.
Advantages
Excellent biocidal activity.
Disadvantages
Toxic, environmentally unacceptable.
( iv) Oxidants
e. g. Hydrogen peroxide
Advantages
Ease of handling, cheap.
Disadvantages
Their strong oxidising potential precludes their
use in many systems.
v) Aldehydes
e.g. Formaldehyde
Glutaraldehyde
r t u P
Quaternary Ammonium Compounds in the Control ofSulphate- reducing Bacteria 161
Advantages
Cheap, long time of activity.
Disadvantages
Toxic
Can have handling problems.
Advantages
Cheap, long time of activity.
Disadvantages
Require careful selection for sea water compatibility.
Readily absorb on surfaces (can also be an advantage).
Foaming.
3. Mechanism of Operation
i) Chlorine
TABLE 1
MIC ppm
Biocide g + g - fungi
-Quaternaries
alkyltrimethylammonium
chloride 5 200 25 -100
alkyldimethylbenzylammonium
chloride 2 50 1-50
heteraoaromaticammonium
chloride 80 150 1500-3000
-Formaline
formaldehyde 30 30 30-1000
formaldehyde release compounds 50 50 1000
-Phenolic compounds
phenolics 1000 1000 300-1000
alkylphenolics 200 3000 5000
chlorinephenolics 4 200 25-150
diphenyl derivatives 100 500 500
-N containing compounds
biguanidines 20 100-250 1000
chlorhexine 3-25 10-25 10-100
triazine
thiocynates 5-60 10-15 4-35
-Halogen compounds
chlorine 1-5 100
chlorine release compounds 100 300 20 -300
iodophors
r t u P
Quaternary Ammonium Compounds in the Control ofSulphate-reducing Bacteria 163
( ii) Aldehydes
Amines
Primary Secondary Tertiary
R1 R3
'-N/
I
R2
Ethoxylated Amines
Cl
r t u P
164 Chemicals in the Oil Industry
Cl
Ethoxylated Quaternaries
Cl
Amine Salts
R'COO
5. Test Methods
Bact~ricidal Activity
TABLE 2
MIC in ppm
Quaternaries
Trimethyltallowammonium chloride I N S 0 L U B L E
Trimethyldecylammonium chloride 800 800
Dimethyld~decylammonium chloride 100-200 100-200
Trimethyldodecylammonium chloride 100-200 100-200
Trimethylcocoammonium chloride 50 50-100
Dimethyldicocoammonium chloride 3200 3200
Dimethylcocobenzylammonium chloride* 400 100-200
200 50-100
(Middle cut)
Dimethyltetradecylbenzylammonium chloride* 400 400
Amines
N,N-dimethyldodecylamine 3200 800-1600
N,N-dimethyltetradecylamine 3200 3200
N,N-dimethylcocoamine 3200 3200
Ethoxylated Amines
bis (2-hydroxyethyl) cocoa~ine 3200 3200
polyoxyethylene (5) cocoamine 3200 3200
Ethoxylated Quaternaries
Methylbis (2hydroxyethyl) cocoammonium 800 200-800
chloride
Methylpolyoxylene(15)cocoammonium chloride 3200 3200
Amine Salts
Cocoamine acetate 3200 400-800
N,N-dimethylcocoamine acetate 400-800 200-800
N-coco-1,3-diaminopropane diacetate 50 50-100
(Q
:;::
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~
~
;:::::
~
~
~
~
~
a
r
;:::::
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TABLE 3 Chain Length Distributions ~
g
~a
:;::
;:::::
~
t
C C C C C C C 18=
8 1D 12 14 16 18
5
So
~
6 19
Trimethylcocoammonium chloride 5 53 9 2 6
g
;:::::
u
Trimethyldodecylammonium chloride - 1 98 1 - - -
~
Dimethyltetradecylbenzylammonium chloride - - 3 94 3 - - ~
~
~
~
P
~
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5
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r t u P
168 Chemicals in the Oil Industry
TABLE 4
SRB
- -
Synergistic Effects
TABLE 5
MIC
SRB 1 SRB 2
Monitoring
REFERENCES
242 (1972).
r t u P
The Role of the Service Company in Offshore Operations
By G. E. Payne
CONOCO (U.K.) LIMITED, RUBISLAW HOUSE, ANDERSON DRIVE, ABERDEEN AB2 4AZ, U.K.
Introduction
Chemical service companies have been involved with the U.K. Offshore
oil industry since the first well was drilled. Drilling muds are
sophisticated blends of chemicals supplied by service companies.
When oil is found and production starts another whole range of
chemicals may be required as outlined in other papers. Some of
the service companies specialise in mud chemicals and some in
production and treating chemicals. A few companies can supply products
for both the drilling and production phases. Yet another group
tend to deal more with maintenance products.
Some cynics might say that all a service company does is to buy
bulk chemicals from the manufacturer and blend them with other materials
which may be only water or cheap solvent and then sell them at a
handsome profit. Whilst this has undoubtedly happened at different
times in different places the offshore oil industry generally requires
such a diverse range of chemicals that this approach is not generally
possible.
The service company must supply chemicals which effectively solve the
problems being encountered. If the existing products are not wholly
suitable new ones need to be developed. Having chosen the chemical
it must then be supplied in a form suitable for shipping to the offshore
installation and for its safe use there. If required chemical service
company personnel must also visit the rig or platform to help ensure
that the chemical does the job that it is supposed to do.
Selection of Chemicals
In some cases an operator may only carry out plant trials. In this
instance generally only a few products will be tested. These may
be from different companies or perhaps only fro@ one company.
Supply Arrangement
Because the volumes o~ fluid being treated are often very large
even modest chemical treatment rates at the part per million level
may mean substantial quantities of chemical are being consumed.
The unit quantities quuted above for liquids at least are too small
in this instance. Many liquid chemicals are now supplied offshore
in intermediate bulk containers which range from about 100 to 500
gallons in size .,-
Even when the service company personnel do not visit the offshore
installation they will generally be expected to give advice pertinent
to the use of their company's products. The type of injection equipment
required including material of construction requirements and the point
of injection into the system illustrate the type of information
required. The level of treatment to be applied to the system will also
need to be given if this has not already been determined.
r t u P
The Role ofthe Service Company in Offshore Operations 175
Monitoring of Effectiven~~
Safety
Many goods may not be classified as dangerous but may still require
special handling in the case of spillage. Some chemicals which are
not dangerous by themselv~s may be potentially hazardous when mixed
with other materials. Such information must be supplied preferably
on the container itself.
Environmental ASPects
Any chemical used offshore will sooner or later find its way into
the sea. This may be deliberate or accidental. Whilst those chemicals
which are deliberately added to overboard discharges must be scrutinised
closest the consequences of accidental discharges of all chemicals
should be known.
In 1979 the Department of Energy introduced a notification scheme
for chemicals used offshore. Service companies were invited on a
voluntary basis'to submit information to the Department of Energy
to enable a category of useage to be allocated to each chemical.
The categories range from 1 to 5 for the different levels of usage
for which notification is requested. category 0 requires no
notification.
Conclusion
By R. C. Parker
SYNOPSIS
A review of the market for chemicals in oil and gas development will be
presented with particular emphasis on types and quantities of chemicals,
reasons for application and future trends.
1. GENERAL
Oil and gas development follows a logical and sequential course of events. In
its broadest terms, an exploration well will be drilled in an unknown area to
prove (or otherwise) the presence of hydrocarbons. Should the well
successfully encounter hydrocarbons, so-called appraisal wells will be
drilled in the immediate vicinity to gain more knowledge of the extent of the
accumulation and the approximate quantity of hydrocarbon present. Thereafter,
should the size of the discovered field prove attractive for development in
the prevailing economic climate, development wells will be drilled according
to an optimised subsurface pattern to efficiently produce and drain the
reservoir. Production facilities will be installed close to the development
wells to process the oil and/or gas and water streams which will be produced
from the reservoir. The oil and/or gas will then be evacuated from the field
by the most appropriate method e.g. pipeline or tanker.
The use of chemicals in oil and gas development can be more specifically
indicated by itemising the numerous activities.
Drilling a well requires the use of a drilling fluid, also known as a "mud".
Significant quantities of commodity and speciality chemicals are used in
formulating drilling fluid systems.
Once a borehole has been drilled, steel pipe known as casing must be cemented
in the hole to prevent borehole collapse and allow drilling to continue to
deeper geological horizons. Correct cementing formulations are critical to
the integrity of the well and necessitate the use of chemical additives.
Primary production of oil, which usually relies upon the natural driving
forces in the reservoir to produce the oil to surface, seldom recovers an
appreciable quantity of the total oil present in the subsurface strata. In a
typical sandstone reservoir, primary recoveries of 30-50% may be obtained,
whilst in limestone reservoirs, recoveries can often vary from 5% to 25%. In
order to maximise recovery of oil, alternative production methods are
required to augment the primary process.
Typical secondary recovery processes are water injection and gas injection.
So called enhanced recovery processes aim to recover oil left behind or not
producible by the natural drive mechanisms or secondary recovery methods. The
enhanced recovery processes may be arbitrarily split into thermal methods and
miscible/chemical methods. Thermal methods encompass hot water injection,
steam injection and in situ combustion. Miscible methods involve the
injection of enriched hydrocarbon gases, or carbon dioxide or nitrogen.
Chemical processes involve the injection of polymers and/or surfactants or
caustic. In all these additional recovery processes, significant quantities
of speciality chemicals are used, especially in chemical/surfactant flooding.
1. ACTIVITY SCENE
for example the North Sea. The operating cost of an offshore drilling rig can
amount to 60,000 per day (40 per minute). The cost of a well itself in such
an area can range from 2 million to 20 million, depending upon the severity
and complexity of the operating and drilling conditions. The cost of
chemicals utilised in drilling and completion operations can typically vary
between 5% and 15% of the total well cost.
2. DRILLING CHEMICALS
The majority of chemicals used in the drilling and completion of a well are
utilised in preparation and maintenance of a suitable drilling fluid or
"mud". In the conventional rotary drilling process, mud is pumped down
through the drillpipe string, out through the bottom of the drilling bit and
circulated back to the surface. The mud circulation system is the heart of
the drilling process and it would be impossible to drill a well without a
suitable drilling fluid. The principal functions of the drilling fluid are as
follows:
i) Transportation of drilled rock cuttings out of the borehole
ii) Maintenance of the stability of the borehole
iii) Prevention of the ingress of oil, gas or water into the borehole during
the drilling process
iv) Provision of lubrication and cooling to the drilling bit.
i) ~~!~~!!~~_~~~~!~
Materials with high specific gravity utilised to provide the required density
of the drilling flGid. Barytes (BaS0 ), iron oxides (haematite, ilmenite),
4
calcium carbonate. Barytes is the most commonly used weighting agent.
ii) ~!~~~~!i!~E~
Materials used mainly to build fluid viscosity. Bentonite clay is the most
commonly used product, together with lesser amounts of other clays e.g.
attapulgite. Polymers are also now being increasingly used e.g. partially
hydrolysed polyacrylamides, cellulose ethers, copolymers of vinyl acetate and
maleic anhydride.
iii) ~!~~E~~~~
Materials which disperse solid particles in the drilling fluid. Examples are
ferrochrome lignosulphonates, chrome-free lignosulphonates, sodium
polyacrylates, phosphates.
iv) ~!~!~_!~~~_~~~!!~~~
Materials which prevent the loss of fluid from the mud to permeable and
porous rock formations. Examples are carboxymethyl cellulose, xanthan gum,
guar gum, polyacrylates, pre-gelatinised starch and lignite.
v) ~~~~~~!~Z_~~~~!~~!~
Appreciable quantities of lime and sodium hydroxide are used for pH
adjustment. Also other chemicals are used to provide correct ionic balance in
the fluid e.g. sodium chloride, potassium chloride, lime and calcium
chloride.
vi) 2~~E_~~~!~!!~Z_~~~~!~~!~
To a limited extent, biocides, corrosion inhibitors, surfactants and
defoamers. Since these chemicals are used more extensively in
production-related problems they will be described in more detail in a later
section.
2.5 Quantities and Costs of Chemicals used in Water Based Drilling Fluids
The mud cost for an average well in the United States is of the order of
15,000 whilst for a deep well (> 15,000 ft) it can accumulate to 300,000.
Approximately 1.5% of the 80,000 wells drilled in the U.S. can be classified
as deep. The total world market value of chemicals used for water based,
drilling chemicals is estimated at around 2500 million per year and an
approximate breakdown would be as follows:
r t u P
184 Chemicals in the Oil Industry
3 6
Category of chemical MT x 10 ( x 10 ) (%)
MT = Metric tons
The mud cost of an average well drilled with water based drilling fluids in
Western Euro~e is estimated at around 100,000. The total market value of the
drilling chemicals used in Western Europe is therefore estimated at
approximately at 24 million, broken down as follows:
6
Category of chemical ( x 10 ) (%)
Oil based drilling fluids are used for special drilling applications. They
consist of either 100% base oil (e.g. diesel or a "non-toxic" oil) or invert
emulsions with water contents up to 30% to 40%. In common with water based
drilling fluids, weighting agents (e.g. barytes) and commodity chemicals
(e.g. sodium chloride, calcium chloride, lime) are used in the preparation of
these systems. Examples of other types of chemicals utilised in the make-up
are as follows:
i) ~E!~~E~_~~~!~!~!~E~
Materials required to emulsify water into the base oil to provide a stable
invert oil emulsion mud. Typical chemicals are polymerised/oxidised tall oil
soaps; animal fatty acids plus alkanol amides; oleyl amide + oleic acid +
dimerised oleic acid; magnesium soaps of fatty acids + tall oil resin + fatty
amides; fatty imidazoline derivatives.
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The Market/or Chemicals in the Oil Industry 185
ii) ~~!!!~~_~~~~!~L~~~~~~~E~_~~~!~!~!~E~
Materials designed to preferentially oil-wet solids introduced in the mud and
provide additional stability to the system. Examples are amide derivitives of
tall oil; long chain fatty amides; oleyl amide lignosulphonate; fatty
diamine; imidazolines and ethoxylated alkyl phenols.
iii) Y!~~~~!~!~E~
Materials required to impart viscosity to the system. The main product used
is an organophilic bentonite.
iv) ~!~!~_!~~~_~~~!!!~~~
Materials which prevent the loss of the continuous phase of the mud (i.e.
oil) to permeable and porous rock formations. Examples are oxidised asphalt;
organophillic lignite or mixtures of polyphenols.
v) Q!~~E_~~~~!~!!!~_~~~~!~~!~
To a limited extent, thinners are used e.g. petroleum sulphonates or
naphthenic acids.
As indicated in section 2.3 the use of oil base drilling muds in the United
States is very limited. In relation to world activity, a significant
proportion of oil base mud application takes place in Western Europe. The mud
cost for an average well using an invert oil emulsion (20% water) is of the
order of 150,000, of which some 30% of the cost may be attributed to the
diesel oil. Hence chemical additive cost per well would be about 110,000,
and the total market value of these drilling chemicals in Western Europe may
be estimated at around 18 million, broken down as follows:
6
Category of Chemical ( x 10 ) (%)
3. CEMENTING CHEMICALS
The cement commonly used is Portland cement with various additives. The
additives modify the properties of the cement to allow acceptable rheology,
setting timea and to match the formation characteristics of the individual
well.
i) ~~!~~!!~~_~~~~!~
These products are usually required when high pressure conditions are
encountered. They are similar additives as those used for drilling fluids
i.e. barytes, iron oxides.
ii) ~~~!_!E~!~!!~~_~~!~E!~~~
Products which prevent the loss of cement slurry to the formation when low
pressure conditions are encountered. Examples are gilsonite and mica.
iii) ~~!~E~!~E~
Products which will accelerate the setting time of the cement in order to
speed up operations. Examples are sodium chloride (up to 5% by weight),
calcium chloride and sodium silicate.
iv) ~~!~E~~E~
Products which will extend the normal cement setting time to render the
slurry pumpable over an extended period. This feature is often required when
placing cement slurries in deep hot wells. Examples are lignin
retarders-calcium lignosulphonate and calcium sodium lignosulphonate;
carboxymethyl hydroxyethyl cellulose (CMHEC) and saturated salt water.
v) ~!~!~_!~~~_~~~!!!~~~
Products to control the loss of water from the slurry to the formation.
Examples are carboxymethyl cellulose (CMC), polyacrylamides and silica flour.
vi) ~!~E~E~~~!~L~E!!!~~_E~~~~E~
Products designed to improve the rheology of the slurry. Examples are
lignosulphonates, lignins, sodium chloride, aryl alkyl sulphonates.
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The Market for Chemicals in the Oil Industry 187
vii) Q!~~E_~~~!!!~~~
Other chemicals such as bentonite, pozzolan (volcanic ash) and latex are used
in varying amounts for specific applications.
The chemical additive market for cementing is appreciably less than that for
drilling fluids. The total world market value of chemicals associated with
cementing operations is estimated at around 300 million. An approximate
breakdown would be as follows:
6
Category of chemical ( x 10 ) (%)
,- Weighting agents/
other additives 90 30
Lost circulation
materials 23 8
Accelerators 44 15
Retarders 46 15
Fluid loss additives 76 25
Dispersants 21 7
In the UK sector of the North Sea an average cost for cementing additives
would be around 12,000 per well. Hence the approximate total market value of
these chemicals in this area is 2~ million, i.e. about 1% of the world
market.
4. COMPLETION/STIMULATION CHEMICALS
Completion of a well often involves the use of clean non-damaging (to the
reservoir rock) fluids. The principal fluids used are brines e.g. sodium or
calcium chloride, calcium bromide and in extreme case zinc bromide. In some
cases, the rock may have been damaged by the drilling process and/or is of
poor quality such that a less than optimum productivity is obtained. In such
circumstances, the well may be stimulated to improve the productivity. The
two principal methods of stimulation are acidising and hydraulic fracturing.
In certain specific instances, stimulation can also be achieved by injection
of solvents, surfactants, enzymes, gas-generating compounds or polymers.
4. 1 Acidising
iii) Fluid loss additives e.g. guar gums, hydroxyethy1 cellulose po1yamines.
These chemicals prevent loss of fluid to the formation and assist in
fracture propagation.
Acidising Chemicals
Acids 190
Corrosion Inhibitors 6
Clay Stabilisers 5
Friction Reducers 5
Others 5
Fracturing chemicals
Viscosifiers 165
Fluid Loss Additives 20
Surfactants 20
Others 20
In the UK sector of the North Sea, the total market value of these chemicals
is estimated to be about 14 million, i.e. about 3% of the US market.
Acidising is useg extensively in the carbonate reservoirs of the Middle East
and that may be expected to contribute a further approximate 50 million
resulting in a world market of around 500 million. Market growth, dependent
on future activity can be expected to be of the order 10-14%.
5. FUTURE TRENDS
Drilling activity is moving towards more hostile environments. The search for
oil and gas is becoming more difficult and new and deeper geological horizons
must be explored. Consequently, new chemicals must be developed to perform
under extremes of temperature, pressure and environment e.g. 400-500F;
25,000 psi and appreciable quantities of H S and CO (10-50%). Increased
2 2
emphasis will be directed towards polymers. The industry trend towards
low-solids fluids requires polymers that do not undergo shear degradation,
have good salt tolerance and filtration control and are stable at
temperatures up to 300F. No single polymer displays all these properties and
blends are currently used. Further work is required on polyacrylamides and
polyacrylates to improve their temperature stability and effective use at
lower dosage rates. A final and most important trend is towards the use of
environmentally acceptable chemicals. Increased environmental awareness and
legislation is having a significant impact on drilling operations and
disposal of chemicals.
5.2 Cementing
In line with the future trends for drilling fluids, cementing chemical
additives will also need to be developed to withstand extremes of temperature
and pressure. A continual problem facing the industry is the prevention of
gas migration through cement columns. As a result many wells are
inefficiently cemented and require costly repair work. Extensive research
work is presently being directed towards this problem.
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190 Chemicals in the Oil Industry
In hydraulic fracturing the trend will be towards new, improved and more
versatile polymers. Both emulsions and foams are increasing in popularity as
fracturing fluids, and extensive work can be anticipated in this direction.
2. PRODUCTION OPERATIONS
ii) Q~!L~~~L~~~~E_~~e~E~~~~
The produced fluids are separated into their three major constituents under
controlled conditions of temperature and pressure. Not all wells produce
water during the early phase of production, but invariably do during the
latter stages. Principal process chemicals used are defoamers and
demulsifiers, fresh water washing (to remove salt).
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The Marketfor Chemicals in the Oil Industry 191
iii) 2!!_~~~~~~~!~~
Crude oil is normally pumped from the separation facility either to a tanker
or pipeline for evacuation. Typical chemicals used in this process, depending
upon the characteristics of the oil, are wax inhibitors, corrosion
inhibitors, and friction reducers.
iv) ~~~_E!~~~~~!~~_~~~_E!~~~~~!~~
Gas which is either produced (natural) or separated from oil (associated) is
normally processed to recover the heavier components, e.g. propanes, butanes
etc., which are often recombined with the oil stream. The gas is then usually
dried prior to being compressed for transmission to shore. Typical chemicals
used are glycols (for drying), hydrate reducers and corrosion inhibitors.
v) ~!~~~~~~_~~~~!
The water whieh is separated from the oil or gas is subject to a degree of
chemical treatment depending upon its final mode of disposal - usually
subsurface re-injection or surface disposal. Typical chemicals used are
corrosion and scale inhibitors, biocides, de-oiling chemicals and
po1ye1ectro1ytes.
i) !~!~~~!~~_~f_~!!f!~!~_~~~!~!~~~
When oil is initially produced from a well, it usually contains associated
gas but only minor amounts of water (less than 0.5%). With time, and
depending on the production characteristics of the reservoir, the "water-cut"
will increase and it is not uncommon for greater than 50% of the produced
fluids to be water within a period of five years. Under such conditions, the
water is generally emulsified in the oil and it is most important that the
oil and water are efficiently separated from one another.
In forming a normal emulsion (water-in-oi1) there are two forces that are
continually in direct opposition. The surface tension of the water permits
the droplets to form larger droplets which when sufficiently large will yield
to the force of gravity and settle out (Stokes Law).
In opposition, the film of emulsifying agents provides a barrier between
drops and tends to prevent the joining of the water droplets.
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192 Chemicals in the Oil Industry
ii) ~~~E~~!~E!~!!~~_~~~_~!~~!!!!I_~~_~!!_~!~!~_~~~!~!~~~
~b.e st..a'o-\..\:\..t..~ Cl~ a1:\. ~~~\.S\.()1:\. ,-a~ \)cc. aii'C.c::..'t.'C.~ ~1 ~a\.\1 \.a~\.~.Yt~, 0.\\ \)\ ~\\\.t.\\
can be classified into a chemical or physical category or both. The natural
materials (emulsifying agents) which stabilise crude oil emulsions are either
surface active agents or finely divided solids, which have a tendency to
absorb at the oil water interface, lower the surface tension and increase
emulsion stability. Typical surfactants present within crude oil are
asphaltenes, aromatic and naphthenic compounds of varying degrees of
complexity. Finely divided solids also present within the crude oil stream
such as clays, silica, carbon black, insoluble asphaltenes and various
insoluble inorganics such as iron oxide, iron sulphide and barium sulphate
all aid emulsion stability. A further point on emulsion stability is that for
normal oilfield emulsions, interfacial tension decreases with increasing
emulsifying agent concentration. Crude oil contains dissolved compounds whose
degree of ionisation depends on the pH of the water phase. When crude oil is
in contact with acid solutions, the nitrogen compounds are ionised, absorbed
at the oil-wa~er interface and lower the interfacial tension. At intermediate
pH values, the asphaltenes, resins, and organic acids and bases only
moderately affect the interfacial tension. To minimise emulsion formation,
the crude oil should not contact either high or low pH water because the
interfacial tension between the oil and water droplets is low at either end
of the pH scale.
iii) ~E~~~_~!!_~~~l~E~!!~~_i~~~!~!~~_~~~!~~!!!~~!!~~2
For effective dehydration, the following sequential steps are required:
destabilisation of the emulsion
coalescence of the destabilised water droplets
separation of the water from the oil phase
Final conclusions on the best demulsifier for a certain emulsion can only be
drawn from a comparison of several promising chemicals in a field test. Such
field trials are usually conducted under supervision of the chemical supplier
on a no-cure, no-pay basis. The ultimate objective is to find a chemical
which, at acceptable cost, effectively separates oil and water at the lowest
possible temperature, yielding dry oil, clean water and a minimum of
interfacial sludge.
Traditionally, the Oil Companies have not become involved in the development
of demulsifiers; this was usually left to the Service Companies.
However, to a certain extent this approach is changing and now some of the
major international Oil Companies are diversifying their interests into this
business. Furthermore, in the face of increased operating costs, Oil
Companies are concentrating their attention on optimising the application
aspects of chemical demulsification in creating favourable conditions for
chemical destabilisation, coalescence, settling and liquid phase separation.
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194 Chemicals in the Oil Industry
During 1981, the cost of demulsifiers in North Sea applications was estimated
at around 3 million (in the United States some 60 million).
Silicones have appeared compatible with most other chemicals added to the
crude and their effect on downstream processes is minimal.
As crude oil containing parraffin wax cools, the wax molecules begin to
precipitate and build up a crystalline matrix. The wax crystal is both
hydrophobic and oleophobic and in practical terms this means that the crystal
does not go with either the water or the oil phase. Thus it preferentially
precipitates from solution, adhering to exposed surfaces, for instance pipe
walls.
In a West African oil field, where wax deposition in down-hole tubing and
flowlines necessitated frequent scraping and pigging, application of this
copolymer dramatically reduced clean-out frequencies. This was achieved at
additive concentrations of 100-200 ppm, injected down-hole with the lift gas.
Similar experience has been reported from some Canadian oil fields.
Nett savings reported have been modest, of the order of one penny per barrel
of crude treated. The reason is that - compared with other additives -
comparatively high concentrations of chemical have to be applied;
furthermore, conventional mechanical treatments are in general not very
costly. Most benefit .~ derived from the fact that the chemical treatment -
contrary to mechanical treatment - renders continuous production possible;
therefore, in many cases the major pay-out for chemical treatment is in fact
derived from the elimination of deferred production of crude oil.
The use of these compounds is to improve the pumpability of waxy crude oils
which are subjected to low temperatures. Their principal application is to
reduce the viscosities and gels under such conditions.
When waxy crude oil is cooled off paraffin wax crystallises; this causes a
change in the structure of the crude resulting in viscosity increases and
subsequent increased pumping and flowline pressures. Fluidity improvement is
needed.
These oils also exhibit a yield value. When the crude sits still at a
critical temperature, it sets up. When pressure is applied, a greater amount
of energy is needed to start the fluid flowing than is necessary to maintain
a constant pumping rate. Restartability improvement is needed in this case.
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196 Chemicals in the Oil Industry
Crystal modifiers are used as fluidity and restartability improving
additives. These additives are chemically similar to the compounds used to
prevent wax deposition.
The use of fluidity additives permits waxy crudes to be produced and pumped
over long distances without applying diluents or heat, while the use of
restartability additives permits line shutdown and static cooling of waxy
crude. Depending on the type of crude, additive concentrations of 100 to 200
ppm are usually sufficient to achieve the required results.
In one case waxy crude pumped through a 170 mile pipeline can be kept fluid
at temperatures ranging between 50 and 60F by doping with 150 ppm of a
copolymer of alkylacrylate.
The only extensive practical use of drag reducers has been with aqueous
systems. In the oil industry these compounds have been used in hydraulic
fracturing treatments. Water soluble polymers such as guar gum or high
molecular weight carboxymethyl cellulose have been effective in reducing
horsepower requirements and/or increasing injection rates during treatments.
The state of the art of drag reduction in oil pipelines is just beyond the
experimental stage because it was difficult to find suitable materials able
to reduce drag in aliphatic hydrocarbons.
Long chain polymers of high (one to ten million) molecular weight, such as
synthetic rubber compounds, have been found effective drag reducers for crude
oil. An almost unsurmountable problem appeared to be the shear degradability
of these compounds; the effect of high-shear conditions encountered in
centrifugal pumps causes a degradation of the long-chain polymers whereby
less effective, short-chain compounds are formed. A solution was found by
adding these chemicals in solid form. This allows the chemical to dissolve
slowly, producing drag reduction as it moves through the line. At the same
time, useful polymer in the form of undissolved solids passes undegraded
through the pump stations and continues to dissolve down-stream of the pump.
Deoiling of produced water is usually carried out with the help of equipment
operating on the principles of gravity (skim tank, API separator, Corrugated
Plate Interceptor or Tilted Corrugated Plate Interceptor) or gas flotation.
In some cases, where very low oil contents are required (e.g. for
re-injection, the generation of steam), the gas flotation stage is followed
by either filtration or a combined treatment of flocculation and filtration.
For oil removal by gas flotation often other chemicals, so called flocculants,
are used. Their task is to increase the size of the oil droplets by
flocculation. Mostly organic flocculants are used for gas flotation; they are
polyelectrolytes, which have cationic, anionic or non-ionic functional
groups. Inorganic flocculants have been found unsuitable, because they make
the floc heavy and are detrimental when returned with the oily froth to the
oil treating system.
Gas hydrates are solid compounds formed by the reaction of gas with water.
They resemble snow in appearance and form as crystals. When formed in well
tubulars, pipelines and gathering systems gas hydrates cause partial or
complete blocking, reducing or stopping gas flow ("Line freezing").
Methane Hydrate CH 7 H 0
4 2
Ethane Hydrat~ C H S H 0
2 6 2
Propane Hydrate C H IS H 0
3 S 2
Also CO and H S form hydrates.
2 2
The temperature at which hydrates form increases with pressure and gas
density. For instance, methane hydrate can be formed at 40F and 500 psi.
When the pressure is increased to 2000 psi, the temperature critical for the
formation of hydrate increases to 60F.
Dehydration
Chemical additives
Heating
Free water is necessary for the formation of hydrates. If the water dew point
of the gas is lower than its temperature, no hydrates are formed.
The chemical additives used depress the hydrate temperature of gas. Although
ammonia, sodium chloride or calcium chloride have been used, one of the more
widely used chemicals for this purpose is methyl alcohol. It is more
effective than ethyl or isopropyl alcohol, and is also the least expensive.
Alcohol is not readily reclaimed from an aqueous solution, so its use is
restricted to applications where it is expendable. The amount of alcohol
required for any specific condition is usually calculated. A general practice
is to inject alcohol into a flowline near the well head. This eliminates the
need for a header and permits the total production to be transported to a
central facility where the free liquids can be removed and the gas processed.
Gas produced offshore is treated with alcohol before transportation by
pipeline to an onshore facility.
Glycol has also been used and has the advantage that it can be recovered from
an aqueous solution by boiling off the water. The regenerated glycol is then
returned to the injection point. Ethylene glycol is the preferred glycol.
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The Market/or Chemicals in the Oil Industry 199
Typical production speciality chemicals, over and above those outlined in the
foregoing sections are corrosion inhibitors, scale inhibitors and biocides.
Oil Environment
The type of corrosion which can take place in oil wells, pipelines and
facilities is usually sweet (C0 ) or sour (H S); oxygen corrosion seldom
2 2
occurs. No corrosion takes place when dry oil is produced or handled; as
ionic reactions between CO or H S are the cause of metal corrosion, the
2
presence of water in the system 2~s essential for these reactions.
The corrosion inhibitors used for this application are usually the surface
active - adsorptive type, the so called film formers. Almost 90 percent of
the inhibitors in successful use today are either based on the long chain
aliphatic diamines or on long carbon chain imidazolines. Various
modifications have been made of these structures to change the physical
properties of the material. For example, ethylene oxide is commonly reacted
with these compounds in various molecular percentages to give polyoxyethylene
derivatives that have varying degrees of brine dispersibility. Many
carboxylic acids are used to make salts of these amines or imidazolines.
Water Environment
In produced water systems corrosion can be caused by dissolved oxygen, carbon
dioxide, hydrogen sulphide or bacteria. Dissolved salts, the pH, the
temperature and the water velocity in the system strongly affect the rate of
corrosion. Depending on the final destination of the produced water, a
decision should be made whether measures have to be taken to prevent
corrosion or not. If so, several methods can be applied, including removal of
the corrosive gases, using corrosion resistant material or applying corrosion
inhibitors. A combination of one or more methods is also practised.
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200 Chemicals in the Oil Industry
When oxygen is the cause of corrosion in a given system then, in most cases,
oxygen will be removed or corrosion resistant materials will be used. This is
because there are hardly any suitable compounds available. The classic
passivating inhibitors such as chromates or nitrites, or inorganic barrier
formers such as zinc salt phosphate combinations or the silicates, are ruled
out for once-through systems because very high concentrations are required
particularly in the presence of a significant chloride content. Combinations
of amino methylene phosphate and zinc salts have been successfully used in
circulating water systems and proved more effective than the inorganic
phosphate-zinc salt combination. Recently an organic sulphophosphate was
introduced which shows promising results as an oxygen corrosion inhibitor.
When HZS and/or COZ cause corrosioq in a given system, barrier forming or
"filming" inhibitors will be used. Because oil is usually absent or only
present in low concentrations, these inhibitors should be water soluble, i.e.
the balance between the hydrophobic hydrocarbon chain and the polar portion
of the inhibitor molecule should be changed in favour of the latter. However,
as the inhibitor film stability is determined by the interplay of a number of
factors involving both the hydrophobic and hydrophylic portions of the
molecule, a delicate balance has to be attained because changes in the
molecule that promote water solubility tend to decrease film stability. This
conflict between solubility and film stability has been one of the basic
obstacles to be overcome in formulating an effective water soluble inhibitor.
After transformation into the final product, the resulting ingredients are
usually dissolved in an alcohol-water solution. Actual inhibitor content
ranges from ZO to as much as 65-70%, depending on the solubility of the
compound. Often, more than one type of inhibitor molecule will be used.
Gas Environment
---------------
Corrosion in gas production wells and surface system is usually caused by
COZ' HZS or a combination of these two acid gases. Protection of off-the-
shelf carbon steel is needed when the partial pressure of CO 2 in the system
exceeds 7 psi and that of H S exceeds 0.05 psi*). In the latEer case stress
corrosion cracking occurs. tn all cases the presence of condensated water is
required to have any corrosion at all.
The corrosion inhibitors used resemble those applied in oil wells; they are
film-forming and adsorb onto metal surfaces. They create a hydrophobic layer
that prevents the corrosive gases from contacting the metal surface
intimately enough to allow chemical reactions to proceed.
To keep the inhibition system manageable, the viscosity had to be low enough
to be pumped in cold weather.
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202 Chemicals in the Oil Industry
The ability to separate water from the inhibitor system is important. This
water is picked up from the water-saturated sour gas system at a rate of
6-8 barrels per million cu ft gas produced. A low vapour pressure of the
system is an economic necessity, because carrier oil and inhibitors are both
expensive. It is an obvious prerequisite that the inhibitor system is
non-scaling or non-fouling; it reduces well production and inhibitor
circulation and necessitates expensive work-overs.
4.3 Biocides
The problems caused by SRB are therefore associated with the generation of
H S and CO and the removal of hydrogen from an aqueous system.
2 2
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204 Chemicals in the Oil Industry
SRB are often insensitive to chlorine and more potent biocides such as
quaternary ammonium compounds, aldehydes or a mixture of these compounds are
required. Shock treatments are given; weekly or twice weekly 3-6 hour, 50-100
ppm slugs of biocide are added. Every 2-3 months the biocide is changed to
eliminate the possibility of the SRB becoming immune to treatment.
Demulsifiers 135
Corrosion Inhibitors 85
Surfactants 15
Biocides 10
Scale Inhibitors 35
Wax Inhibitors 10
Others 10
300
Primary recovery of oil and gas generally relies on the natural drive energy
(usually pressure) within the reservoir. Typical recoveries (as a percentage
of original oil in place) vary, among other parameters, on the nature of the
crude oil. For example, heavy and viscous crudes may yield only 1-5% whilst
light crudes can yield from 10-40%. Secondary recovery processes such as
water injection and gas injection are often utilised to recover additional
oil. Enhanced oil recovery is the description applied by the oil industry to
non-conventional techniques for getting more oil out of subsurface reservoirs
than is possible by primary or secondary recovery processes. The oil not
producible, or left behind, by these conventional recovery methods may be too
viscous or too difficult to displace. It may also be trapped by capillary
forces in the flooded parts of the reservoir, or by-passed by the injected
water or gas. In general, the aim of enhanced oil recovery techniques is to
recover more oil by improving the displacement efficiency. Enhanced oil
recovery techniques are conveniently subdivided into various categories, i.e.
miscible, chemical and thermal processes.
Over the years it has been established that maintaining reservoir pressure
can yield more oil than can be obtained by primary recovery alone. By such
techniques, the reservoirs natural energy and displacing mechani~m, which are
responsible for primary recover~ are supplemented by the injection of water
or gas.
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206 Chemicals in the Oil Industry
In the case of water injection, over 90% of the North Sea fields have on
their platforms a seawater injection facility, capable of producing
sufficient treated water to replace the extracted oil and gas volumetrically.
Typical chemicals used in water treatment are biocides (sodium hypochlorite,
glutaraldehydes etc.), scale inhibitors, corrosion inhibitors and oxygen
scavengers (sodium bisulphite, ammonium bisulphite) most of these chemicals
have already been mentioned in the foregoing sections.
Little or no chemical treatment is required for gas injection, since the gas
is usually dried and compressed prior to re-injection.
3.1 General
Although each_EaR method (chemical, miscible or thermal) has its own range of
application, 'these methods are to a large extent complementary and thus
together cover a wide range of reservoir conditions.
Most successful so far have been thermal recovery methods, particularly those
employing steam. For many years steam drive and steam soak have been applied
on a large scale in e.g. Venezuela, the USA and the Netherlands. Obvious
targets for the application of thermal recovery are the large heavy oil
accumulations in Venezuela.
The long-term future for enhanced oil recovery is promising, but it is not
expected to contribute significantly on a world scale before the end of the
century. Even that will require a considerable further technical and
financial effort.
The purpose of these methods is primarily to reduce the oil viscosity and
thereby improve the sweep efficiency for heavy oil (specific gravity 0.95 to
1.01 at 60F).
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The Market/or Chemicals in the Oil Industry 207
Steam Drive
Because-of tts relatively low density and viscosity, steam tends to by-pass
the oil along the top of the reservoir. This negative effect is, however,
more than compensated by several positive aspects:
ii) the relatively high pressure gradient in the steam zone due to the
high velocity of the condensing steam
iv) low residual oil saturation in the steam zone due to (partial)
vaporisation
As a result, steam drive has been a very effective recovery method for
heavy-oil reservoirs, and has found wide application during the last few
decades.
Steam Soak
This process,-also referred to as "cyclic steam injection", "steam
stimulation" or "huff and puff", was developed in the late 1950s for the
heavy-oil fields on the Bolivar Coast in Venezuela. Steam soak is
essentially a stimulation method which will activate natural drive mechanisms
(rock compaction, solution gas drive, gravity segregation) which are dormant
under "cold" conditions. It is also applied in combination with steam drive.
ii) the effective redistribution of heat around the well bore due to
the fact that steam overruns the oil and thus forms a thin steam
zone on top of the oil
iii) storage of a large fraction of the heat injected in the rock, which
acts as an effective heat exchanger slowing down shrinkage of the
hot zone around the well bore during the production phase.
!!o!. ~a!.e.!:.i.nie~ti.0E.
Although less effective, both as a heat carrier and as a displacement fluid,
hot water may find application in reservoirs where pressures are too high for
steam injection. At very high temperatures (around 350C) hot water may act
as a solvent for oil and thus bring about a reduction of the residual oil
saturation.
In-situ combustion
Two pri~cipal-techniq~es have been tested, both in the laboratory and in the
field - forward and reversed combustion. In forward combustion, the
combustion front moves in the same direction as the injected air, whereas in
the reversed combustion process, it moves in the opposite direction. Forward
combustion is now generally preferred to reversed combustion.
On the other hand, of course, energy is needed for compression of the air to
be injected. There are no heat losses in injection wells. Furthermore, by
injecting water together with the air, the process can, in principle, be
turned into an in situ steam generation process.
f.h~m..!:c~~ ~t..!:l..!:s~d_i~.!..h~r~al.E.r~c~s~e~
In steam projects, water treatment chemicals (inhibitors, softeners, oxygen
scavengers) are used extensively to render the source water suitable for
boiler feed water for steam generation. On the processing side, steam-
affected crude is notoriously difficult to dehydrate and requires specialist
expertise and chemicals for both demulsification and de-oiling of the produced
water. Furthermore, thermally affected crude often generates significant
quantities of H2 S and CO 2 which require appropriate inhibition chemicals.
Processes of this kind, based on the injection into the oil reservoir of a
suitable solvent or gas, have been studied since the early 1920s, and in
theory they can recover all the hydrocarbons left behind by conventional
recovery methods. But, since the miscible drive fluid is often more mobile
and less dense, it tends to by-pass the oil by over-running it or fingering
through it, thus leading to low displacement efficiency.
Hydrocarbon solvents
Any s;l;e~t-miscibl~ ;ith oil (for example, LPG, kerosine or gasoline) can be
injected into a reservoir. But, since the cost of such refined products is
high, the miscible fluid is not injected continuously but in the form of a
slug - typically 10 to 20 per cent of the reservoir pore volume - followed by
a gas or water drive. This technique is effective at low pressure and
temperatures. Nevertheless, the cost of these solvents will usually be
prohibitive.
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The Market/or Chemicals in the Oil Industry 209
!!.Y.Q.r~c~rE..0~.&a~
A lean gas is miscible with the crude at high reservoir pressures. In the
case of developed miscibility, the injected gas contacts the oil, and the
intermediate hydrocarbon components evaporate from the oil into the gas. At
the displacing front a rich gas mixture develops, and this may become
miscible with the oil. By, adding intermediate components (C3-CS) miscibility
is achieved at lower pressures. Because of its high value natural gas
injection is usually justified only as a combined EOR/gas conservation
project.
Carbon dioxide
The minim~m-miscibility pressure for CO 2 varies, depending on temperature and
purity. In addition to miscibility CO 2 injection has several other
favourable effects, such as swelling and viscosity reduction of the oil and
reduction of the gas-oil interfacial tension. It also dissolves to a
significant extent in the water and lowers the pH, which may effect
wettability.
Nitrogen
Increas~d-i~terest in the use of nitrogen developed when it became cheaper to
manufacture and inject this inert gas than a hydrocarbon gas. At first,
waste gases such as stack gas, flue gas and exhaust gas were considered and
field tested. But the problem with these is that they contain waste products
such as nitrogen oxides and sulphur oxides which give rise to corrosion and
pollution problems. Later, attention turned to producing nitrogen
cryogenically.
Although nitrogen is not miscible with the reservoir oil at low pressures, it
can develop miscibility at sufficiently high pressures. Its application is
not, however, limited to miscible recovery pressures; in view of its
unlimited supply it can be used to replace non-miscible hydrocarbon gas
injection in secondary recovery projects, or as a drive fluid for more
expensive miscible slugs.
The increased viscosity of the displacing fluid resulting from the addition
of polymer leads to more efficient displacement of the oil but reduces the
fluid's injectivity. Depending on oil viscosity, a polymer flood project
could double the recovery obtainable with a conventional water drive. With
the high cost of polymers and reduced injectivity, however, there is a limit
to the maximum concentration that can be used. For all practical purposes
the application of this technique is restricted to reservoirs containing oil
with viscosities in the range 10 to 100 cP at temperatures below 80C.
Surfactant flooding
This process,-llke ;iscfble drive, aims at producing the residual oil left
behind by water drive by reducing the oil-water interfacial tension. The
surfactant solution is followed up by a polymer slug (for stability) and,
finally, by water.
Caustic flooding
Caustfc-floodfng(dflute solutions of sodium hydroxide or sodium
orthosilicate) is based on the principle that the organic acids naturally
present (e.g. naphthenic) in some oils can react with the alkali in a caustic
solution. This reaction leads to the in situ formation of surfactants and
emulsification at the oil/water interface. The result is a decrease in
interfacial tension between the oil and the water, comparable to that brought
about by surfactant flooding.
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The Market/or Chemicals in the Oil Industry 211
The caustic solution reacts not only with the oil but also with the reservoir
rock and brine. ConsequentlYt it is rapidly depleted t and it is this effect
that complicates the design and control of caustic flooding projects. More
laboratory and field testing will have to be done before this method t which
is promising in principle t can be implemented on a large scale.
R.l~g.B.iE.g_oif_tE.i~f_z~n~s
The target of miscible and surfactant drives is the residual oil in the
water-swept part of (primarily) light oil reservoirs. In addition t a large
volume of oil is left behind in the non-swept part of the reservoir.
Recovery rif this oil would require in-depth plugging of the swept zones or
areas without t however t damaging the remaining, oil-saturated parts.
Obviously, this is one of the most delicate problems to be solved in recovery
process research. ,No satisfactory solution has been offered as yet t but in
view of the large possible rewards a continued research effort in this area
seems fully justified.
Steam plays a predominant role, with more than two-thirds of the projects and
of the total EOR production. Most of the activity is in the USA, Venezuela
and the Netherlands. Steam injection is likely to continue its relatively
rapid expansion, in view of the very large scope for further application in
the various heavy oil provinces of the world.
The other EOR methods together show a very slow growth in activity, without,
however, a corresponding increase in oil production. These processes still
suffer from technical problems and/or high costs. There are, however, a
number of large-scale gas injection projects in operation and others planned
in the North Sea, Middle East, Africa, the USA and Canada. There are also
encouraging signs for carbon dioxIde and polymer injection, which have both
seen a relatively rapid growth in recent years.
Nitrogen injection is a newcomer, but shows promise for one or more large
North Sea reservoirs.
The scope for EOR world-wide is large: perhaps an additional 400 billion
barrels recoverable from conventional reservoirs and an additional
300 billion barrels from "tar-sands". However, even under the most
favourable crude price scenario, the build-up of enhanced oil recovery
potential will be severely constrained by long lead times and by the heavy
technical and financial effort required.
The size and concentration of the surfactant slug depends on the expected
loss of surfactant in the formation due to absorption on rock and the
interaction with reservoir fluids. Thus the amount of surfactant needed is
primarily determined by relevant formation properties, irrespective of the
amount of residual oil present. The concentration of the polymer slug is
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The Market/or Chemicals in the Oi/Industry 213
In the following table the chemical requirements per barrel oil additionally
produced used for the surfactant and polymer flood are presented. These
figures serve as bases for cost estimates and the estimated future
requirements of polymers and surfactants.
Polymer flooding
Polymers 500 - 1,500 1.5 - 3.0
Surfactant flooding
Surfactant 40,000 - 60,000 12 - 24
Polymers 500 - 1,500
As an example of unit costs for chemical flooding, with a world oil price of
US $35/barrel, the total cost per barrel of oil produced by a surfactant
flood could be US $15-35, while the cost of a barrel produced by a polymer
flood could be US $15-25.
To put these cost figures in perspective, they are compared with those of
alternative energy sources in Table 2.
Coal 3 - 15
Conventional oil 1 - 15
Liquid Gas 10 - 23
Liquid from heavy oil/tar 15 - 25
Liquids from shales 15 - 35
Liquids from coal 30 -+40
Biomass for fuel 30+
Solar hot water 50
On the long term the potential of chemical flooding cannot be neglected. For
some 30% of the medium and light oil found so far, chemical flooding is
considered to be the only possibility to increase the ultimate recovery,
above what can be obtained by conventional proven processes (i.e. water or
gas injection). Hence, it appears reasonable to assume that by the year
2000 chemical flooding will claim its appropriate share of the total EOR
production.
5. Future Trends
From the performance point of view, there is an evident demand for novel and
improved polymers, which can be tailored to meet specific field conditions.
So far no polymer has been obtained which possesses all the properties
required (see Table 3). Biopolymers appear to be highly effective
viscosifiers, with low salt and shear sensitivity and generally favourable
filterability. The present polymer types, however, are relatively
temperature sensitive, not very storage stable and rather costly. Hydrolysed
polyacrylamides have excellent water solubility and good storage stability
and low temperature sensitivity. They are, however, shear and salt-sensitive
and some exhibit filterability defects. Their viscosifying power under
reservoir conditions is probably restricted.
Service companies are presently looking into the possibility of using on-site
polymerisation techniques with the objective to reduce transportation costs
and allow complete tailoring of the polymer to the reservoir.
In the longer term, certain oil companies are looking at microbes to generate
polymers in situ.
v. CONCLUSIONS
The world market for chemicals in the oil industry is presently estimated at
around 3750 million. Market growth rate will depend to a major extent on the
world demand for hydrocarbons; however a value of at least 10% per annum may
be foreseen. Significant potential lies in the development of new polymeric
chemicals which are multi-functional, cost effective and stable at extremes
of temperature and pressure. There will be an increasing trend towards
expansion of chemical recovery methods for oil but economic techniques are
not expected to be fully developed until the next decade.
A final point of emphasis is that the world market for chemicals in oil and
gas exploration and production is highly diversified, specialised and
application invariably necessitates dedicated service back-up and operational
expertise. As such, it is a highly competitive and well established business
and great care should be exercised if considering market participation,
especially since the success or otherwise of participation may often depend
on the now very unpredictable value of a barrel of oil at any particular
moment in time.
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The Market for Chemicals in the Oil Industry 215
TABLE 3
COMPARATIVE PROPERTIES OF POLYMERS
AND THE IR AQUEOUS SOLUTIONS EVALUATED FOR EOR
Ease of disso- Both hydration and High shear mix- Hydration takes
lution gel dispers ion ing required to a long time. Ge 1
proceed rapidly. disperse (dis- can be dispersed
'ro avoid mechanical integrate) gel. at low shear.
degradation low
shear mixing should
be applied.
17. "\Alinning More Oil, Increasing Importance for Enhanced Oil Recovery"
R. Dafter, 1981, Financial Times Business Information Ltd, London