U.S. patent application number 13/446639 was filed with the patent office on 2013-04-25 for method for reducing the viscosity of viscous fluids.
This patent application is currently assigned to Oilflow Solutions Holdings Limited. The applicant listed for this patent is Michael John Crabtree, Nicholas John Crowther, Donald Eagland, Philip Fletcher. Invention is credited to Michael John Crabtree, Nicholas John Crowther, Donald Eagland, Philip Fletcher.
Application Number | 20130102816 13/446639 |
Document ID | / |
Family ID | 34525040 |
Filed Date | 2013-04-25 |
United States Patent
Application |
20130102816 |
Kind Code |
A1 |
Fletcher; Philip ; et
al. |
April 25, 2013 |
METHOD FOR REDUCING THE VISCOSITY OF VISCOUS FLUIDS
Abstract
A viscous fluid, such as heavy crude oil which is too viscous to
enable it to be pumped from a flowing phase of a reservoir into and
along a pipeline for delivery to a refinery or other storage
facility, may be contacted with a formulation to reduce its
viscosity. The formulation comprises a polymeric material AA which
includes --O-- moieties pendent from a polymeric backbone thereof
and said material is optionally cross-linked. In one embodiment,
the formulation may comprise polyvinyl alcohol. In an alternative
embodiment, the formulation may comprise a cross-linked polymeric
material, such as cross-linked polyvinyl alcohol. After the viscous
composition has been transported to a desired location, it may be
separated from the other components.
Inventors: |
Fletcher; Philip;
(Cambridgeshire, GB) ; Crabtree; Michael John;
(Tyne & Wear, GB) ; Eagland; Donald; (West
Yorkshire, GB) ; Crowther; Nicholas John; (West
Yorkshire, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Fletcher; Philip
Crabtree; Michael John
Eagland; Donald
Crowther; Nicholas John |
Cambridgeshire
Tyne & Wear
West Yorkshire
West Yorkshire |
|
GB
GB
GB
GB |
|
|
Assignee: |
Oilflow Solutions Holdings
Limited
Lancashire
GB
|
Family ID: |
34525040 |
Appl. No.: |
13/446639 |
Filed: |
April 13, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12801142 |
May 25, 2010 |
8178586 |
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13446639 |
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10574232 |
Jul 13, 2006 |
7745500 |
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PCT/GB2004/004083 |
Sep 27, 2004 |
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12801142 |
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Current U.S.
Class: |
585/3 ;
137/561R |
Current CPC
Class: |
C10N 2020/091 20200501;
C10M 145/40 20130101; Y10T 137/8593 20150401; C10M 161/00 20130101;
C10N 2030/02 20130101; C10M 145/08 20130101; C10M 2209/04 20130101;
C10M 2209/12 20130101; Y02E 60/34 20130101; C10M 145/04 20130101;
C09K 8/86 20130101; C10M 2209/10 20130101; F17D 1/17 20130101; C10N
2020/00 20130101; C10M 2201/02 20130101; C10M 2209/062 20130101;
C10M 177/00 20130101; C09K 8/588 20130101; C10L 10/08 20130101 |
Class at
Publication: |
585/3 ;
137/561.R |
International
Class: |
C10L 10/08 20060101
C10L010/08 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 2, 2003 |
GB |
0323067.9 |
Feb 24, 2004 |
GB |
0404051.5 |
Claims
1-61. (canceled)
62. A method for reducing the viscosity of a viscous composition
which is arranged to flow along a fluid flow path, said method
comprising contacting the viscous composition with a treatment
fluid formulation, said treatment fluid formulation comprising a
polymeric material AA which includes --O-- moieties pendent from a
polymeric backbone thereof, wherein polymeric material AA is an
optionally cross-linked polysaccharide.
63. A method according to claim 62, wherein the viscosity of the
viscous composition after contact with the treatment fluid
formulation is less than 300 cP measured at 25.degree. C. and 1000
s.sup.-1.
64. A method according to claim 62, wherein the viscous
composition, after contact with the treatment fluid formulation,
exhibits shear thinning.
65. A method according to claim 62, wherein said viscous
composition is an oil.
66. A method according to claim 62, wherein said treatment fluid
formulation is initially contacted with said viscous composition at
or downstream of a production means.
67. A method according to claim 62, wherein said treatment fluid
formulation is initially contacted with said viscous composition
below ground.
68. A method according to claim 62, wherein said fluid flow path is
defined, in part, by a conduit which extends upwardly from below
ground to above ground.
69. A method according to claim 62, wherein said treatment fluid
formulation is arranged to disperse and/or emulsify said viscous
composition on contact therewith.
70. A method according to claim 62, wherein flow is turbulent at
the point of initial contact of said viscous composition with said
treatment fluid formulation so that said composition is dispersed
and/or emulsified on contact with said formulation.
71. A method according to claim 62, wherein the amount of water in
the composition in said fluid flow path immediately after contact
between said viscous composition and said treatment fluid
formulation is less than 70 wt %.
72. A method according to claim 62, wherein said treatment fluid
formulation has a viscosity at 25.degree. C. and 1000 s.sup.-1 of
greater than 1 cP and not greater than 50 cP.
73. A method according to claim 62, wherein said treatment fluid
formulation includes at least 70 wt % water.
74. A method according to claim 62, wherein said treatment fluid
formulation includes at least 0.2 wt % and less than 10 wt % of
said polymeric material AA.
75. A method according to claim 62, wherein said treatment fluid
formulation includes 94.5 to 99.6 wt % water and 0.4 to 5.5 wt % of
said polymeric material AA; and the ratio of the wt % of said
treatment fluid formulation to the wt % of said viscous composition
contacted in the method is in the range 0.4 to 0.9.
76. A method according to claim 62, wherein said polymeric material
AA is wholly soluble in water at 25.degree. C.
77. A method according to claim 62, wherein said polymeric material
AA includes, on average, at least 10 --O-- moieties pendent from
the polymeric backbone thereof.
78. A method according to claim 62, wherein the free bond to the
oxygen atom in the --O-- moiety pendent from the polymeric backbone
of polymeric material AA is bonded to a group R.sup.10 which
comprises fewer than 10 carbon atoms and only includes atoms
selected from carbon, hydrogen and oxygen atoms.
79. A method according to claim 62, wherein said polymeric material
AA includes a multiplicity of hydroxyl groups pendant from said
polymeric backbone.
80. A method according to claim 62, wherein said polymeric material
AA is not cross-linked.
81. A method according to claim 62, wherein after the viscous
composition has been delivered to a desired location the viscous
composition is caused to separate from other components of the
treatment fluid formulation.
82. A method according to claim 81, wherein separation is achieved
by reducing mixing or turbulent movement of the mixture and
allowing the viscous composition to settle out from the water and
optionally cross-linked polymeric material AA.
83. A method of reducing the viscosity of an oil which is arranged
to flow along a fluid flow path, said method comprising contacting
the viscous composition with a treatment fluid formulation, wherein
said treatment fluid formulation includes a polymeric material
which is an optionally cross-linked polysaccharide which: (a)
associates with said oil in order to enable droplets of said oil to
be formed and/or stabilised; and/or (b) forms a coating around
droplets of said oil; and/or (c) forms a hydrogel which is able to
stabilise droplets of said oil.
84. A fluid flow path positioned at or downstream of a producing
face of a subterranean formation, wherein said flow path contains a
fluid comprising petroleum, water and a polysaccharide.
Description
[0001] This invention relates to viscous fluids and particularly,
although not exclusively, relates to the reduction of the viscosity
of viscous fluids to facilitate their flow between two locations.
Preferred embodiments relate to the reduction of the viscosity of
viscous petroleum to facilitate its transport between a place where
it is produced and a point downstream thereof.
[0002] There are many known petroleum-containing formations from
which very little petroleum can be obtained by normal production
techniques because the petroleum viscosity is so high that the
petroleum will not flow at formation conditions even if a
substantial pressure differential, either natural or artificially
induced as by injecting water or other fluids into the formation,
is applied to the petroleum. These petroleum formations are
sometimes referred to as heavy oil formations, and for the purpose
of this disclosure, by heavy oil or viscous petroleum it is meant
crude petroleum having an API gravity less than about 25.degree.
API at 75.degree. F.
[0003] Various techniques have been disclosed for stimulating the
recovery of viscous petroleum or heavy oil and facilitating its
transport along pipelines from a production facility to a refinery.
However, there still exists a problem, especially where the
petroleum is extremely viscous such as that found in heavy oil
reservoirs or tar sand deposits.
[0004] It is an object of the present invention to address problems
associated with the flow and/or transport of viscous fluids.
[0005] According to a first aspect of the invention, there is
provided'a method of reducing the viscosity of a viscous
composition which is arranged to flow along a fluid flow path, said
method comprising contacting the viscous composition with a
treatment fluid formulation, said treatment fluid formulation
comprising a polymeric material AA which includes --O-- moieties
pendent from a polymeric backbone thereof, wherein polymeric
material AA is optionally cross-linked.
[0006] The ratio of the viscosity of the viscous composition
immediately prior to contact with the treatment fluid formulation
to the viscosity after contact with the treatment fluid formulation
is preferably at least 1.2, more preferably at least 1.5.
[0007] The viscosity of the viscous composition after contact with
the treatment fluid formulation is preferably less than 300 cP,
more preferably less than 200 cP, especially less than 100 cP
measured at 25.degree. C. and 1000 s.sup.-1 more preferably when
measured at 100 s.sup.-1.
[0008] The viscosity of the viscous composition after contact with
the treatment fluid formulation is preferably less than 4000 cP for
all shear rates in the range 20-1000 s.sup.-1.
[0009] The viscous composition after contact with the treatment
fluid formulation preferably exhibits shear thinning--i.e. the
viscosity preferably falls as the shear rate increases. This may
advantageously improve the mobility of the viscous composition.
Said viscous composition may exhibit shear thinning as aforesaid at
least over the shear rate range 0.1 to 100 s.sup.-1. The shear
thinning property may facilitate the re-commencement of flow of the
viscous composition after flow in the fluid path has been stopped,
for any reason. Advantageously, even if the viscous composition
separates from parts of the treatment fluid formulation, for
example during suspension of flow along the fluid flow path, on
commencement of flow, the viscous composition and treatment fluid
formulation may again become intimately mixed and the viscosity may
be reduced as described.
[0010] The method may be used to reduce the viscosity of many types
of viscous compositions provided that the viscous compositions can
be caused to form a dispersion when contacted with said treatment
fluid formulation. Said viscous composition is preferably organic.
It is preferably a viscous fluid. It is preferably an oil. It
preferably comprises petroleum. It preferably comprises a viscous
petroleum.
[0011] Said viscous composition may be derived from a heavy oil
reservoir and/or from tar sand deposits. It may be derived from a
deep well wherein the composition may be sufficiently warm down the
well to enable it to flow; but the viscosity rises as the
composition is withdrawn from the well (and cools) making it more
difficult to flow.
[0012] Said treatment fluid formulation preferably comprises a
hydrogel.
[0013] Said treatment fluid formulation is preferably not injected
into an injection well of a subterranean formation in order to
contact said viscous composition.
[0014] Said treatment fluid formulation is preferably initially
contacted with said viscous composition at or downstream of a
production means, for example at or downstream of a producing face
of a subterranean formation. In one embodiment, said treatment
fluid formulation may be initially contacted with said viscous
composition below ground (for example at or adjacent to a producing
face of a subterranean formation) to reduce the viscosity of said
viscous composition below ground and facilitate its transport to
the surface. In another embodiment, said treatment fluid
formulation may be contacted with said viscous composition at or
adjacent the surface of the ground after the viscous composition
has been transported to the surface, for example using heavy
pumps.
[0015] Said treatment fluid formulation is preferably not used to
drive the viscous composition through a subterranean formation.
[0016] Said fluid flow path is preferably defined by a conduit
means.
[0017] Said conduit means preferably includes a first conduit part
(e.g. a pipeline) which is arranged downstream of a production
means, preferably above ground level. Said first conduit part
preferably contains said viscous composition after contact with the
treatment fluid formulation.
[0018] Said first conduit part may be circular in cross-section.
Said part may have a cross-sectional area for at least part of its
length of at least 5 cm, preferably at least 10 cm. In some cases,
the cross-section may have a diameter of up to 0.5 m. Said first
conduit part preferably extends away from a position where the
viscous composition is produced, suitably in a transverse direction
to the vertical. Said first conduit part may have a length of at
least 5 m, preferably at least 20 m, especially at least 100 m. In
some cases, said first conduit part may have a length of more than
1,000 m, more than 5,000 m, more than 10,000 m, even more than 500
km. Long pipes may be arranged to deliver petroleum to a refinery;
such pipes may extend partly above and partly below ground.
[0019] Said fluid flow path (e.g. said conduit means) may extend
between a first point, remote from the point of production of the
viscous composition, and a second point closer to, for example at
or adjacent to, the point of production of the viscous composition.
Said first point may be above ground and may be, for example, a
refinery; said second point may be closer to the producing face of
a subterranean formation. It may be at or adjacent to the producing
face.
[0020] Said fluid flow path may be defined, in part, by a second
conduit part which extends upwardly from below ground to above
ground. Said second conduit part may be a riser pipe. Said second
conduit part may contain said viscous composition after contact
with the treatment fluid formulation.
[0021] Said treatment fluid formulation is preferably arranged to
disperse and/or emulsify said viscous composition on contact
therewith. Said viscous composition may not be substantially
particulate prior to contact with said treatment fluid, formulation
- it may be in the form of a substantially homogenous fluidic mass.
Preferably, flow along said fluid flow path is turbulent, at least
in part, thereby to facilitate formation of said dispersion and/or
emulsion. Preferably, flow is turbulent at the point of initial
contact of said viscous composition with said treatment fluid
formulation so that said composition is dispersed and/or emulsified
on contact with said formulation.
[0022] In the method, a delivery flow path is preferably defined
which is arranged to communicate with said fluid flow path wherein
said treatment fluid formulation is dosed into said viscous
composition in said fluid flow path via said delivery flow path.
Said delivery flow path preferably communicates with said fluid
flow path at or downstream of a producing face of the subterranean
formation.
[0023] The ratio of the flow rate (in weight per unit time) of
treatment fluid formulation in said delivery flow path to the flow
rate (in the same units) of viscous composition in said fluid flow
path may be in the range 0.1 to 2.5, preferably in the range 0.2 to
1, more preferably in the range 0.4 to 0.8, especially in the range
0.6 to 0.7.
[0024] The mass fraction of viscous composition in said fluid flow
path after contact with said treatment fluid formulation is
preferably in the range 0.4 to 0.8.
[0025] Preferably, immediately after contact between said viscous
composition and said treatment fluid formulation, the composition
in said fluid flow path includes 30 to 80 wt % (preferably 40 to 80
wt %, more preferably 50 to 70 wt %) of material derived from said
viscous composition and 20 to 70 wt %, (preferably 20 to 60 wt %,
more preferably 30 to 50 wt %, especially 30 to 45 wt %) of
material derived from said treatment fluid formulation.
[0026] Suitably, immediately after contact between said viscous
composition and said treatment fluid formulation, the composition
in said fluid flow path includes at least 20 wt %, preferably at
least 25 wt %, more preferably at least 30 wt %, water; and at
least 40 wt %, preferably at least 50 wt %, more preferably at
least 55 wt % of said viscous composition, especially of oil.
[0027] The amount of water in the composition in said fluid flow
path immediately after contact between said viscous composition and
said treatment fluid formulation is preferably less than 70 wt %,
more preferably less than 60 wt %, especially less than 50 wt %,
more preferably 40 wt % or less. The amount of water may be in the
range 20 to 50 wt %.
[0028] Said treatment fluid formulation suitably has a viscosity at
25.degree. C. and 1000 s.sup.-1 of greater than 1 cP, preferably
greater than 2 cP. Said treatment fluid formulation preferably has
a viscosity under the conditions described of not greater than 50
cP, preferably of 10 cP %.or less.
[0029] Said treatment fluid formulation is preferably aqueous. It
may include at least 70 wt %, preferably at least 80 wt %, more
preferably at least 90 wt %, especially at least 95 wt % water. The
amount of water may be less than 99.6 wt %. Said treatment fluid
formulation preferably includes 90 to 99.6 wt % water.
[0030] Said treatment fluid formulation suitably includes at least
0.2 wt %, preferably at least 0.4 wt %, especially at least 0.5 wt
% of said polymeric material AA. Said formulation preferably
includes less than 10 wt %, more preferably less than 8 wt %,
especially less than 5.5 wt % of said polymeric material AA.
[0031] In a preferred embodiment, said treatment fluid formulation
includes 94.5 to 99.6 wt % water and 0.4 to 5.5. wt % of said
polymeric material AA; and the ratio of the wt % of said treatment
fluid formulation to the wt % of said viscous composition contacted
in the method is in the range 0.4 to 0.9.
[0032] Water for use in the treatment fluid formulation may be
derived from any convenient source. It may be potable water,
surface water, sea water, aquifer water, deionised production water
and filtered water derived from any of the aforementioned sources.
The water may be treated so that it is suitable for use in the
method. For example, it may be treated by addition of oxygen
scavengers, biocides, corrosion inhibitors, scale inhibitors,
anti-foaming agents and flow improvers. Sea water and/or water from
other sources may be deoxygenated and/or desulphonated.
[0033] Said polymeric material AA is preferably soluble in water at
25.degree. C. Preferably, when said polymeric material AA is not
cross-linked, polymeric material AA in said treatment fluid
formulation is wholly or partially dissolved therein to define a
solution or dispersion.
[0034] Whilst the applicant does not wish to be bound by any
theory, said optionally cross-linked polymeric material AA may be
arranged to coat particles of the viscous composition, whereby the
coated particles may then be more easily dispersed compared to
uncoated particles such as oil. Said polymeric material AA may be
arranged to be absorbed onto the viscous composition, for example
oil, to enable said particles to form. Said polymeric material AA
is preferably not a conventional surfactant having, a hydrophobic
portion, for example a hydrophobic tail and a hydrophilic portion,
for example an ionic head. Thus, it is believed that formation of
said coated particles preferably does not involve a hydrophobic
tail part interacting with, for example oil, and a hydrophilic part
interacting with, for example water. According to the applicant's
theory, the polymeric material AA may form "balls" made up of
"threads" of the polymeric material. It is believed that a
multiplicity of such balls associate with the surface of oil
droplets formed in the method, to surround the droplets and thereby
stabilise them. When the polymeric material AA is cross-linked the
cross-links may formalise the shape of the balls and make them
robust.
[0035] Said polymeric backbone of polymeric material AA preferably
includes carbon atoms. Said carbon atoms are preferably part of
--CH.sub.2-- moieties. Preferably, a repeat unit of said polymeric
backbone includes carbon to carbon bonds, preferably C-C single
bonds. Preferably, said polymeric material AA includes a repeat
unit which includes a --CH.sub.2-- moiety. Preferably, said
polymeric backbone does not include any --O-- moieties, for
examples --C--O-- moieties such as are found in an alkyleneoxy
polymer, such as polyethyleneglycol. Said polymeric backbone is
preferably not defined by an aromatic moiety such as a phenyl
moiety such as is found in polyethersulphones. Said polymeric
backbone preferably does not include any --S-- moieties. Said
polymeric backbone preferably does not include any nitrogen atoms.
Said polymeric backbone preferably consists essentially of carbon
atoms, preferably in the form of C--C single bonds.
[0036] Said treatment fluid formulation may include a hydrogel
which may be an optionally cross-linked polysaccharide,
polyvinylalcohol or polyvinylacetate.
[0037] Said --O-- moieties are preferably directly bonded to the
polymeric backbone.
[0038] Said polymeric material AA preferably includes, on average,
at least 10, more preferably at least 50, --O-- moieties pendent
from the polymeric backbone thereof. Said --O-- moieties are
preferably a part of a repeat unit of said polymeric material
A.
[0039] Preferably, said --O-- moieties are directly bonded to a
carbon atom in said polymeric backbone of polymeric material AA,
suitably so that said polymeric material AA includes a moiety
(which is preferably part of a repeat unit) of formula:
##STR00001##
where G.sup.1 and G.sup.2 are other parts of the polymeric backbone
and G.sup.2 is another moiety pendent from the polymeric backbone.
Preferably, G.sup.3 represents a hydrogen atom.
[0040] Preferably, said polymeric material AA includes a moiety
##STR00002##
[0041] Said moiety III is preferably part of a repeat unit. Said
moiety III may be part of a copolymer which includes a repeat unit
which includes a moiety of a different type compared to moiety III.
Suitably, at least 60 mole %, preferably at least 80 mole %, more
preferably at least 90 mole % of polymeric material AA comprises
repeat units which comprise (preferably consists of) moieties III.
Preferably, said polymeric material AA consists essentially of
repeat units which comprise (preferably consist of) moieties
III.
[0042] Suitably, 60 mole %, preferably 80 mole %, more preferably
90 mole %, especially substantially all of said polymeric material
AA comprises vinyl moieties which are optionally cross-linked.
[0043] Preferably, the free bond to the oxygen atom in the --O--
moiety pendent from the polymeric backbone of polymeric material AA
(and preferably also in moieties II and III) is bonded to a group
R.sup.10 (so that the moiety pendent from the polymeric backbone of
polymeric material AA is of formula --O--R.sup.10). Preferably
group R.sup.10 comprises fewer than 10, more preferably fewer than
5, especially 3 or fewer carbon atoms. It preferably only includes
atoms selected from carbon, hydrogen and oxygen atoms. R.sup.10 is
preferably selected from a hydrogen atom and an alkylcarbonyl,
especially a methylcarbonyl group. Preferably moiety --O--R.sup.10
in said polymeric material AA is an hydroxyl or acetate group.
[0044] Said polymeric material AA may include a plurality,
preferably a multiplicity, of functional groups (which incorporate
the --O-- moieties described) selected from hydroxyl and acetate
groups. Said polymeric material AA preferably includes a
multiplicity of hydroxyl groups pendent from said polymeric
backbone. Said polymeric material AA preferably includes a
multiplicity of acetate groups pendent from the polymeric
backbone.
[0045] Preferably, each free bond to the oxygen atoms in --O--
moieties pendent from the polymeric backbone in polymeric material
AA, except for any free bonds which are involved in cross-linking
the polymeric material AA, is of formula --O--R.sup.10 wherein each
group --OR.sup.10 is selected from hydroxyl and acetate.
[0046] Preferably, said polymeric material AA includes a vinyl
alcohol moiety, especially a vinyl alcohol repeat unit. Said
polymeric material AA preferably includes a vinyl acetate moiety,
especially a vinylacetate repeat unit. Polyvinylalcohol is
generally made by hydrolysis of polyvinylacetate. Said polymeric
material AA may comprise a 0-100% hydrolysed, preferably a 5 to 95%
hydrolysed, more preferably a 60 to 90 wt %, especially a 70 to 85
wt % hydrolysed polyvinylacetate
[0047] Said polymeric material AA may have a number average
molecular weight (Mn) of at least 10,000, preferably at least
50,000, especially at least 75,000. Mn may be less than 500,000,
preferably less than 400,000. Said polymeric material AA is
preferably a polyvinyl polymer. Said polymeric material AA may be a
copolymer.
[0048] Said polymeric material AA is preferably a polyvinyl alcohol
polymer or copolymer.
[0049] Preferably, said polymeric material AA includes at least one
vinyl alcohol/vinyl acetate copolymer which may include greater
than 5%, suitably includes greater than 30 wt %, preferably greater
than 65%, more preferably greater than 80 wt % of vinyl alcohol
moieties.
[0050] Said polymeric material AA may be a random or block
copolymer.
[0051] As described above, polymeric material AA is optionally
cross-linked. A cross-linked material may be used in the method
when the chemical or physical conditions to which the treatment
fluid formulation may be subjected during the reduction in
viscosity of the viscous composition and/or during flow in a
conduit means, for example in said first conduit part (when
provided) as described above, may be relatively harsh. In many
applications, it is not be necessary to cross-link polymeric
material AA.
[0052] A cross-linked material as described is preferably a
hydrogel. Such a hydrogel may be selected from a cross-linked
natural or synthetic polysaccharide, polyvinylalcohol or
polyvinylacetate.
[0053] When a cross-linked material is used in the method, said
method preferably comprises selecting a said polymeric material AA;
selecting a material BB which includes- a functional group which is
able to react in the presence of said polymeric material AA to
cross-link polymeric material AA and form a polymeric material CC;
and causing the formation of said polymeric material CC by a
reaction involving said polymeric material AA and material BB.
[0054] The ratio of the wt % of said material BB to the wt % of
said polymeric material AA selected for preparation of said
polymeric material CC is suitably less than 0.15, preferably less
than 0.10, more preferably less than 0.05, especially less than
0.035. Said ratio may be at least 0.005, preferably at least 0.01,
more preferably at least 0.015, especially at least 0.02.
[0055] The sum of the wt % of the polymeric material AA and
material BB selected for preparation of said polymeric material CC
may be at least 0.4 wt %. The sum may be less than 5 wt %,
preferably less than 4 wt %, more preferably less than 3 wt %,
especially less than 2.5 wt %.
[0056] Suitably, the amounts of "polymeric material AA" and
"material BE" described refer to the sum of the amounts of
polymeric materials AA (if more than one type is provided) and the
sum of the amounts of materials BB (if more than one type is
provided).
[0057] Preferably, formation of said polymeric material CC from
said polymeric material AA and material BB involves a condensation
reaction. Preferably, formation of said polymeric material CC
involves an acid catalysed reaction. Preferably, said polymeric
material AA and material BE include functional groups which are
arranged to react, for example to undergo a condensation reaction,
thereby to form said polymeric material CC. Preferably, said
polymeric material AA and material BB include functional groups
which are arranged to react for example to undergo an acid
catalysted reaction thereby to form said polymeric material CC.
[0058] Said material BB may be an aldehyde, carboxylic acid, urea,
acroleine, isocyanate, vinyl sulphate or vinyl chloride of a diacid
or include any functional group capable of condensing with one or
more groups on said polymeric material AA. Examples of the
aforementioned include formaldehyde, acetaldehyde, glyoxal and
glutaraldehyde, as well as maleic acid, oxalic acid, dimethylurea,
polyacroleines, diisocyanates, divinyl sulphate and the chlorides
of diacids.
[0059] Said material BE is preferably an aldehyde containing or
generating compound. Preferably, material BB is an aldehyde
containing compound.
[0060] Material BE may include one or more aldehyde groups. Whilst
it could be a monoaldehyde such as formaldehyde it preferably
includes a plurality of aldehyde groups.
[0061] Material BB may have a general formula
##STR00003##
where G.sup.5 represents a direct link or a linking moiety.
[0062] G.sup.5 may be arranged to space apart the --CHO groups
thereby to affect the spacing of the cross-linking of polymeric
material AA.
[0063] In one embodiment, group G.sup.5 may be a
--(CH.sub.2).sub.y-- moiety wherein y represents 0 to 8, and one or
more of the H atoms may be replaced by but preferably are not
replaced by) another atom or group. Preferably, y represents 0 to
6, more preferably 0 to 4, especially 0 to 2.
[0064] Group G.sup.5 may be arranged to introduce some rigidity
into the cross-linking of polymeric material AA. For example, group
G.sup.5 may include at least some covalent bonds which are not
freely rotatable. For example, group G.sup.5 preferably does not
consist exclusively of a --CH.sub.2-- chain wherein each
carbon-carbon bond will be freely rotatable but preferably includes
an atom or group or other means which restricts free rotation
compared to a case wherein G.sup.5 consists of a --CH.sub.2--
chain. For example G.sup.5 may incorporate bulky atoms or groups;
and/or unsaturated atoms or groups; and/or atoms or groups which
hinder free rotation due to electronic effects.
[0065] Group G.sup.5 may include at least 1, preferably at least 2,
more preferably at least 3, especially at least 4, carbon atoms in
a chain extending between the two -CHO groups.
[0066] In one embodiment, group G.sup.5 incorporates one or more
aromatic or heteroaromatic groups. Such groups may be arranged to
restrict rotation as described. Preferred heteroaromatic groups
include N-containing heteroaromatic groups. Preferred aromatic and
heteroaromatic groups are selected from optionally-substituted
phenyl and N-containing aromatic groups, such as pyridinyl
groups.
[0067] Group G.sup.5 preferably includes both an aromatic and
N-containing heteroaromatic group.
[0068] Group G.sup.5 preferably includes some charge separation. It
preferably includes a polar group. It preferably includes a
cationic group. A preferred cationic group is one which includes a
N moiety.
[0069] Group G.sup.5 may itself include one or more aldehyde (or
other) functional groups.
[0070] Said polymeric material CO may include a moiety
##STR00004##
wherein the free bonds of the oxygen atoms are bonded to the
polymeric backbone and the free bond of the carbon atom is bonded
to a residue of the material BB. The residue of material BB may
also be bonded to the polymeric backbone of another polymeric chain
(for example of a polymeric material AA as described), thereby to
cross-link polymeric material AA.
[0071] Said material BB may comprise:
[0072] (i) a first polymeric material having a repeat unit of
formula
##STR00005##
wherein A and B are the same or different, are selected from
optionally-substituted aromatic and heteroaromatic groups and at
least one comprises a relatively polar atom or group and R.sup.1
and R.sup.2 independently comprise relatively non-polar atoms or
groups; or
[0073] (ii) a first polymeric material prepared or preparable by
providing a compound of general formula
##STR00006##
wherein A, B, R.sup.1 and R.sup.2 are as described above, in an
aqueous solvent and causing the groups C.dbd.C in said compound to
react with one another to form said first polymeric material.
[0074] In the first polymeric material described above, A and/or B
could be multi-cyclic aromatic or heteroaromatic groups.
Preferably, A and B are independently selected from
optionally-substituted five or more preferably six-membered
aromatic and heteroaromatic groups. Preferred heteroatoms of said
heteroaromatic groups include nitrogen, oxygen and sulphur atoms of
which oxygen and especially nitrogen, are preferred. Preferred
heteroaromatic groups include only one heteroatom. Preferably, a or
said heteroatom is positioned furthest away from the position of
attachment of the heteroaromatic group to the polymer backbone. For
example, where the heteroaromatic group comprises a six-membered
ring, the heteroatom is preferably provided at the 4-position
relative to the position of the bond of the ring with the polymeric
backbone.
[0075] Preferably, A and B represent different groups. Preferably,
one of A or B represents an optionally-substituted aromatic group
and the other one represents an optionally-substituted
heteroaromatic group. Preferably A represents an
optionally-substituted aromatic group and B represents an
optionally-substituted heteroaromatic group especially one
including a nitrogen heteroatom such as a pyridinyl group.
[0076] Unless otherwise stated, optionally-substituted groups
described herein, for example groups A and B, may be substituted by
halogen atoms, and optionally substituted alkyl, acyl, acetal,
hemiacetal, acetalalkyloxy, hemiacetalalkyloxy, nitro, cyano,
alkoxy, hydroxy, amino, alkylamino, sulphinyl, alkylsulphinyl,
sulphonyl, alkylsulphonyl, sulphonate, amido, alkylamido,
alkylcarbonyl, alkoxycarbonyl, halocarbonyl and haloalkyl groups.
Preferably, up to 3, more preferably up to 1 optional substituents
may be provided on an optionally substituted group.
[0077] Unless otherwise stated, an alkyl group may have up to 10,
preferably up to 6, more preferably up to 4 carbon atoms, with
methyl and ethyl groups being especially preferred.
[0078] Preferably, A and B each represent polar atoms or
group--that is, there is preferably some charge separation in
groups A and B and/or groups A and B do not include carbon and
hydrogen atoms only.
[0079] Preferably, at least one of A or B includes a functional
group which can undergo a condensation reaction, for example on
reaction with said polymeric material AA. Preferably, A includes a
said functional group which can undergo a condensation
reaction.
[0080] Preferably, one of groups A and B includes an optional
substituent which includes a carbonyl or acetal group with a formyl
group being especially preferred. The other one of groups A and B
may include an optional substituent which is an alkyl group, with
an optionally substituted, preferably unsubstituted, C.sub.1-4
alkyl group, for example a methyl group, being especially
preferred.
[0081] Preferably, A represents a group, for example an aromatic
group, especially a phenyl group, substituted (preferably at the
4-position relative to polymeric backbone when A represents an
optionally-substituted phenyl group) by a formyl group or a group
of general formula
##STR00007##
where x is an integer from 1 to 6 and each R.sup.3 is independently
an alkyl or phenyl group or together form an alkalene group.
[0082] Preferably, B represents an optionally-substituted
heteroaromatic group, especially a nitrogen-containing
heteraromatic group, substituted on the heteroatom with a hydrogen
atom or an alkyl or aralkyl group. More preferably, B represents a
group of general formula
##STR00008##
wherein R.sup.4 represents a hydrogen atom or an alkyl or aralkyl
group, R.sup.5 represents a hydrogen atom or an alkyl group and
X.sup.- represents a strongly acidic ion.
[0083] Preferably, R.sup.1 and R.sup.2 are independently selected
from a hydrogen atom or an optionally-substituted, preferably
unsubstituted, alkyl group. Preferably, R.sup.1 and R.sup.2
represent the same atom or group. Preferably, R.sup.1 and R.sup.2
represent a hydrogen atom.
[0084] Preferred first polymeric materials may be prepared from any
of the compounds described on page 3 line 8 to line 39 of
GB2030575B by the method described in WO98/12239 and the contents
of the aforementioned documents are incorporated herein by
reference.
[0085] Said first polymeric material may be of formula
##STR00009##
wherein A, B, R.sup.1 and R.sup.2 are as described above and n is
an integer. Integer n is suitably 10 or less, preferably 8 or less,
more preferably 6 or less, especially 5 or less. Integer n is
suitably at least 1, preferably at least 2, more preferably at
least 3.
[0086] Said polymeric material CC suitably includes a moiety of
formula
##STR00010##
wherein R.sup.1, R.sup.2 and B are as described above, A.sup.1
represents a residue of group A described above after the reaction
involving said first polymeric material and polymeric material AA,
Y represents a residue of said polymeric material AA after said
reaction involving said first polymeric material and polymeric
material AA and X represents a linking atom or group extending
between the residues of said first polymeric material and said
polymeric material AA. In one preferred embodiment A.sup.1
represents an optionally-substituted phenyl group, X represents a
group
##STR00011##
which is bonded via the oxygen atoms to a residue of said polymeric
material AA. For example, group X may be bonded to the polymeric
backbone of said polymeric material AA.
[0087] When said treatment fluid formulation comprises a polymeric
material AA which is cross-linked, preferably, prior to the
treatment fluid formulation contacting the viscous composition, it
has attained at least 70% of the maximum viscosity attainable for
the formulation at the temperature at which it is to contact the
viscous composition. Preferably, it has attained at least 80%, more
preferably 90%, especially about 100% of its maximum viscosity.
Thus, in an especially preferred embodiment, said polymeric
material AA and material BE are substantially completely reacted to
form said polymeric material CC prior to contact with said viscous
composition.
[0088] After the viscous composition has been delivered to a
desired location (for example a refinery) the viscous composition
may be caused to separate from other components of the treatment
fluid formulation. This may be achieved by simply reducing any
mixing or turbulent movement of the mixture and allowing the
viscous composition to settle out from the water and optionally
cross-linked polymeric material AA (which may be substantially
soluble in the water under the conditions of settling). The rate of
setting may be increased by increasing the temperature of the
viscous composition. Additionally, the viscous composition may be
diluted with light oil or mechanical means may be used to encourage
settling. In some cases, for example, when said polymeric material
AA is cross-linked, it may settle out as described. In other cases,
wherein polymeric material AA is cross-linked, the method of the
first aspect may include the step of contacting the mixture with a
breaker means arranged to break an aqueous emulsion of the viscous
composition. When polymeric material CC comprises 1.2-diol
linkages, the breaker means is preferably arranged to cleave
1,2-diol linkages. Said breaker means preferably comprises a
periodate (e.g. sodium or potassium periodate) in water.
[0089] The method of the first aspect preferably includes the step
of separating at least a part of the treatment fluid formulation
from the viscous composition after the viscous composition has
flowed along said fluid flow path. After separation, said viscous
composition suitably includes less than 10 wt %, preferably less
than 5 wt %, especially less than 2 wt % water. After separation
said viscous composition suitably includes less than 2 wt %,
preferably less than 1 wt %, more preferably less than 0.5 wt %,
especially less than 0.2 wt %, of said optionally-cross-linked
polymeric material AA.
[0090] When the method includes the separating step as described,
the treatment fluid formulation which is separated from the viscous
composition may be re-used to reduce the viscosity of further
viscous composition. For example, the method may involve a
continuous or semi-continuous process wherein treatment fluid
formulation is contacted with viscous composition to reduce its
viscosity; the mixture is then caused to flow downstream along a
fluid flow path thereby to deliver the viscous composition to a
desired location; the viscous composition and treatment fluid
formulation are separated; the viscous composition is used and/or
stored as required in said desired location; the treatment fluid
formulation is delivered to a location thereby to contact further
viscous composition upstream of said desired location; and the
process is suitably repeated.
[0091] According to a second aspect of the present invention there
is provided a method of preparing a treatment fluid formulation
(e.g. for reducing the viscosity of a viscous composition)
comprising: contacting an optionally cross-linked polymeric
material AA as described according to the first aspect with
water.
[0092] Preferably, the polymeric material AA is dissolved in the
water thereby to prepare an aqueous solution of said polymeric
material AA. Preferably, the polymeric material AA is in the form
of a solid prior to contact with water.
[0093] Preferably, at least 100 litres more preferably at least
1000 litres of said treatment fluid formulation is prepared.
[0094] When the treatment fluid formulation is cross-linked, the
method may comprise: selecting a polymeric material AA (for example
a polyvinylalcohol) and a material BB as described according to
said first aspect; and causing the formation of a said polymeric
material CC by a reaction involving said polymeric material AA and
said material BE.
[0095] In the preparation of said polymeric material CC, a catalyst
is preferably provided for catalysing the reaction of the polymeric
material AA and said material BB. Said catalyst is preferably a
protic acid. Said catalyst is preferably phosphoric acid.
Advantageously, when the fluid flow path of the first aspect is
defined by steel pipes the phosphoric acid may facilitate the
formation of an anti-corrosive layer on the pipes.
[0096] The method is preferably carried out adjacent or close to an
oil field, for examples within 1 mile of a production well thereof.
The method is preferably carried out within mile of an oil supply
line which is arranged to transport oil between two locations.
[0097] According to a third aspect of the invention, there is
provided a treatment fluid formulation comprising: [0098] at least
95 wt % water [0099] 4 wt % or less of said polymeric material AA
which has optionally been cross-linked as described above.
[0100] According to a fourth aspect of the invention, there is
provided a method of reducing the viscosity of a viscous
composition which is arranged to flow along a fluid flow path, said
method comprising contacting the viscous composition with a
treatment fluid formulation, wherein said treatment fluid
formulation includes a polymeric material which:
[0101] (a) is arranged to associate with, for example absorb onto,
said viscous composition, especially oil, in order to enable
droplets of said viscous composition to be formed, and/or
stablised; and/or
[0102] (b) is arranged to form a coating (which may be
discontinuous) around droplets of said viscous composition;
[0103] (c) is arranged to form a hydrogel which is able to
stabilise droplets of said viscous composition, especially oil.
[0104] Preferably, said polymeric material in said treatment fluid
formulation (which is preferably optionally cross-linked polymeric
material AA described above) is arranged to form a material, for
example a hydrogel which is arranged to associate with, for example
coat, droplets of said viscous composition, especially oil, in
order to enable the formulation of a dispersion comprising said
droplets.
[0105] Preferably, said polymeric material has each of the effects
described in (a), (b) and (c) of the fourth aspect.
[0106] According to a fifth aspect of the invention, there is
provided a method of reducing the viscosity of a viscous
composition which is arranged to flow along a fluid flow path, said
method comprising contacting the viscous composition with a
treatment fluid formulation which includes a hydrogel, for example
of an optionally cross-linked polymeric material AA as described
herein.
[0107] The invention extends to a receptacle containing at least
100 litres, preferably at least 200 litres, especially at least
1000 litres of a said treatment fluid formulation as described
herein.
[0108] According to a sixth aspect of the invention, there is
provided a fluid flow path, for example a conduit means (preferably
having a cross-sectional diameter at least in part of at least 5 cm
and a length of at least 5 m) which contains a fluid comprising
petroleum, water and an optionally cross-linked polymeric material
AA as described herein. Said polymeric material may be a hydrogel,
preferably as described herein.
[0109] Any feature of any aspect of any invention or embodiment
described herein may be combined with any feature of any aspect of
any other invention or embodiment described herein mutatis
mutandis.
[0110] Specific embodiments of the invention will now be described,
by way of example, with reference to FIG. 1 which is a plot of
viscosity vs. shear rate for various formulations.
[0111] In general terms, heavy crude oil (and associated material)
which may be too viscous to enable it to be pumped from the flowing
face of a reservoir into and along a pipeline, for example to a
refinery or other storage facility, may be contacted with a
formulation at any point where it is desirable to reduce the oil
viscosity. In a first embodiment, the formulation may comprise
polyvinyl alcohol which alone has been found to be capable
advantageously of reducing the viscosity of crude oil thereby
enabling it to flow. In a second embodiment, the formulation may
comprise a cross-linked polymeric material, for example
cross-linked polyvinyl alcohol. The material of the second
embodiment may be more robust compared to that of the first
embodiment and may therefore be used in more challenging
situations.
[0112] After, the oil has been transported to a desired location it
may be separated from the other components in the mixture by
allowing it to settle; by increasing its temperature; by dilution
with light oil; by mechanical separation such as centrifugation (or
the like); or by treatment with a chemical means such as a breaker
which is arranged to break down cross-linked polymeric
material.
[0113] Further details on the process are provided below.
EXAMPLE 1
[0114] 60 g of an aqueous solution comprising 0.5% by weight
polyvinylalcohol (80-95% hydrolyzed) of molecular weight 110,000
was added to a screw-capped glass vessel. To this was added 40 g of
a crude oil which had a viscosity between 5800 cP and 6500 cP at a
shear rate of 1 reciprocal second. The glass vessel was capped and
the mixture was agitated by hand-shaking for approximately 30
seconds. [0115] The viscosity of the subsequent mixture was
determined to be between 1200 cP and 1800 cP at a shear rate of 1
reciprocal second and less than 200 cP at 100 s.sup.-1.
EXAMPLE 2
[0116] The procedure described in example 1 was followed with the
exception that mixing was performed under high shear. The viscosity
of the final mixture was observed to be in the range 1200 cP to
1800 cP at a shear rate of 1 reciprocal second and less than 200 cP
at 100 s.sup.-1.
EXAMPLE 3
Preparation of
poly(1,4-di(4-(N-methylpyridinyl))-2,3-di(4-(1-formylphenyl)butylidene
[0117] This was prepared as described in Example 1 of
PCT/GB97/02529, the contents of which are incorporated herein by
reference. In the method, an aqueous solution of greater than 1 wt
% of 4-(4-formylphenylethenyl)-1-methylpyridinium methosulphonate
(SbQ) is prepared by mixing the SbQ with water at ambient
temperature. Under such conditions, the SbQ molecules form
aggregates. The solution was then exposed to ultraviolet light.
This results in a photochemical reaction between the carbon-carbon
double bonds of adjacent
4-(4-formylphenylethenyl)-1-methylpyridinium methosulphate
molecules (I) in the aggregate, producing a polymer, poly
(1,4-di(4-(N-methylpyridinyl))-2,3-di(4-(1-formylphenyl)butylidene
methosulphonate (II).
EXAMPLE 4
Preparation of Poly(vinylalcohol) Solution
[0118] A 10 wt % poly(vinylalcohol) solution was prepared by slowly
stirring a known amount of water and adding a known amount of 88%
hydrolysed poly(vinylalcohol) of molecular weight 300,000 to the
stirred water. The suspension was stirred for 1 hour and,
thereafter, the suspension was heated at a temperature of
60.degree. C. until the suspended particles dissolved and the
solution was clear. The solution was then allowed to cool to less
than 5.degree. C. and maintained at this temperature until
used.
EXAMPLE 5
Preparation of Butylidene polymer/poly(vinylalcohol)
Formulation
[0119] 997.5 g of the poly(vinylalcohol) solution prepared in
Example 4 and 2.5 g of the butylidene polymer prepared in Example 3
were mixed together at ambient temperature to give a 10 wt %
poly(vinylalcohol)/0.25 wt % butylidene polymer solution. This was
diluted down to give a 2 wt % poly(vinyl alcohol)/0.05 wt %
butylidene polymer solution. this solution was acidified to pH 1.5
with phosphoric acid and left to cure for 1 hour. After curing the
solution was neutralised using 5M NaOH. This cured and neutralised
solution was then further diluted to give a 1 wt %
poly(vinylalcohol)/0.025 wt % butylidene polymer solution; and a
0.05 wt % polyvinylalcohol/0.0125 wt % butylidene polymer
solutions.
[0120] On acidification of the polyvinylalcohol/butylidene polymer
blend as described, the two polymers react as described in
PCT/GB97/02529.
EXAMPLE 6
Protocol for Preparation of Oil Emulsions
[0121] Emulsions of oil and the aqueous formulations of Example 5
were prepared at ratios of oil: aqueous formulation of 70:30 and
60:40 with the aqueous phase containing 2 wt %, 1wt % or 0.5 wt %
poly(vinylalcohol). The oil and aqueous formulations were initially
mixed using a spatula, then homogenized.
EXAMPLE 7
Protocol for Evaluation of Oil Emulsions
[0122] The viscosity against shear rate of the emulsions was
measured on 0.65 m1 samples at 25.degree. C. taking 60 measuring
points at 10 second intervals and a shear rate of 0.1 to 1000
s.sup.-1 followed immediately by a rate of 1000 to 0.1 s.sup.-1.
Results are provided in FIG. 1 wherein: [0123] Lines A and. A.sup.1
are comparative examples detailing the results for two runs
undertaken without inclusion of an aqueous formulation of Example
4. [0124] Lines B and B.sup.1 are the results for two runs
undertaken using the aqueous formulation of Example 5 with 2 wt %
poly(vinylalcohol). [0125] Lines C and C.sup.1 are the results for
two runs undertaken using the aqueous formulation of Example 5 with
1 wt % of poly(vinylalcohol). [0126] Lines D and D.sup.1 are the
results for two runs undertaken using the aqueous formulation of
Example 5 with 0.5 wt % of polyvinylalcohol.
[0127] FIG. 1 shows that without the addition of any formulation
described in Example 5, the viscosity is relatively high. When the
formulation is added, there is a significant reduction in
viscosity.
[0128] Thus, the formulation may be dosed into a oil flow at any
point at which it is desired to reduce the oil's viscosity to
enable it to be transported. For example, it may be closed in at
the bottom of a riser pipe to reduce the viscosity of oil flowing
upwardly in the pipe. Alternatively, it may be closed in at or near
the surface. Once closed in, the oil may be transported long
distances through a pipeline to a refinery or other oil storage
facility.
[0129] After completion of the transport stage, it is necessary to
recover the oil from the emulsion. This may be achieved by allowing
the mixture to settle; by mechanical means or by chemical means. An
example of the latter may involve the addition of 0.1 to 0.3 wt %
(preferably about 0.2 wt %) of a periodate salt (preferably the
sodium salt) to the emulsion. This causes the destruction of the
emulsion and enables the oil to be recovered for further
processing.
EXAMPLE 8
Preparation of Glutaraldehyde/poly(vinylalcohol) Formulation
[0130] A poly(vinylalcohol) solution of a 88% hydrolysed
poly(vinylalcohol) having a molecular weight of about 160,000 is
prepared by dissolving 87 g of the poly(vinylalcohol) in 1000 ml of
water by stirring the components for 24 hours at 80-90.degree. C.
The solution is then allowed to cool to 50.degree. C. and 1.29 ml
of a 25% solution of glutaraldehyde added with stirring for about 1
hour. Then, 100 ml of 1M HCl is added with stirring and a gel forms
which may be used as described above.
EXAMPLE 9
Preparation of Glyoxal/poly(vinylalcohol) Formulation
[0131] By a process analogous to Example 8 a glyoxal cross-linked
poly(vinylalcohol) may be prepared.
[0132] The materials of Examples 8 and 9 may be used in viscosity
reduction as described herein.
[0133] Attention is directed to all papers and documents which are
filed concurrently with or previous to this specification in
connection with this application and which are open to public
inspection with this specification, and the contents of all such
papers and documents are incorporated herein by reference.
[0134] All of the features disclosed in this specification
(including any accompanying claims, abstract and drawings), and/or
all of the steps of any method or process so disclosed, may be
combined in any combination, except combinations where at least
some of such features and/or steps are mutually exclusive.
[0135] Each feature disclosed in this specification (including any
accompanying claims, abstract and drawings) may be replaced by
alternative features serving the same, equivalent or similar
purpose, unless expressly stated otherwise. Thus, unless expressly
stated otherwise, each feature disclosed is one example only of a
generic series of equivalent or similar features.
[0136] The invention is not restricted to the details of the
foregoing embodiment(s). The invention extends to any novel one, or
any novel combination, of the features disclosed in this
specification (including any accompanying claims, abstract and
drawings), or to any novel one, or any novel combination, of the
steps of any method or process so disclosed.
* * * * *