GB2422857A

GB2422857A - Control of water production in a well

Info

Publication number: GB2422857A
Application number: GB0502171A
Authority: GB
Inventors: Hans Kristian Kotlar
Original assignee: Statoil ASA
Current assignee: Equinor ASA
Priority date: 2005-02-02
Filing date: 2005-02-02
Publication date: 2006-08-09
Anticipated expiration: 2025-02-02
Also published as: GB0502171D0; GB2422857B

Abstract

This invention provides a method of controlling water in a subterranean formation, said method comprising contacting said formation with a water control treatment agent which comprises an organosilane in an amount effective to reduce the water permeability of at least part of said formation. At the same time, any decrease in the overall hydrocarbon (e.g. oil) permeability of said formation is preferably minimised.

Description

WELL TREATMENT

This invention relates to a method of modifying the permeability of subterranean formations and, more specifically, to a method for reducing the water permeability of such formations In particular the invention concerns a method for selectively reducing the production of aqueous fluids (e.g. water) from hydrocarbon - producing formations Hydrocarbons (e g oil and gas) are generally recovered from subterranean formations by drilling a well bore into the formation and extracting the hydrocarbon One of the factors which influences the rate of hydrocarbon production and therefore the productivity of the well is the ratio of hydrocarbon to water which is produced from the formation The production of water and other aqueous fluids from subterranean formations is a common phenomenon, particularly with mature wells and a certain level of water production is in fact necessary for the efficient extraction of hydrocarbon. The water produced may be, for example, water that is injected in to the well to facilitate recovery of the hydrocarbon Alternatively or additionally the water may be "formation water" (i e that which is naturally present in the formation) As the hydrocarbons are extracted from a formation, water and aqueous fluids tend to move through channels in the formation and into the well bore where they are produced along with the hydrocarbon In fact as water is less viscous than hydrocarbon, it has a greater ability to flow and may therefore channel around the oil into the well bore Other mechanisms that tend to result in water production include "coning" into the well bore from a water column and movement of water through different strata of the formation Excess production of water (i e the production of more water than is necessary for efficient production of hydrocarbon) from wells causes a number of problems Aside from leading to a reduction in the rate of hydrocarbon production, water production can result in scaling of downhole equipment (e g pipelines, valves, sand screens, etc) as well as surface facilities Repair or replacement of such equipment can only be carried out during periods of shut-down in production which has a significant economic impact on the production process Excess production of water further increases the cost of recovering the hydrocarbon in a form suitable for transportation and/or further refining. In particular, the over production of water necessitates the use of expensive equipment to separate the water and other aqueous fluids from the hydrocarbon. The costs associated with disposal of produced water in an environmentally safe manner causes further economic drawbacks.

Typically, in hydrocarbon-producing formations the amount of water produced increases over the lifetime of the well Thus, when production first begins, very little excess water may be produced but the ratio of produced water to hydrocarbon tends to increase over time As a result, there comes a point at which more water than is necessary for efficient hydrocarbon extraction is produced and the cost of handling the volume of water becomes greater than the value of the hydrocarbon recovered At this point, the well bore may be described as "watered- out" (i.e it becomes uneconomical to work) Thus, although hydrocarbon material may still remain in a "watered-out" well reservoir zone, it can no longer be extracted economically A number of methods for controlling water production from subterranean formations have been proposed These include processes designed to block pores or channels within a formation by, for example, gellation using polymer materials such as polyvinyl alcohol and polyacrylic acid Another method that has been proposed involves introducing a barrier, such as a concrete resin, adjacent to the well bore in order to prevent the movement of water into the bore Such treatments can in some cases provide a desired level of water control by effectively blocking water producing channels and pores These methods are not, however, selective to water producing channels and also tend to block those channels and pores facilitating hydrocarbon production Thus, unless zonal isolation methods are used during delivery of the treatment chemicals, the rate of hydrocarbon production also tends to be drastically reduced as it becomes difficult for hydrocarbon to reach the well bore (i e the permeability of the formation to hydrocarbon is also decreased) Use of zonal isolation methods to overcome this problem is, however, both expensive and time-consuming It also necessitates the use of specialised equipment More recently, methods to achieve selective water control without the need for zonal isolation techniques have been proposed. These methods typically involve introducing a composition comprising a hydrophilic polymer (e g. a polyacrylamicle) into the formation. Whilst the size of the polymer impedes the movement of fluids (e g. water) in the formation, it is thought that the hydrophilicjty of the polymer affords the desired selectivity More specifically, it is believed that the hydrophilic nature of the polymer materials causes these to preferentially partition into those channels and pores of the formation which contain high levels of water The use of hydrophilic polymers is not, however, without its disadvantages One drawback is that the polymers tend to have only limited retention time in the formation Despite suggestions for improving their retention, it is still the case that forn-iatjons often have to be re-treated with further polymer material after a relatively short period of time It is also not uncommon for a reduction in hydrocarbon production to be associated with the use of such polymers since at least a proportion of these locate into primarily hydrocarbonproducing channels or pores thereby blocking the production of hydrocarbon (e.g. oil).

A further disadvantage associated with the use of polymer materials to control water production arises from the fact that they are often at least partially unstable in acids and heavy brines which are commonly used in hydrocarbon production Exposure to such chemicals can cause the polymers to decompose and/or degrade thereby nullifying their blocking effect When this occurs, the formation then has to be re-treated thus further increasing costs There is thus a continuing need for alternative (e g improved) methods for controlling water flow in subterranean formations, especially during the production of hydrocarbon (e g oil) from a well and, in particular, for methods which are capable of reducing the volume of water produced during hydrocarbon recoveiy More particularly, a need exists for such methods that are capable of selectively reducing the production of aqueous fluids (e g water) from hydrocarbonproducing formations, i e methods in which the production of water is reduced or eliminated without substantially affecting the production of hydrocarbon Surprisingly, we have now found that the flow of water in a subterranean formation, e g the production of water from such a formation, can effectively be controlled by a water control treatment agent comprising an organosilane. In particular, we have found that an organosilane is capable of selectively reducing the production of aqueous fluids (e.g. water) from a hydrocarbonproducjng well without adversely affecting the recovery of hydrocarbon.

Viewed from one aspect the present invention thus provides a method of controlhng water in a subterranean formation, said method comprising contacting said formation with a water control treatment agent which comprises an organosilane in an amount effective to reduce the water permeability of at least part of said formation In a preferred embodiment of the method of the invention any decrease in the overall hydrocarbon (e. g oil) permeability of said formation is minim ised Viewed from another aspect the invention provides the use of a water control treatment agent comprising an organosilane in a method of controlling water in a subterranean formation, said method comprising contacting said formation with said agent in an amount effective to reduce the water permeability of at least part of said formation, preferably whilst minimising any decrease in the overall hydrocarbon (e.g. oil) permeability of said formation Viewed from a still further aspect the Invention provides the use of an organosilane as a water control treatment agent to control water in a subterranean formation wherein said agent is effective to reduce the water permeability of at least part of said formation, preferably whilst minimising any decrease in the overall hydrocarbon (e g oil) permeability of said formation Viewed from a yet still further aspect the invention provides a water control treatment agent comprising an organosilane in an amount effective to control water in a subterranean formation, e g by reducing the water permeability of at least part of said formation, preferably whilst minimising any decrease in the overall hydrocarbon (e g oil) permeability of said formation As used herein, the term "permeability' refers to the capacity of a porous medium to transmit a fluid It therefore provides a measure of the resistance of a formation to flow of a liquid (e g. water and/or hydrocarbon) through the pores and channels forming its structure Thus, "hydrocarbon permeability" means the capacity of a porous medium such as a subterranean formation to transmit hydrocarbon (e.g. oil) and "water permeabilityt' means the corresponding capacity to transmit water.

Permeability may be measured using Darcy's Law.

Q k.AP A/pt where Q = flow rate (cm3/s) AP = pressure drop (atm) across a cylinder having a length L (cm) and a cross-sectional area A (cm2) m = fluid viscosity (cp) k permeability (Darcy) In the method of the present invention, the permeability to water of at least part of the formation is reduced At the same time, the overall hydrocarbon permeability of the formation may also be reduced Preferably, however, the hydrocarbon permeability is reduced to a lesser extent (e g 50 % less, more preferably 70 % less) than the water permeability In any case, hydrocarbon may still be extracted from the formation more economically than prior to treatment as a result of the decrease in water production It should also be noted that the method of the present invention may, for example, be combined with the use of a higher draw down in order to compensate for any decrease in the hydrocarbon permeability of the formation In a preferred embodiment of the method of the present invention, the permeability to water of at least part of the formation is reduced whilst at the same time any decrease in the overall hydrocarbon permeability of the firmation is minimised This may be achieved, for example, by selectively blocking or impeding fluid flow (e g the flow of water) in those zones of the formation through which water predominantly flows whilst at the same time leaving those zones through which hydrocarbon predominantly flows substantially unchanged (I e substantially maintaining the flow of hydrocarbon in the formation) For example, if the formation to he treated is a multi-layered formation (e g a sandstone formation) with two or more hydrocarbon-rich layers the method of the invention may be used to treat the first drained or depleted layer (i.e. that from which essentially all hydrocarbon has been recovered) before starting production from the next hydrocarbon layer. In this way the method of the invention may be used to effectively isolate or "shut-off' the first layer which, following depletion, would otherwise produce water The production of hydrocarbon is therefore facilitated without the need for mechanical isolation in the well bore Thus, in a preferred aspect of the invention the permeability of water-rich regions of the formation is reduced (e.g decreased by at least 25 %, more preferably by at least 50 %, e g. by at least 80%) By a "water-rich region" is meant an area of the formation comprising greater than 50 %, preferably greater than 70 %, still more preferably greater than 80 %, water and/or aqueous fluids In a further preferred aspect of the invention the permeability of hydrocarbon-rich regions of the formation is substantially unchanged prior to, and after, treatment according to the methods herein described. For example, the hydrocarbonpermeabjljty is preferably decreased by less than 55 %, more preferably less than 30%, e g. less than 20% By a "hydrocarbon-rich region" is meant an area of the formation comprising greater than 50 % hydrocarbon, preferably greater than 70 % hydrocarbon, still more preferably greater than 80 % hydrocarbon The effect of reducing the permeability of water-rich regions of the formation is to reduce the overall water permeability of the formation Preferably, the overall water permeability of the formation is reduced by 40-100%, preferably 60-100%, e.g 80-100% The overall hydrocarbon permeability of the formation is preferably reduced by 0-50 %, more preferably 0-30 %, e g 0 - 20 % Still more preferably the hydrocarbon permeability of the formation will be substantially the same both prior to and after treatment in accordance with the methods of the invention The reduction in permeability of a subterranean formation to a given fluid may alternatively be expressed in terms of a resistance factor, R1 For example, the quotient of permeability to water at irreducible oil saturation prior to treatment (K) to the permeability to water at irreducible oil saturation after treatment (K) j defined herein as the resistance factor for water Preferably, the method of the invention provides a water resistance factor, Rf of at least 10, more preferably at least 50, e g. at least 100 as measured at a flow rate of 1 mI/mm across a core of diameter 65 mm The quotient of permeability to oil at irreducible water saturation before treatment (K0) to permeability to oil at irreducible water saturation after treatment (K0) is analogously defined herein as the resistance factor for oil Preferably, the method of the invention provides an oil resistance factor, Rf of 50 or less, more preferably 10 or less, e g 5 or less as measured at a flow rate of I mI/rn in across a core of diameter 65 mm Still more preferably a formation treated in accordance with the method of the invention may have a post-treatment resistance factor for water of at least 50 and a post-treatment resistance factor for oil of 10 or less as measured at a flow rate of I mi/ruin across a core of diameter 65 mm A desired effect of reducing the permeability of at least part of the formation (e.g water-rich regions of the formation) is to reduce the volume of water obtained during production of hydrocarbon. Preferably, the production of water from the formation is reduced by 5 to 90%, preferably 10 to 95 %, more preferably 20 to 99 %, e g. at least 40 % after treatment in accordance with the methods herein described Still more preferably the v/v ratio of hydrocarbon to water produced from a well following treatment according to the invention is at least 70 30, more preferably at least 80 20, e g at least 90 10 In the method of the invention permeability modification (e.g selective permeability modification) as hereinbefore described may be achieved using a water control treatment agent comprising an organosilane Whilst not wishing to be bound by theory, it is believed that the organosilanes herein described, upon contact with water, form polymers which when present in sufficient amounts form a polymer network which serves to prevent or impede fluid (e g water) flow in or through the formation In contrast, in those parts of the formation mainly containing hydrocarbon (i e only low levels of water) little, if any, polymer may be formed and these parts of the formation are essentially unaffected by the treatment In this way, the permeability of those parts of the formation containing the highest levels of water may be reduced whilst the permeability of those parts containing mainly hydrocarbon (i e little water) essentially remain unchanged Hence any decrease in the overall permeability of the formation to hydrocarbon (e.g. oil) may be minimised Hence, unlike conventional prior art methods, the method of the invention does not rely upon the preferential partitioning of a water control agent into water, rather than hydrocarbon. Instead the water control treatment agent herein described may flow throughout the entire formation and selectivity may be achieved by the fact that sufficient polymer to block or impede fluid flow is only formed in regions comprising high levels of water. The method of the invention is accordingly more selective than those conventionally used Organosilanes for use in the invention are preferably dispersible or soluble in a hydrocarbon (e g a CI2J alkane) Still more preferably, the organosilanes for use in the invention are also at least partially water soluble (e g. water soluble) In some cases the material for use in the invention will be more soluble in hydrocarbon than in water More preferably, however, the organosilanes for use in the invention will be more soluble in water than in hydrocarbon. The organosilanes for use in the invention may, for example, partition between hydrocarbon and water at a ratio in the range 5 95 to 90.10, more preferably 10.90 to 7030, for example, about 40:60 The ability to partition in this way enables the organosilanes to be delivered to the formation in a hydrocarbon carrier (e g substantially without undergoing reaction) whilst at the same time enabling it to undergo reaction on contact with water at the desired point of action.

Organosilanes for use in the invention include, for example, organosilane hydrides, organosi lane alkoxi des and organosilane am ines Organosi lane compounds have the advantage that tlìey are typically oil-soluble and have the necessary reactivity with water These are also biodegradable and environmentally acceptable (e g. for DYNASYLAN AMEO LC50 fish = 934 mg/I, EC50 daphnia = 33 1 mg/I; IC50 algae = 603 mg/I, biodegradability 67 %, for DYNASYLAN his- AMEO LC50 fish >200 mg/I, EC0 daphnia >200 mg/I, IC50 algae = 125 mg/I, biodegradability 64 5 %, as tested according to OECD 306) Organosilanes for use in the invention preferably have a biodegradability of at least 60% Whilst not wishing to be bound by theory, it is believed that organosilane compounds undergo hydrolysis upon contact with water The resulting chemicals then react with each other as well as with siliceous surfaces in the formation (e g the surface of silica sand). The result is the formation of a polymer and in come cases a polymer network capable of blocking or impeding the flow of fluid Particularly preferred organosilane compounds include those having at least one hydrolysable bond. By a "hydrolysable bond' is meant a bond that is capable of being cleaved on reaction with water. Preferably the hydrolysable bond will be attached to a silicon atom. In other words, the hydrolysable bond is preferably between Si and a second atom/group in the molecule Still more preferably the hydrolysable bond is one which may hydrolyse to produce a silanol (i e. -Si -OH) It is believed that the hydrolysis of an organosilane may be critical to the success of the method herein described More specifically it is thought that the organosilane, upon contact with water in the formation, hydrolyses to form a silanol RRRS i- 0-Group + water ---> RRRSi-OH + HO-Group This silanol is then believed to react with other silanol molecules by forming -Si-0-Si- bonds and/or active sites (e g SiOH bonds) on the surface of the formation (e g sand particles) In fact the various reactions which the silanol molecules undergo serve to form a polymer that may act to impede or eliminate the movement of water through the formation (see Figure 1) Whilst reaction of a silanol molecule with the surface of the formation serves to covalently bond the organosilane to particles (see Figure 1 a) comprising the formation, the reaction between two silanols enables them to covalently bond to each other to form a dimer (see Figure Ib).

Subsequent reaction of the dirner with further silanols and/or the molecules of the formation facilitates the production of a polymer (see Figure Ic) and eventually formation of a polymer that substantially fills the space (e g pores) between the particles comprising the formation (see Figure id) In this way, the permeability of those parts of the formation comprising mainly water is substantially reduced.

Advantageously the method of the present invention also affords a polymer that is extremely stable (e.g it can withstand a wide range of pH, temperature and pressure), hence following treatment other conventional treatments and/or strategies to facilitate hydrocarbon recovery may be employed (e g use of a higher draw down) - 10 - The amount by which the permeability of the formation is reduced may depend on the extent of polymerisation and therefore on the number of bonds the organosilane forms with the particles of the formation and/or the extent to which reaction occurs between different organosilane compounds This, in turn, at least partially depends on how many silanol groups can be formed per molecule.

Preferred organosilane compounds for use in the invention comprise 1 to 12 hydrolysable bonds, more preferably 3 to 9 hydrolysable bonds, still more preferably about 6 hydrolysable bonds. Such compounds possessing hydrolysable bonds may well be able to self-condense and/or polymerise after hydrolysis of one or more of the hydrolysable bonds The aforementioned preferred numbers of hydrolysable bonds therefore relates to the number present in the monomeric form of the compound (I e one which has not undergone oligomerisation or polymerisation) For example, aminotriethoxysilane contains 3 hydrolysable bonds (1 e 3 x Si-OEt) and bis(triethoxysily1propyJ)amine contains 6 hydrolysable bonds (i e. 6 x SiOEt) In the organosilane compounds for use in the invention, the hydrolysable bonds present may be different, but more preferably are the same In preferred organosilane compounds for use in the invention at least one hydrolysable bond comprises part of a terminal group More preferably, all of the hydrolysable bonds comprise part of a terminal group By a "terminal group" is meant a group that is located at one end of the molecule This is in contrast to a side group or pendant group that is attached to another part of the molecule For example, in the compound aminotriethoxysilane the amino group and the -Si(OEt) groups are terminal groups In contrast in the compound bis-(triethoxysilylpropyl).

amine the -Si(OEt)3 groups are terminal groups, whereas the amine group is not In particularly preferred compounds for use in the invention all bonds other than the afore-mentioned hydrolysable bonds, are stable to the conditions to which it is exposed in use (e.g stable to hydrolysis in sea water) Preferably the remaining bonds in the molecule are carbon- carbon, carbon-hydrogen, silicon-carbon, nitrogen-carbon, oxygen-carbon and/or nitrogen-hydrogen bonds Preferred organosilane compounds may also include an amine group Whilst not wishing to he bound by theory the presence of the amine function is thought to result in better adsorption of the organosilane to the formation The presence of an amine group may therefore result in stronger adhesion of the organosilane to the particulates of the formation and/or increase the stability of the organosilane to high temperatures and/or pressures. This may be due to the fact that the amine group may form further bonds (e.g covalent, hydrogen and/or ionic bonds) between the organosilane and the formation and/or other organosilanes Preferably the amine is a primary amine (i.e - NT-I2), still more preferably a secondary amine (i.e. -NH-) Particularly preferred are those organosilane compounds which include more than one functional group, e.g. bifunctional organosilanes, or those compounds which are capable of self-polymerisatjon to produce bifunctional molecules By "bifunctjonal organosilane" is meant an organosilane comprising two separate Si atoms, each of which forms part of at least one hydrolysable bond Bifunctional organosilanes therefore advantageously afford, upon contact with water, at least two separate -Si-OH groups, which may each undergo any of the above-described reactions (e g with another silanol) Bifunctional organosilanes therefore increase the extent of polymerisation and therefore the size of the polymers produced Bifunctiona! organosilanes containing an amine group are particularly preferred Monofunctional organosilanes are also useful in the method of the invention By monofunctional organosilane is meant an organosilane comprising one Si atom that forms part of at least one hydrolysable bond. hi contrast to bifunctional organosilanes, monofunctional organosilanes tend to allow for less bonding to occur between different organosilanes, particularly those bound to different particles in the form ati on It is particularly preferred in the method of the invention to use a mixture of a bifunctional and a monofunctional organosilane For instance, the mixture may comprise a bifunctional to monofunctional organosilane ratio of 75 25 to 25:75, more preferably 60 40 to 40 60, still more preferably about 50 50 These ratios of bifunctional to monofunctional organosilanes have, in many cases, been found to yield the desired balance of providing sufficient polymer network formation to significantly reduce the permeability of the formation in areas of high water concentration without drastically reducing the formation's permeability in oil predominant areas This, in turn, enables hydrocarbon (e.g oil) to be extracted from treated wells more economically - 12- Representative examples of organosilanes that are suitable for use in the invention are organosilane alkoxides, organosilane esters, organosilane oximes, organosilane halides and organosilane hydrides. These compounds contain at least one -Si-OR, -S1O(O)CR, -SiO-N=CRR', -SiX and -SiH group respectively (wherein Rand R' may be C120 alkyl and Xis a halogen). Hydrolysis of compounds containing these groups yields, in addition to a silanol (i e. -Si-OH), - ROH, RC(O)OH, RtRC=zNOH -HX and -H2 respectively wherein R, R' and X are as hereinhefore defined.

Particularly preferred organosil ane compounds are organos ilane alkoxides and organosilane esters These undergo hydrolysis to afford, in addition to a silanol, alkanols and weak acids respectively Neither of these compounds generally cause problems (e g. due to side reactions) in hydrocarbon wells Preferred organosilane compounds for use in the Invention comprise a group of the formula - Si-OR wherein R is C12() alkyl, more preferably C26 alkyl, e.g ethyl Other preferred organosilane compounds comprise a group of the formula Si-O(O)CR wherein R is C12o alkyl, more preferably C26 alkyl, e g methyl.

Organosilanes suitable for use in the invention include those compounds of formula I R'R2R3Si-R4 (I) (wherein R', R2 and R3 are each independently selected from hydrogen and organic radicals having from 1 to 50 carbon atoms; and R4 is hydrogen, an organic radical having from I to 50 carbon atoms, or a group -OR5 in which R5 is an organic radical having from 1 to 50 carbon atoms, with the proviso that at least one of R', R2, R3 and R4 is other than hydrogen) In the compounds of formula I, R'-R5 are preferably selected from optionally substituted alkyl, alkenyl, aryl and alkoxy groups having from I to 1 8, preferably from 1 to 10, e g I to 6, carbon atoms Optional substituents which may be present include alkoxy (e.g C6 alkoxy), amino, silyl and silyloxy groups Particularly preferred organosilanes for use in the invention are those represented by formula II: (RO)3Si - (CH2) - A - (CH2) - Si(OR)3 (II) (wherein each R is independently a substituted or unsubstituted, preferably unsubstituted, alkyl group having from 1 to 18 carbon atoms, e g ito 6 carbons or a -COR group wherein R is as hereinbefore defined; 1 (1 A is an organic linking group or a group comprising an atom having a lone pair of electrons (e g a N, P or S atom); x is 0 or a positive integer, preferably from I to 10, more preferably 1 to 4, eg 2or3, and y is 0 or a positive integer, preferably from 1 to 10, more preferably I to 4, e.g 2or3).

In formula II, the function of group A is as a linking moiety and itsprecise chemical nature is of lesser importance provided this function is fulfilled Generally, however, it will comprise a chain 1 to 20 atoms long, preferably I to 10, especially I to 5 Examples of suitable linkers include both linear and branched alkylene chains which may be interrupted by heteroatorns such as nitrogen and oxygen In formula 11, x and y will generally be identical In preferred compounds of formula 11, R is a C1 alkyl group, more preferably a C24 alkyl group, for example, methyl or ethyl In particularly preferred compounds each R is the same Preferred compounds of formula II are also those wherein A is a group comprising an atom having a lone pair of electrons, especially nitrogen Preferably A will be a group -NH or -NR6 where R6 is C16 alkyl Unless otherwise specified, any alkyl, alkenyl or atyl group referred to herein may be mono- or poly-substituted and, with the exception of aryl, may be branched or unbranched Other preferred organosilanes for use in the invention are those represented by formula Ill.

(III) (wherein R7 and R8 are independently hydrogen or a substituted or unsubstituted, preferably unsubstituted, alkyl group having from I to 6 carbon atoms; z is a positive integer, preferably from I to 20, more preferably I to 8, e.g 3 or 8, a is zero or a positive integer from I to 3, preferably 0 or I (e g 0), R9 is a substituted or unsubstituted, preferably unsubstituted, alkyl group having from I to 6 carbon atoms (e. g C1), and R is as hereinbefore defined in relation to formula II) in preferred compounds of formula III, at least one of R7 and R8 is hydrogen More preferably both R7 and R8 are hydrogen Further preferred compounds of formula III are those wherein z is at least 2, still more preferably z is at least 3 (e.g z is 3).

It is particularly preferred in the method of the invention to use a mixture of a compound of formula H and a compound of formula 111 For instance, the mixture may comprise a compound of formula II to a compound of formula Ill in a ratio of 75 25 to 2575, more preferably 60 40 to 40 60, still more preferably about 50 50 Suitable organosilanes include 3-amino-propyltriethoxysi lane, bis(triethoxysi I ylpropyl)amine, 3 -(diethoxymethylsilyl)propylamine trimethoxyoctylsilane, triethoxyoctylsilane, 4,4,15,1 5-tetraethoxy-3, 16- dioxa- 8,9,10,1 l-tetrathia-4, 1 5-disilaoctadecane, and any combination thereof Such compounds are available commercially, e g from Degussa (Hanau, Germany) under the tradenames DYNASYLAN 1126, DYNASYLAN 1122, DYNASYLAN 1506, DYNASYLAN OCTMO, DYNASYLAN OCTEO, DYNASYLAN AMEO and Si 69 A preferred combination of organosilanes for use in the invention is that comprising 3-am inopropyltriethoxys i lane and bis(triethoxy si lylpropyl)amine, preferably in a ratio of 75 25 to 25 75, more preferably 60 40 to 40 60, still more preferably about 50 50 A particularly preferred mixture is that sold under the tradename DYNASYLAN 1126 - 15- The amount of organosilane to be used will vary widely depending on factors such as the nature of the particular organosilane used, the nature (e g. permeability, temperature, etc) of the rock formation, the volume of water naturally present and so on. In general, the amount of organosilane used will be sufficient to reduce the permeability of at least part of the formation (e.g water-rich regions) such that hydrocarbon can be produced economically and appropriate amounts may readily be determined by those skilled in the art The organosilanes for use in the method of the invention are preferably applied as a dispersion or solution in a liquid carrier Thus the water control treatment agent preferably comprises a liquid carrier The liquid carrier may be aqueous or non-aqueous Preferably, this will comprise a non-aqueous organic liquid, e g a hydrocarbon or hydrocarbon mixture, typically a C to C15 hydrocarbon, or oil, e g crude oil or lamp oil Other suitable carrier liquids include aromatic hydrocarbons such as naphtha and diesel Diesel is particularly preferred In the water control treatment agent of the invention it is generally preferred to use a hydrocarbon carrier since these this will minimise the exposure of the organosilane to water l'his means that reaction (e.g hydrolysis) during passage down into the well to the formation to be treated is minimised or prevented.

Preferably the hydrocarbon carrier is substantially anhydrous For example the hydrocarbon carrier preferably contains less than 5 % water, more preferably less than 2 % water, still more preferably less than 0 5 % water, e.g less than 0 1 % water Thus, viewed from a further aspect the invention provides a water control treatment agent comprising (e g consisting essentially of) an organosilane as hereinbefore defined and optionally a substantially anhydrous hydrocarbon carrier, wherein said organosilane is present in an amount effective to control water in a subterranean formation, e g to reduce the water permeability of at least part of said formation, preferably whilst minimising any decrease in the overall hydrocarbon (e g oil) permeability of the formation Preferably, the water control treatment agent for use in the invention will be substantially free from other polymer materials such as the hydrophilic polymer materials proposed in the prior art The water control treatment agent may, for - 16 - example, be substantially free from polymer material other than that formed by polymerisation of the organosilane therein. For example, the amount of any other polymer material will typically be less than 10 wt.%, preferably less than 0.5 wt.%, e g. less than 0.1 wt.%.

Suitable hydrocarbon carrier liquids include crude oil, base oil, lamp oil, an aliphatic hydrocarbon (e.g. hexane), an aromatic hydrocarbon (e.g. benzene or toluene) or a petroleum distillation product or fraction (e g kerosene, naphthas or diesel fuel) Preferably the hydrocarbon comprises a petroleum distillation product, especially diesel fuel The liquid carrier (e g hydrocarbon carrier) may also contain other additives known in the art for use in well treatment Such additives may include surfactants, thickeners, diversion agents, pH buffers and catalysts Preferably the carrier does not contain a catalyst and/or a polymer, especially a polymer. It will be appreciated that the organosilanes for use in the invention are capable of forming polymers upon contact with water in the formation Thus the preferred absence of a polymer refers to the water control treatment agent prior to its contact with water. Still more preferably the water control treatment agent consists essentially of (e g consists of) an organosilane and a liquid (e g hydrocarbon) carrier Preferably, the concentration of the organosilane in the liquid carrier will be in the range of 0 05-50 % w/v, preferably 10 to 30% w/v, more preferably 20 to 25 % w/v, e.g about 25 % w/v A higher concentration will generally be used for deeper perforations Typically about 50 to 1000 litres (e g 100 to 400 litres) of hydrocarbon carrier per m of formation to be treated will be used It is envisaged that treatment with an organosilane in accordance with the method herein described could be at any stage in hydrocarbon production, i e before and/or after hydrocarbon production (i e extraction of oil or gas from the well) has begun In some cases, the treatment will be prior to hydrocarbon production in order to facilitate maximum extraction of hydrocarbon More preferably, treatment is carried out once a water problem (e g coning or channeling) is identified or potential for a water problem is identified It may often be beneficial to carry out treatment in accordance with the invention before water production becomes severe Nevertheless the treatment method herein described may be repeated as necessary in - 17- order to minimise or prevent water production Thus, a well may be treated prior to production and then again after a potential water problem is identified.

Other conventional well treatments such as stimulation treatment, hydraulic fracture treatment and scale reduction treatment may also be used in conjunction with the method of the invention These may precede or follow the method of the invention Preferably, however, the well is ready to be put back onto production immediately after treatment in accordance with the method of the invention.

Treatment is conducted by contacting the formation with a water control treatment agent, generally through a well bore, and typically employing pressures sufficient to penetrate the fonnation By contacting' is meant pumping, injecting, pouring, releasing, circulating or otherwise placing the water control treatment agent within a well, well bore and/or formation Any method known in the art may he used. Treatment times or period of shut-in will depend on a number of factors including the nature of the formation and the volume of water present, the nature and concentration of the organosilane employed, the depth of perforations, etc Typical shut-in times may be determined by those skilled in the art and will generally range from 2 to 10 hours, preferably from 3 to 8 hours, e g about 4 to 6 hours Any conventional treatment methods may be used to supply the water control treatment agent to the well Such methods will include bull -heading and coil tubing Preferably zonal isolation (e g with packers) is not required. Of these methods, bull-heading will generally be preferred This is in contrast to many prior art methods where treatment chemicals are generally placed at various points in the formation, e.g placed by coiled tubing to spot this at the desired site This is a more costly operation to perform An advantage of bull-heading is that the whole well is treated and at relatively low cost Bull-heading can be used for treatment of both vertical and horizontal wells and treatment can be effected during short production intervals Suitable injection flow rates may be readily determined by those skilled in the art, however preferred flow rates may lie in the range 2500 to 3000 litres/mm In general, the injection flow rate will not be lower than about 500 litres/rn in Coiled tubing (CT) methods are less desirable for economic reasons but may nevertheless be successfully used to supply the materials to the well. Such methods are generally more appropriate for treating long horizontal sections of the well.

Suitable CT methods include those conventionally used in the field, e.g. roto pulse method, concentric coiled tubing, etc. In a preferred method of the invention the water treatment agent is shut-in following its entry into the formation. The shut-in period is a function of the conditions in the well (e g. temperature, pressure etc) which affect the rate at which polymerisation of the organosilane occurs. Typically, however, the shutin period will be from 3 to 24 hours, preferably 4 to 12 hours, for example, 6 to 9 hours Following shut in, the well is preferably put back onto production Preferably the ratio of water to hydrocarbon then produced is lower than that prior to the treatment For example, the v/v ratio of hydrocarbon to water is preferably at least 20 80, more preferably at least 30 70 (e g l090 to 95.5) since at these ratios hydrocarbon can generally be produced economically Thus, viewed from a further aspect the invention provides a method of treating a water and hydrocarbon producing subterranean formation whereby to reduce (preferably by 5 to 90 %, more preferably by 10 to 95 %, e g by at least 40 %) the amount of water produced therefrom during hydrocarbon recovery, said method comprising (a) providing a water control treatment agent comprising an organosilane as hereinbefore described, and (b) contacting said formation with an amount of said agent effective to reduce the amount of water produced therefrom during hydrocarbon recovery The process of the invention is particularly effective in increasing tail- end production in more mature wells where the ratio of water to hydrocarbon produced is high (e g 80 20 v/v or more) Hitherto, such wells would tend to he shut down once the production rate of water reaches a level at which the cost of handling the water outweighs the value of the hydrocarbon (e g oil) recovered However, by treating these wells in accordance with the method herein described the production of water may be reduced to the extent that economic production from the well may be continued In this way the lifetime of the well can be prolonged and the huge costs involves in establishing a new formation are avoided or at least delayed - 19- It is also envisaged that the method of the present invention may be used to treat (e.g. "shut off') a water-rich subterranean formation, e g. a subterranean formation from which hydrocarbon production has been completed. Very little, if any, hydrocarbon may remain in such a formation, therefore high levels of water are usually present As a result when treatment in accordance with the method of the invention is carried out, the entire formation contacted with the agent tends to become blocked or plugged In this way, both the water and hydrocarbon permeability of the formation may be reduced and the movement of fluid (e g water) into other parts of the formation or connected formations may be prevented Thus viewed from a still further aspect the invention provides a method of sealing or plugging a water-rich (e g oil depleted) subterranean formation, said method comprising contacting said formation with a water control treatment agent which comprises an organosilane as hereinbefore defined in an amount effective to reduce the permeability of said formation.

In a preferred embodiment of this aspect of the invention, the water permeability of the formation is decreased by at least 80 %, more preferably by at least 90 %, still more preferably by at least 99 % In a further preferred aspect, the hydrocarbon permeability is also decreased (e.g by at least 80 %, more preferably by at least 90 %, still more preferably by at least 99 %) Still more preferably, this aspect of the invention affords an essentially impermeable formation Typically the formation to be treated will be "water-rich" as a result of prior extraction of hydrocarbon If necessary, however, additional water may be introduced (e g injected) into the formation prior to addition of the water control treatment agent to maximise polyrnerisation and ensure synthesis of an extended polymer network As mentioned above, the polymer formed by the treatment agent is extremely stable (e g it can withstand a wide range of pH, temperature and pressure), hence following treatment in accordance with the method of the invention the formation may remain plugged or scaled for many years without need for follow up treatments Application of the methods of the Invention is particularly suited to formations comprising a multi-layered structure (e g a sandstone structure) with two or more layers that are saturated with hydrocarbon, more particularly to such - 20 - structures in which there is no cross flow between the layers. However, any formation structure having watered out conditions may be treated in accordance with the method of the invention. Treatment in accordance with the method of the invention may be especially useful in formations wherein the formation permeability is about 10 mDarcy to 15 Darcy, preferably 0 5 to 5 Darcy The invention will now be described further with reference to the following non-limiting Example: -21 -

Example I

The ability of 25 % vol DYNASYLAN 1126 (Degussa AG, Germany) to reduce the permeability of Heidrun sand was tested using a cylindrical sand pack holder as illustrated in Figure 2 and having the following dimensions. 209 mm (length) x 65 mm (diameter) and a total sand volume of 157 cm2 The sand pack holder was connected with differential pressure transducers and placed inside a heating cabinet.

A pulse-free pump was used to generate a flow velocity of I or 2 mI/mm Experimental procedure The sand (Heidrun sand) was packed in the sleeve and the sand pack vertically oriented 2 The line and sleeve pressures were 15 and 55 bar respectively 3 10 pore volumes (PV) of formation water (FW) were injected (1 mI/mm) from the bottom of the vertical sand pack 4 was measured 5. S was established by injection of lamp oil from the top of the sand pack 6 K0 was measured 7 S was established by injection of FW from the bottom of the sand pack 8 K at S was measured 9 3 PV of 25 vol% DSI 126 in lamp oil was injected (2 mI/mm) into the sand pack 1 0 The heating cabinet was heated to 85 C 11 The core was shut-in for 3 hours after the core reached 85 C 12 Lamp oil was injected 13 K0 was measured.

- 22 - Results: Pre-treatment K0 = 2 54 Darcy (as measured at step 6) K, = 3 47 Darcy (as measured at step 8) Post-treatment K0 < I m Darcy (the differential pressure was higher than the measuring limit of the pressure transducer therefore it can be concluded that K0 is less than 1 mDarcy) This corresponds to a reduction in permeability to oil of more than 99 96% K could not be measured as the flow of water was completely blocked The reduction in permeability to water is therefore 100% Discussion: The results show that DYNASYLAN 1126 is capable of reducing the water permeability of a water-saturated sand formation At the same time, oil permeability was also significantly reduced In contrast a selective reduction in water permeability occurs in those formations comprising a mixture of hydrocarbon and water prior to treatment

Claims

- 23 - Claims: 1 A method of controlling water in a subterranean

formation, said method comprising contacting said formation with a water control treatment agent which comprises an organosilane in an amount effective to reduce the water permeability of at least part of said formation 2. A method as claimed in claim 1, wherein any decrease in the overall hydrocarbon (e g oil) permeability of said formation is minim ised 3 A method as claimed in claim I or claim 2, wherein the permeability of water-rich regions of said formation is reduced 4 A method as claimed in any preceding claim, wherein the water permeability of said formation is reduced by 40-100 %, preferably 60-100 % A method as claimed in any preceding claim, wherein the hydrocarbon (e g oil) permeability of said formation is reduced by 0-50 %, preferably 0- 30 %.

6 A method as claimed in any preceding claim, wherein the production of water from said formation is reduced by at least 10 % 7 A method as claimed in any preceding claim, wherein said water control treatment agent is substantially free from any polymer 8 A method as claimed in any preceding claim, wherein the organosilane is an organosilane hydride, an organosilane alkoxide or an organosilane amine 9 A method as claimed in any preceding claim, wherein said organosilane comprises an amine group 10. A method as claimed in any preceding claim, wherein said organosilane is bifunctional II A method as claimed in any preceding claim, wherein the organosilane comprises a compound of formula I R'R2R3Si-R4 (I) (wherein R', R2 and R are each independently selected from hydrogen and organic radicals having from 1 to 50 carbon atoms, and R4 is hydrogen, an organic radical having from I to 50 carbon atoms, or a group -OR5 in which R5 is an organic radical having from I to 50 carbon atoms, with the proviso that at least one of R', R2, R3 and R4 is other than hydrogen) 12 A method as claimed in claim 11, wherein in formula I, R is -OR5 where R5 is C1 alkyl, e.g C16 alkyl 13 A method as claimed in any one of claims I to 10, wherein the organosilane comprises a compound of formula II.

(RO)Si - (CH2) - A - (CH2) - Si(OR)3 (U) (wherein each R is independently a substituted or unsubstituted, preferably unsubstituted, alkyl group having from I to I 8 carbon atoms, e.g 1 to 6 carbons or a -COR group wherein R is as hereinbefore defined, A is an organic linking group or a group comprising an atom having a lone pair of electrons (e g a N, P or S atom), x is 0 or a positive integer, preferably from 1 to 10, more preferably 1 to 4, e.g. 2or3; and y is 0 or a positive integer, preferably from 1 to 10, more preferably I to 4, eg. 2or3).

14 A method as claimed in any one of claims Ito 10, wherein the organosilane comprises a compound of formula III: R94(RO)3aSj -(CH2)7NR7R8 (III) (wherein R7 and Rx are independently hydrogen or a substituted or unsubstituted, preferably unsubstituted, alky! group having from 1 to 6 carbon atoms, z is a positive integer, preferably from 1 to 20, more preferably I to 8, e g 3 or 8, a is zero or a positive integer from 1 to 3, preferably 0 or 1 (e.g 0), R9 is a substituted or unsubstituted, preferably unsubstituted, alkyl group having from Ito 6 carbon atoms (e.g Ci); and R is as hereinbefore defined in relation to formula 11) I S A method as claimed in any one of claims I to I 0 wherein said material comprises a mixture of a compound of formula 11 and a compound of formula 111 16 A method as claimed in any one of claims Ito 10, wherein the organosilane comprises 3 -aminopropyltriethoxysjlane, bis(triethoxysilylpropyl)atnjne, 3- (diethoxymethylsilyl)propylamine trimethoxyoctylsilane, triethoxyoctylsilane, 3- aminopropyltriethoxysi lane 4,4, 15,1 5-tetraethoxy-3, I 6-dioxa-8,9, 10, 11 -tetrathia- 4, I S-disilaoctadecane, or any combination thereof 17 A method as claimed in any preceding claim wherein said water control treatment agent further comprises a substantially an hydrous hydrocarbon carrier 1 8 Use of a water control treatment agent comprising an organosilane in a method of controlling water in a subterranean formation, said method comprising contacting said formation with said agent in an amount effective to reduce the water permeability of at least part of said formation, preferably whilst minimising any decrease in the overall hydrocarbon (e.g oil) permeability of said formation, 19. Use of an organosilane as a water control treatment agent to control water in a subterranean formation wherein said agent is effective to reduce the water permeability of at least part of said formation, preferably whilst minimising any decrease in the overall hydrocarbon (e g. oil) permeability of said formation 20 A method of treating a water and hydrocarbon producing subterranean formation whereby to reduce the amount of water produced therefrom during hydrocarbon recovery, said method comprising (a) providing a water control treatment agent comprising an organosilane, and (b) contacting said formation with an amount of said agent effective to reduce the amount of water produced therefrom during hydrocarbon recovery 21 A water control treatment agent comprising an organosilane in an amount effective to control water in a subterranean formation, e g by reducing the water permeability of at least part of said formation, preferably whilst minimising any decrease in the overall hydrocarbon (e g. oil) permeability of said formation 22 A method of sealing or plugging a water-rich subterranean formation, said method comprising contacting said formation with a water control treatment agent which comprises an organosilane in an amount effective to reduce the permeability of said tormation Amendments to the claims have been filed as follows 1 A method of controlling water in a subterranean formation, said method comprising contacting said formation with a water control treatment agent which comprises a substantially anhydrous hydrocarbon carrier and an organosilane in an amount effective to reduce the water permeability of at least part of said formation 2 A method as claimed in claim I, wherein any decrease in the overall hydrocarbon (e.g oil) permeability of said formation is minimised.

3 A method as claimed in claim I or claim 2, wherein the permeability of water-rich regions of said formation is reduced r(t 4 A method as claimed in any preceding claim, wherein the water permeability of said formation is reduced by 40-100%, preferably 60-100% A method as claimed in any preceding claim, wherein the hydrocarbon (e.g oil) permeability of said formation is reduced by 0-50 %, preferably 0-30 % 1 6 A method as claimed in any preceding claim, wherein the production of water from said formation is reduced by at least 10 % 7 A method as claimed in any preceding claim, wherein said water control treatment agent contains less than 10% wt of polymer material other than that formed by polymerisation of the organosilane therein 8 A method as claimed in any preceding claim, wherein the organosilane is an organosilane hydride, an organosilane alkoxide or an organosilane amine 9 A method as claimed in any preceding claim, wherein said organosilanc comprises an amine group A method as claimed in any preceding claim, wherein said organosilane is bifunctional.

11. A method as claimed in any preceding claim, wherein the organosilane comprises a compound of formula 1: RR2R3Si-R4 (I) (wherein R1, R2 and R3 are each independently selected from hydrogen and organic radicals having from 1 to 50 carbon atoms; and R4 is hydrogen, an organic radical having from I to 50 carbon atoms, or a group -OR5 in which R5 is an organic radical having from I to 50 carbon atonis, with the proviso that at least one of R', R2, R3 and R4 is other than hydrogen) 12 A method as claimed in claim 11, wherein n formula I, R4 is *-0R5 where R5 is C1 alkyl, e g C1 aikyl.

13 A method as claimed in any one of claims I to 10, wherein the organosilane comprises a conipound of formula IT (RO)3Si - (CIi2) - A (CH2) - Si(OR)3 (II) (wherein- each R is independently a substituted or unsubstituted, preferably unsubstituted, alkyl group having from I to I 8 carbon atoms, e g I to 6 carbons or a -COR group wherein R is as hereinbefore defined, A is an organic linking group or a group comprising an atom having a lone pair of electrons (e.g aN, P or S atom); x is 0 or a positive integer, preferably from 1 to 10, more preferably 1 to 4, eg 2or3, and y is 0 or a positive integer, preferably from I to 10, more preferably I to 4, eg. 2or3) 14 A method as claimed in any one of claims Ito 10, wherein the organosilane comprises a compound of formula 111.

R9a(RO)3.aSj(CH2)7NR7 R (III) (wherein R7 and R8 are independently hydrogen or a substituted or unsubstituted, preferably unsubstituted, alkyl group having from 1 to 6 carbon atoms; z is a positive integer, preferably from 1 to 20, more preferably 1 to 8, e g 3 or 8, a is zero or a positive integer from 1 to 3, preferably 0 or 1 (e g 0), R9 is a substituted or unsubstituted, preferably unsubstituted, alkyl group having from Ito 6 carbon atoms (c g C1), and R is as hereinbefore defined in relation to formula ii) 1 5 A method as claimed in any one of claims 1 to 1 0 wherein said mateiial comprises a mixture of a compound of formula II and a compound of formula lii 16 A method as claimed in any one of claims 1 to 10, wherein the organosilane comprises 3-aininopropyltriethoxysilane, bis(triethoxysilylpropyl)amine, 3- (diethoxymcthylsilyl)propylamine, trimethoxyoctylsilane, triethoxyoctylsilane, 3- aminopropyltiethoxysi1ane, 4,4, 1 5,1 5-tetraethoxy-3, I 6-dioxa-8,9, 1 0, 11 -tetrathia- 4,1 5-disilaoctadecane, or any combination thereof.

17 A method of treating a water and hydrocarbon producing subterranean formation whereby to reduce the amount of water produced therefrom during hydrocarbon recovery, said method comprising (a) providing a water control treatment agent comprising a substantially anhydrous hydrocarbon cariier and an organosilane, and (b) contacting said formation with au amount of said agent effective to reduce the amount of water produced therefrom during hydrocarbon recovery 18 A water control treatment agent comprising a substantially anhydrous hydrocarbon carrier and an organosilane in an amount effective to reduce the water permeability of at leat part of a subterranean, formation.

1 9 A treatment agei.ut as claimed in claim 18, wherein any decrease in the overall hydrocarbon (e.g oil) permeability of said formation is minirnised A method of sealing or plugging a water-rich subterranean formation, said method comprising contacting said formation with a water control treatment agent which comprises a substantially anhydrous hydrocarbon carrier and an organosilane in an amount effective to reduce the permeability of said formation 21 A method as substantially hereinbefore described and/or with reference to

the example

22 A water control treatment agent as substantially hereinbefore described andlor with reference to the example