CA2208440A1 - Oil and gas field chemicals - Google Patents
Oil and gas field chemicalsInfo
- Publication number
- CA2208440A1 CA2208440A1 CA002208440A CA2208440A CA2208440A1 CA 2208440 A1 CA2208440 A1 CA 2208440A1 CA 002208440 A CA002208440 A CA 002208440A CA 2208440 A CA2208440 A CA 2208440A CA 2208440 A1 CA2208440 A1 CA 2208440A1
- Authority
- CA
- Canada
- Prior art keywords
- copolymer
- composition
- water soluble
- soluble copolymer
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
Abstract
A composition for conformance of an oil or gas field reservoir consists of (i) at least one non acidic ethylenically unsatured polar monomer such as acrylamide, and (ii) at least one copolymerisable ethylenically unsaturated ester such as an alkyl or aralkyl acrylate which is gelled in the reservoir using a polyvalent metal ion gelling agent such as a chromium or zirconium salt.
Description
Oil and Gas Field Chemir,~l~
The present invention relates to polymers and their plel)al~ion and their use in oil and gas fields.
Oil and gas fields produce water as well as oil and/or gas, especially when the well is depleted. In addition, secondary recovery techniques such as water flooding to stim~ te production of oil involve injection of water under pressureat a ~i~t~nre from a production well to sq~ler7:e the oil out. However, in both cases the water moves in the formation along least hindered paths, so that the recovery technique may be inefficient and in the direct recovery increased proportions of water are produced.
To enh~nre reservoir co.~~ ce control, i.e. mobilise the oil that may be present in less permeable areas, blocking agents may be injected to obstruct thehigh permeability r.h~nnel~ thereby encouraging plererence for liquid movement via the lower permeability r.h~nnrl~ Among known blocking agents are polymer gels, in particular, gels of polyacrylic acid or polyacrylamide/polyacrylic copolymers, cross-linked with cl~OIl~iulll ions as di~cl(!sed in US Patents 4,744,418 and 4,844,168. The copolymer, mixed with cross-linker, is injected into the formation from the production well, often after a flood of cold water to pre-cool the formation rock, to stop premature cross-linking and gelling before the mixture reaches its desired position. Much work has been described to reduce the rate of cross-linking, by red~lcing the activity of the cross-linking metal ion, e.g. by co-o~ A~ g the chromium with a ligand, e.g. lactate.
An improved cross-linking system has now been discovered which comprises a composition in which the tendency of the polymer to cross-link prematurely has been reduced further by use of a copolymer of a polyacrylamide with a polar monomer.
The present invention provides a water soluble copolymer of:
(i) at least one non acidic ethylenically unsaturated polar monomer and ~ii) at least one copolymerisable ethylenically unsaturated ester.
The invention also comprises composilions comprising the water soluble copolymer and a polyvalent metal ion gelling agent.
The present invention also provides a process for delaying the rate of gelling of an acrylic polymer with a gelling agent, in which the acrylic polymer is said copolymer comprising (i) and (ii).
The invention also provides a method for co~ llallce control of a reservoir, especially one with high formation teml,e~ res, which method colll~lises:
(a) injecting into the formation an aqueous solution of said composition, (b) allowing the solution to flow through at least one zone of high permeability in said formation under increasing telll~w~lule conditions, (c) allowing the composition to gel under said con~itions.
The copolymer is formed from at least one, e.g. 1-3 polar ~llolloll.~l(s) and atleast one, e.g. 1-3 ester(s), and comprises structural units derived from said monomer(s) and ester(s); p.e~.~bly the copolymer consists e~senti~lly of said structural units. The ester is ~ulJsl~lially neutral as it is a fully esterifiedderivative of an acid, i.e. complete ester, rather than a partial ester with free acid group(s).
The ester is usually formed from a hydroxyl compound and an ethylenically unsaturated carboxylic acid. The ethylenically ullsa~ul~led group may be in the alpha-beta or beta gamma position relative to the carboxyl group or may be further distant; p~re~ d acids have 3-20 carbons, such as 3-12, e.g. alkenoic and aralkenoic acids with 3-6 or 9-12 carbons respectively. Examples of the acids are acrylic, meth~r.rylic, crotonic and rinn~mic acids. The hydroxyl compound is usually an alcohol and may be of formula ROH, where R is a hydrocarbyl group, preferably an alkyl group, e.g. of 1-30 or 2-30 such as 1-6, 2-6, 7-30 or 7-24 carbons, alkenyl groups, e.g. of 2-20 carbons such as 2-6 carbons, cycloalkyl group, e.g. of 5-8 carbons, aryl group, e.g. aromatic hydrocarbyl group such as 6- y 20 carbons or aralkyl group, e.g. of 7-24 carbons. Examples of such R groups are methyl, ethyl, n- and iso propyl, n, sec, iso and tert butyl, n, sec, iso and tert amyl and hexyl, octyl and 2-ethylhexyl, decyl, allyl, cyclohexyl, palmityl, steryl, phenyl and benzyl. The R group may also be a hydrocarbyl group, subsLiLuLed by at least one substituent e.g. 1-3 substitll~nt~, especially from hydlo~yl, ether, and thio ether groups; electron donating groups are pler~ d. Ether substitllçntc areprtrelled, especially alkoxy, aryloxy and aralkoxy, in which the alkyl, aryl andaralkyl groups may be as described above. Preferably the sub~LilLIell~ is on thesame carbon atom of the R group as is bonded to the hydroxyl group in the hydroxyl compound; alkoxymethyl and aralkoxy methyl groups are plerellèd.
The hydroxyl compound may be a primary, secondary, iso or tertiary compound, especially with a tertiary carbon atom bonded to the hydroxyl group, e.g. tert butyl and trityl. The group R may also comprise a heterocyclic group either for bonding directly to the hydroxyl group of ROH or separated ~helerlolll by an alkylene group, e.g. of 1-4 carbons such as methylene. Thus group R may be a saturated or unsaturated heterocyclic or heterocyclic alkylene group, e.g. of 3-8 carbons and at least one, e.g. one or two ring heteroatoms selected from 0, N and S, especially 0 and/or N, examples of such groups are furyl, tetrahydrofuryl, furfuryl and tetrahydrofurfuryl, pyranyl and tetra hydlopyl~lyl. Most pl~r~;llèd R
groups are tert-butyl, trityl, metho~yln~;~hyl, benzyloxymethyl and tetrahydl~yl~lyl; stearyl, iso propyl, ethyl and methyl may also be pl~relled.
The ester (i) may also be derived from a hydroxyl compound, e.g. of formula ROH and an ethylenically unsaLuldled sulphonic or phosphoric acid, which may contain 2-20 carbons, especially 2-6 carbons, such as alkenyl acids, e.g. vinyl sulphonic acid and vinyl phosphonic acid. Thus the ester may be methyl or ethyl vinyl sulphonate or phosphonate. The ester may be derived from an acid cor.l~;.,h-p~ an ethylenically unsaturated carboxamide (e.g. acrylamido) group, as well as the sulphonic or phosphonic acid group; an example of such an acid is 2-acrylamido-2-1ll~lhylplopalle sulphonic acid.
The ester is copolymerised with an ethylenically unsaturated polar monomer, in which the unsaturated group is usually vinyl or alpha methyl vinyl and may be derived from an unsaturated carboxylic acid (the acid being as further describedabove) e.g. ~l;m~y, secondary or tertiary amide thereof, in which the amide is derived from ~mmoni~ or a plillla y or secondary alkylamine, e.g. of 1-10 carbons, which may optionally be substituted by at least one hydroxyl group as in alkylol amides such as eth~nol~mides; examples of such carboxylic derived polar CA 02208440 l997-06-20 monnm~.rs are acrylamide, meth~r.rylamide and acrylic ethanol amide. The polar monomer may also be a vinyl heterocyclic compound e.g. with at least one 0, S orN atom in a ring with 3-8 carbons such as one with at least one carbonyl group in the ring, e.g. N-vinyl-pyrrolidone or -caprolactam, or a vinyl pyridine.
The copolymer may contain 0.01-50% e.g. 0.1-40% or 1-30%, especially 5-15%
mol of structural units from said ester(s) and 99.99-50% e.g. 99.9-60% or 99-70 or 95-85% mol of structural units from said polar monomer(s). The copolymer may be a block or non block copolymer, e.g. a regular or random copolymer or a graft copolymer, especially with ester units gra~ed onto polymeric polar, mnnom~.r, e.g. ester grafted on polyacrylamide.
The copolymer is usually soluble in water to an extent of at least lg/1 e.g. 1-200g/1 such as at least lOg/1 in distilled water at 15~C, especially in aqueous sodium chloride solution co~ ,;,.g 32g/1 NaCI at 25~C. If desired, the copolymer may be mixed with a surfactant (e.g. in amount of 0.01 - 5% by wt of the solution) to help solubilise it in the water or sodium chloride solution.
The copolymer may have a weight average molecular weight of at least 50,000 e.g. 50,000-20 million, such as 100,000 to 10 mi~ion, especially 100,000-500,000or 1-10 million; the molecular weight may be determined by conventional methods, e.g. gel permeation chlomalography or intrinsic viscosity. The low mole wt copolymer may have a viscosity in aqueous 3.6% wt solution at 19~C of 10-500 CpS (measured at 60 rpm with a Haake viscometer). Preferably the copolymer is sheer thinnable, e.g. with the viscosity reducing by at least 10% on inGIeasi~lg the sheer rate by 10%.
The copolymer may be made by conventional methods for copolymerising ethylenically unsaturated monomers in solution, emulsion or suspension, (preferably aqueous~, such as are described in Encyclopaedia of Polymer Science & Fn~illee~ g~ Ed. Mark, Bikales, O~/e~bel~,el and Menges, Publ. Wiley Interscience, New York, 2nd Ed., Vol 1, pp 181-211 and references cited therein,especially L J Young in J Brandrup and E H Immergut Eds Polymer Handbook, J
Wiley, New York, 2nd Ed. 1975, Sec. II and 3rd Ed. Sec. m, especially pp 155/6 and references cited therein and R Z Greenley J Macromol Science Chem. 14, 427, 445 (1980) and G Saini et al Makromol, Chem. 144, 235 (1971), the disclosure of each of which is incorporated herein by reference. Free radical aqueous suspension or emulsion polymerisation is plerel.~d.
The composition of the invention comprises the copolymere and a polyvalent metal ion, capable of cros~linking an acrylic acid polymer in aqueous solution to form a gel. The cross-linking may be at 20-200~C, especially 50-150~C. The metal ion is usually 2, 3 or 4 valent and may be of group 2A, 3A, 4A, 5A, 6A, 7A, 8, 2B, 3B or 4B of the Periodic Table, e.g. Ca, Mg, Ba, Ti, Zr, Fe, Zn, A1 or Sn; preferably the metal ion is 3 or 4 valent and is especially a transition metal such as chromium or iron, though ~lllmininm may also be used. The particularly pler~;;llt;d metals are chromium and zirconium. The weight ratio of the metal tocopolymer is usually 1:1-100 such as 1:10-80, especially 1:25-50. The ratio of the number of g atoms of metal to g moles of copolymer is usually 1000:0.001-100, preferably 1000:0.01-10, such as 1000:0.1-20 or 1-lO, especially for copolymers of Molec. Wt 100,000 - 500,000. The ratio of the number of g atoms of metal to equivalents of ester group in the copolymer is usually 1000:0.5-5000, preferably 1000:5-5000 such as 1000:50-1000 or 1000:500-5000. The metal is usually present as a salt, e.g. an h~ol~l ic salt such as a halide especially chloride, nitrate or slllph~te or as a carboxylate particularly a monodentate carboxylate, such as a hydrocarbyl monocarboxylate, e.g. with 1-24 carbon atoms (e.g. 2-6) in the carboxylic acid, which may be an alkanoic acid such as acetate.
The metal may also be complexed, e.g. with a ligand, such as a carboxylic acid group, having at least 2, e.g. 2-4 dentate groups in particular, as described inC~n~ n Patent 2063877, the disclosure of which is herein incorporated by ;rerence; example of complexing carboxylic acids are hydroxy alkanoic acids, e.g. Iactate, glycollate or tartrate. The salt or complex is water soluble. The composition is usually made just before use by adding the copolymer and the metal ion (e.g. as salt or complex) to an aqueous medium, e.g. sea water and then injecting the aqueous composition made into the formation. The composition is pr~;rt;l~bly kept at below 50~C, e.g. below 30~C before use. The concentration of coplymer in the aqueous composition may be 500-100,000 ppm, in particular 500-10,000 ppm for copolymers of high Molecular wt of at least 1 million and 10,000-50,000 ppm for copolymers of lower Molecular wt. 50,000-1 CA 02208440 l997-06-20 million. The conce.l~.~lion of the cross-linking metal ion in the aqueous composition may be 10-3000 ppm, especially 10-250 ppm and 3000-1500 ppm respectively for said high and low Molec wt copolymers.
The aqueous composition may be injected into the formation via a producing well or via a secondary injection well (for use with a waterflood or squeeze technique). The aqueous composition may also contain other ingredients, e.g.
~ntio~ nt~ and/o-o~ygel scavengers. The injection may, if desired, be preceded by a precooling tr~tm~.nt7 e.g. coldwater to stop pl~;ll-aL,l-t; cross-linking but preferably the injection process is pelrul.lRd in its absence. The aqueous composition may simply be injected with the formation but preferably is forced into it by pumping. The formation is usually at 50-180~C, especially 60-100~C or100-150~C and is generally water bearing rather than oil bearing. It may be of acidic rock, e.g. s~ntl~tone or neutral to basic rock e.g. lim~tone with associated formation water of e.g. pH 3-6.5 such as 4-6 or pH 6.5-8 respectively. The compositions of the invention are especially suitable for use with acidic rocks,especially at 60-150~C.
In particular, copolymers with carboxylic esters from tertiary- alkanols or alyl,~,c~ ols or from ether substituted alkanols or heterocyclic alcohols may beused with acidic rocks at 60-100~C and esters from other hydlu~y compounds e.g. primary or secondary alkanols at 100-150~C. The well may be shut in for 1-70 hr to allow the gelling to occur and then production may be restarted.
The copolymers and compositions of the invention have a benefit of a reduced ten-l~ncy to cross-linking and gelling in the well bore (i.e. reduced aggregate build up) but rapid cross-linking at the high temperatures of the formation. They ther~rc,lt; are less susceptible to process h~n~in~ problems.
The invention is illustrated in the following Examples:-Esample 1 A 90:10 molar copolymer of acrylamide and tertial~ulyl acrylate in aqueous solution was made by free radical copolymerisation, according to the general technique of the references mentioned herein.
The copolymer had a viscosity of 55 cps in 3.6% solution in sea water atl9~C
(the viscosity being dt;Le~ ned as described above). By gel p~ tion cl~olll~lography (GPC) its weight (average molecular weight) was about 295,000, the number average Molec wt was 44,900 and the peak Molec wt was 229,000.
The copolymer solution and a solution of chromium triacetate were added to API
sea water (3.2% total dissolved solids) at 25~C to give an aqueous injection solution co..~ 36,000 ppm copolymer and 1000 ppm Cr ion.
Esample 2 The process of Fx~mrle 1 was repeated to make a 90:10 molarcopolymer of acrylamide and methyl acrylate and an injection solution lhelt;~iulll. The copolymer had a viscosity of 50 cps in 3.6% solution in sea water at 19~C (the viscosity being determined as described above). The Molec wt date ~by GPC) were MW 293,000, Mn 42,600 and Peak Mo. wt. 231,000.
Examples 3 and 4 The polymerisation processes of Examples 1 and 2 are repeated to give copolymers with weight average molecular weight of 5-10 million. Each copolymer and chromium acetate are added to sea water to give an injection solution co-~ g 3000 ppm conct;llll~lion of copolymer and a 75 ppm concellLl~ion of Cr.
.
W 096/19636 PCT/GB9~/030f9 ~Y~p~5 A 10 ft stainless steel tube of internal di~mP,t~r~/4" was packed with quartz sand of average particle size of 90u. API sea water (3.2% Total Dissolved Solids) waspumped into the tube at 80~C until a consl~ll di~elelllial pressure was obl~ned.The absolute pelllleability of the sand pack was ~RIc~ ted by means of Darcy's law to be 1206 MilliDarcies. The tube was then flooded with Forties Crude Oil c~ g 15% toluene followed by another flush of API sea water to consl~ll di~lenlial p,es~Llre. The permeability of the sand pack at residual oil saturation was c~lc~ ted to be 280 MilliDarcies.
The aqueous injection solution of Example 1 was pulllped into the tube P~ at 80~C by means of an oven) at a flow rate of 10 mls/hr and in such a way as to Ill~ a retention time of 1/2 hour in the inlet tube at 80~C prior toentry into the sand pack. The m~imllm pressure limit was set at 100 bar and thislimit was reached after applo~illlalely four hours, after which the injection solution was ~lltom~tic~lly injected at a pro~sles~ t;ly lower flow rate. The injection solution was left to "sq~leP7e" into the tube for al)~lu~llalely a further 16 hours by which time no further flow could be detecte~l A total of 55 mls of the solution had fiowed into the sand pack. In order to asc~;l l~- the depth of the gel block the tube was placed under reverse flow while Ill~;lll;1;ll;ll3O a ~ t;lc;nlial pressure of 100 bar. During this operation, five inch sections of tube were cut from the outlet end (previously the inlet end) until the flow could be deteGte~
The tube was thus found to be blocked to at least 9 feet.
E~ample 6 A 10 foot tube, as in F.Y~mple 5, was found to have an absolute permeability of 1172mD and a permeability of 263mD at residual oil saturation.
The injection solution of FY~mple 2 was used in the gellation test of Example 5 1, under id~ntic~l conditions to Example 5, except that the oven temperature was at110~C. A total of 58 mls of injection of solution had been pumped prior to blocking and the tube was found to be blocked in a depth of 9.5 feet.
E~amples 7 and 8 , The processes of F.~mples ~ and 6 are repeated with the injection solutions of Ex~~ les 3 and 4. Gellation caused blocking.
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The present invention relates to polymers and their plel)al~ion and their use in oil and gas fields.
Oil and gas fields produce water as well as oil and/or gas, especially when the well is depleted. In addition, secondary recovery techniques such as water flooding to stim~ te production of oil involve injection of water under pressureat a ~i~t~nre from a production well to sq~ler7:e the oil out. However, in both cases the water moves in the formation along least hindered paths, so that the recovery technique may be inefficient and in the direct recovery increased proportions of water are produced.
To enh~nre reservoir co.~~ ce control, i.e. mobilise the oil that may be present in less permeable areas, blocking agents may be injected to obstruct thehigh permeability r.h~nnel~ thereby encouraging plererence for liquid movement via the lower permeability r.h~nnrl~ Among known blocking agents are polymer gels, in particular, gels of polyacrylic acid or polyacrylamide/polyacrylic copolymers, cross-linked with cl~OIl~iulll ions as di~cl(!sed in US Patents 4,744,418 and 4,844,168. The copolymer, mixed with cross-linker, is injected into the formation from the production well, often after a flood of cold water to pre-cool the formation rock, to stop premature cross-linking and gelling before the mixture reaches its desired position. Much work has been described to reduce the rate of cross-linking, by red~lcing the activity of the cross-linking metal ion, e.g. by co-o~ A~ g the chromium with a ligand, e.g. lactate.
An improved cross-linking system has now been discovered which comprises a composition in which the tendency of the polymer to cross-link prematurely has been reduced further by use of a copolymer of a polyacrylamide with a polar monomer.
The present invention provides a water soluble copolymer of:
(i) at least one non acidic ethylenically unsaturated polar monomer and ~ii) at least one copolymerisable ethylenically unsaturated ester.
The invention also comprises composilions comprising the water soluble copolymer and a polyvalent metal ion gelling agent.
The present invention also provides a process for delaying the rate of gelling of an acrylic polymer with a gelling agent, in which the acrylic polymer is said copolymer comprising (i) and (ii).
The invention also provides a method for co~ llallce control of a reservoir, especially one with high formation teml,e~ res, which method colll~lises:
(a) injecting into the formation an aqueous solution of said composition, (b) allowing the solution to flow through at least one zone of high permeability in said formation under increasing telll~w~lule conditions, (c) allowing the composition to gel under said con~itions.
The copolymer is formed from at least one, e.g. 1-3 polar ~llolloll.~l(s) and atleast one, e.g. 1-3 ester(s), and comprises structural units derived from said monomer(s) and ester(s); p.e~.~bly the copolymer consists e~senti~lly of said structural units. The ester is ~ulJsl~lially neutral as it is a fully esterifiedderivative of an acid, i.e. complete ester, rather than a partial ester with free acid group(s).
The ester is usually formed from a hydroxyl compound and an ethylenically unsaturated carboxylic acid. The ethylenically ullsa~ul~led group may be in the alpha-beta or beta gamma position relative to the carboxyl group or may be further distant; p~re~ d acids have 3-20 carbons, such as 3-12, e.g. alkenoic and aralkenoic acids with 3-6 or 9-12 carbons respectively. Examples of the acids are acrylic, meth~r.rylic, crotonic and rinn~mic acids. The hydroxyl compound is usually an alcohol and may be of formula ROH, where R is a hydrocarbyl group, preferably an alkyl group, e.g. of 1-30 or 2-30 such as 1-6, 2-6, 7-30 or 7-24 carbons, alkenyl groups, e.g. of 2-20 carbons such as 2-6 carbons, cycloalkyl group, e.g. of 5-8 carbons, aryl group, e.g. aromatic hydrocarbyl group such as 6- y 20 carbons or aralkyl group, e.g. of 7-24 carbons. Examples of such R groups are methyl, ethyl, n- and iso propyl, n, sec, iso and tert butyl, n, sec, iso and tert amyl and hexyl, octyl and 2-ethylhexyl, decyl, allyl, cyclohexyl, palmityl, steryl, phenyl and benzyl. The R group may also be a hydrocarbyl group, subsLiLuLed by at least one substituent e.g. 1-3 substitll~nt~, especially from hydlo~yl, ether, and thio ether groups; electron donating groups are pler~ d. Ether substitllçntc areprtrelled, especially alkoxy, aryloxy and aralkoxy, in which the alkyl, aryl andaralkyl groups may be as described above. Preferably the sub~LilLIell~ is on thesame carbon atom of the R group as is bonded to the hydroxyl group in the hydroxyl compound; alkoxymethyl and aralkoxy methyl groups are plerellèd.
The hydroxyl compound may be a primary, secondary, iso or tertiary compound, especially with a tertiary carbon atom bonded to the hydroxyl group, e.g. tert butyl and trityl. The group R may also comprise a heterocyclic group either for bonding directly to the hydroxyl group of ROH or separated ~helerlolll by an alkylene group, e.g. of 1-4 carbons such as methylene. Thus group R may be a saturated or unsaturated heterocyclic or heterocyclic alkylene group, e.g. of 3-8 carbons and at least one, e.g. one or two ring heteroatoms selected from 0, N and S, especially 0 and/or N, examples of such groups are furyl, tetrahydrofuryl, furfuryl and tetrahydrofurfuryl, pyranyl and tetra hydlopyl~lyl. Most pl~r~;llèd R
groups are tert-butyl, trityl, metho~yln~;~hyl, benzyloxymethyl and tetrahydl~yl~lyl; stearyl, iso propyl, ethyl and methyl may also be pl~relled.
The ester (i) may also be derived from a hydroxyl compound, e.g. of formula ROH and an ethylenically unsaLuldled sulphonic or phosphoric acid, which may contain 2-20 carbons, especially 2-6 carbons, such as alkenyl acids, e.g. vinyl sulphonic acid and vinyl phosphonic acid. Thus the ester may be methyl or ethyl vinyl sulphonate or phosphonate. The ester may be derived from an acid cor.l~;.,h-p~ an ethylenically unsaturated carboxamide (e.g. acrylamido) group, as well as the sulphonic or phosphonic acid group; an example of such an acid is 2-acrylamido-2-1ll~lhylplopalle sulphonic acid.
The ester is copolymerised with an ethylenically unsaturated polar monomer, in which the unsaturated group is usually vinyl or alpha methyl vinyl and may be derived from an unsaturated carboxylic acid (the acid being as further describedabove) e.g. ~l;m~y, secondary or tertiary amide thereof, in which the amide is derived from ~mmoni~ or a plillla y or secondary alkylamine, e.g. of 1-10 carbons, which may optionally be substituted by at least one hydroxyl group as in alkylol amides such as eth~nol~mides; examples of such carboxylic derived polar CA 02208440 l997-06-20 monnm~.rs are acrylamide, meth~r.rylamide and acrylic ethanol amide. The polar monomer may also be a vinyl heterocyclic compound e.g. with at least one 0, S orN atom in a ring with 3-8 carbons such as one with at least one carbonyl group in the ring, e.g. N-vinyl-pyrrolidone or -caprolactam, or a vinyl pyridine.
The copolymer may contain 0.01-50% e.g. 0.1-40% or 1-30%, especially 5-15%
mol of structural units from said ester(s) and 99.99-50% e.g. 99.9-60% or 99-70 or 95-85% mol of structural units from said polar monomer(s). The copolymer may be a block or non block copolymer, e.g. a regular or random copolymer or a graft copolymer, especially with ester units gra~ed onto polymeric polar, mnnom~.r, e.g. ester grafted on polyacrylamide.
The copolymer is usually soluble in water to an extent of at least lg/1 e.g. 1-200g/1 such as at least lOg/1 in distilled water at 15~C, especially in aqueous sodium chloride solution co~ ,;,.g 32g/1 NaCI at 25~C. If desired, the copolymer may be mixed with a surfactant (e.g. in amount of 0.01 - 5% by wt of the solution) to help solubilise it in the water or sodium chloride solution.
The copolymer may have a weight average molecular weight of at least 50,000 e.g. 50,000-20 million, such as 100,000 to 10 mi~ion, especially 100,000-500,000or 1-10 million; the molecular weight may be determined by conventional methods, e.g. gel permeation chlomalography or intrinsic viscosity. The low mole wt copolymer may have a viscosity in aqueous 3.6% wt solution at 19~C of 10-500 CpS (measured at 60 rpm with a Haake viscometer). Preferably the copolymer is sheer thinnable, e.g. with the viscosity reducing by at least 10% on inGIeasi~lg the sheer rate by 10%.
The copolymer may be made by conventional methods for copolymerising ethylenically unsaturated monomers in solution, emulsion or suspension, (preferably aqueous~, such as are described in Encyclopaedia of Polymer Science & Fn~illee~ g~ Ed. Mark, Bikales, O~/e~bel~,el and Menges, Publ. Wiley Interscience, New York, 2nd Ed., Vol 1, pp 181-211 and references cited therein,especially L J Young in J Brandrup and E H Immergut Eds Polymer Handbook, J
Wiley, New York, 2nd Ed. 1975, Sec. II and 3rd Ed. Sec. m, especially pp 155/6 and references cited therein and R Z Greenley J Macromol Science Chem. 14, 427, 445 (1980) and G Saini et al Makromol, Chem. 144, 235 (1971), the disclosure of each of which is incorporated herein by reference. Free radical aqueous suspension or emulsion polymerisation is plerel.~d.
The composition of the invention comprises the copolymere and a polyvalent metal ion, capable of cros~linking an acrylic acid polymer in aqueous solution to form a gel. The cross-linking may be at 20-200~C, especially 50-150~C. The metal ion is usually 2, 3 or 4 valent and may be of group 2A, 3A, 4A, 5A, 6A, 7A, 8, 2B, 3B or 4B of the Periodic Table, e.g. Ca, Mg, Ba, Ti, Zr, Fe, Zn, A1 or Sn; preferably the metal ion is 3 or 4 valent and is especially a transition metal such as chromium or iron, though ~lllmininm may also be used. The particularly pler~;;llt;d metals are chromium and zirconium. The weight ratio of the metal tocopolymer is usually 1:1-100 such as 1:10-80, especially 1:25-50. The ratio of the number of g atoms of metal to g moles of copolymer is usually 1000:0.001-100, preferably 1000:0.01-10, such as 1000:0.1-20 or 1-lO, especially for copolymers of Molec. Wt 100,000 - 500,000. The ratio of the number of g atoms of metal to equivalents of ester group in the copolymer is usually 1000:0.5-5000, preferably 1000:5-5000 such as 1000:50-1000 or 1000:500-5000. The metal is usually present as a salt, e.g. an h~ol~l ic salt such as a halide especially chloride, nitrate or slllph~te or as a carboxylate particularly a monodentate carboxylate, such as a hydrocarbyl monocarboxylate, e.g. with 1-24 carbon atoms (e.g. 2-6) in the carboxylic acid, which may be an alkanoic acid such as acetate.
The metal may also be complexed, e.g. with a ligand, such as a carboxylic acid group, having at least 2, e.g. 2-4 dentate groups in particular, as described inC~n~ n Patent 2063877, the disclosure of which is herein incorporated by ;rerence; example of complexing carboxylic acids are hydroxy alkanoic acids, e.g. Iactate, glycollate or tartrate. The salt or complex is water soluble. The composition is usually made just before use by adding the copolymer and the metal ion (e.g. as salt or complex) to an aqueous medium, e.g. sea water and then injecting the aqueous composition made into the formation. The composition is pr~;rt;l~bly kept at below 50~C, e.g. below 30~C before use. The concentration of coplymer in the aqueous composition may be 500-100,000 ppm, in particular 500-10,000 ppm for copolymers of high Molecular wt of at least 1 million and 10,000-50,000 ppm for copolymers of lower Molecular wt. 50,000-1 CA 02208440 l997-06-20 million. The conce.l~.~lion of the cross-linking metal ion in the aqueous composition may be 10-3000 ppm, especially 10-250 ppm and 3000-1500 ppm respectively for said high and low Molec wt copolymers.
The aqueous composition may be injected into the formation via a producing well or via a secondary injection well (for use with a waterflood or squeeze technique). The aqueous composition may also contain other ingredients, e.g.
~ntio~ nt~ and/o-o~ygel scavengers. The injection may, if desired, be preceded by a precooling tr~tm~.nt7 e.g. coldwater to stop pl~;ll-aL,l-t; cross-linking but preferably the injection process is pelrul.lRd in its absence. The aqueous composition may simply be injected with the formation but preferably is forced into it by pumping. The formation is usually at 50-180~C, especially 60-100~C or100-150~C and is generally water bearing rather than oil bearing. It may be of acidic rock, e.g. s~ntl~tone or neutral to basic rock e.g. lim~tone with associated formation water of e.g. pH 3-6.5 such as 4-6 or pH 6.5-8 respectively. The compositions of the invention are especially suitable for use with acidic rocks,especially at 60-150~C.
In particular, copolymers with carboxylic esters from tertiary- alkanols or alyl,~,c~ ols or from ether substituted alkanols or heterocyclic alcohols may beused with acidic rocks at 60-100~C and esters from other hydlu~y compounds e.g. primary or secondary alkanols at 100-150~C. The well may be shut in for 1-70 hr to allow the gelling to occur and then production may be restarted.
The copolymers and compositions of the invention have a benefit of a reduced ten-l~ncy to cross-linking and gelling in the well bore (i.e. reduced aggregate build up) but rapid cross-linking at the high temperatures of the formation. They ther~rc,lt; are less susceptible to process h~n~in~ problems.
The invention is illustrated in the following Examples:-Esample 1 A 90:10 molar copolymer of acrylamide and tertial~ulyl acrylate in aqueous solution was made by free radical copolymerisation, according to the general technique of the references mentioned herein.
The copolymer had a viscosity of 55 cps in 3.6% solution in sea water atl9~C
(the viscosity being dt;Le~ ned as described above). By gel p~ tion cl~olll~lography (GPC) its weight (average molecular weight) was about 295,000, the number average Molec wt was 44,900 and the peak Molec wt was 229,000.
The copolymer solution and a solution of chromium triacetate were added to API
sea water (3.2% total dissolved solids) at 25~C to give an aqueous injection solution co..~ 36,000 ppm copolymer and 1000 ppm Cr ion.
Esample 2 The process of Fx~mrle 1 was repeated to make a 90:10 molarcopolymer of acrylamide and methyl acrylate and an injection solution lhelt;~iulll. The copolymer had a viscosity of 50 cps in 3.6% solution in sea water at 19~C (the viscosity being determined as described above). The Molec wt date ~by GPC) were MW 293,000, Mn 42,600 and Peak Mo. wt. 231,000.
Examples 3 and 4 The polymerisation processes of Examples 1 and 2 are repeated to give copolymers with weight average molecular weight of 5-10 million. Each copolymer and chromium acetate are added to sea water to give an injection solution co-~ g 3000 ppm conct;llll~lion of copolymer and a 75 ppm concellLl~ion of Cr.
.
W 096/19636 PCT/GB9~/030f9 ~Y~p~5 A 10 ft stainless steel tube of internal di~mP,t~r~/4" was packed with quartz sand of average particle size of 90u. API sea water (3.2% Total Dissolved Solids) waspumped into the tube at 80~C until a consl~ll di~elelllial pressure was obl~ned.The absolute pelllleability of the sand pack was ~RIc~ ted by means of Darcy's law to be 1206 MilliDarcies. The tube was then flooded with Forties Crude Oil c~ g 15% toluene followed by another flush of API sea water to consl~ll di~lenlial p,es~Llre. The permeability of the sand pack at residual oil saturation was c~lc~ ted to be 280 MilliDarcies.
The aqueous injection solution of Example 1 was pulllped into the tube P~ at 80~C by means of an oven) at a flow rate of 10 mls/hr and in such a way as to Ill~ a retention time of 1/2 hour in the inlet tube at 80~C prior toentry into the sand pack. The m~imllm pressure limit was set at 100 bar and thislimit was reached after applo~illlalely four hours, after which the injection solution was ~lltom~tic~lly injected at a pro~sles~ t;ly lower flow rate. The injection solution was left to "sq~leP7e" into the tube for al)~lu~llalely a further 16 hours by which time no further flow could be detecte~l A total of 55 mls of the solution had fiowed into the sand pack. In order to asc~;l l~- the depth of the gel block the tube was placed under reverse flow while Ill~;lll;1;ll;ll3O a ~ t;lc;nlial pressure of 100 bar. During this operation, five inch sections of tube were cut from the outlet end (previously the inlet end) until the flow could be deteGte~
The tube was thus found to be blocked to at least 9 feet.
E~ample 6 A 10 foot tube, as in F.Y~mple 5, was found to have an absolute permeability of 1172mD and a permeability of 263mD at residual oil saturation.
The injection solution of FY~mple 2 was used in the gellation test of Example 5 1, under id~ntic~l conditions to Example 5, except that the oven temperature was at110~C. A total of 58 mls of injection of solution had been pumped prior to blocking and the tube was found to be blocked in a depth of 9.5 feet.
E~amples 7 and 8 , The processes of F.~mples ~ and 6 are repeated with the injection solutions of Ex~~ les 3 and 4. Gellation caused blocking.
-
Claims (24)
1. A water soluble copolymer comprising (i) at least one non acidic ethylenically unsaturated polar monomer and (ii) at least one copolymerisable ethylenically unsaturated ester
2. A water soluble copolymer as claimed in claim 1 in which the ester is formed from a hydroxyl compound and an ethylenically unsaturated carboxylic acid selected from acrylic, methacrylic, crotonic and cinnamic acids.
3. A water soluble copolymer as claimed in claim 2 in which the hydroxyl compound is an alcohol of formula ROH where R is a C 1-30 alkyl, alkenyl, cycloalkyl aryl or aralkyl group, or a hydroxyl, ether or thio ether substitutedhydrocarbyl group.
4. A water soluble copolymer as claimed in claim 1, 2 or 3 in which the ethylenically unsaturated ester is an alkyl or aralkyl acrylate in which the alkyl group is a C 1 to 10 alkyl group and the aralkyl group is an C 1 to 5 alkyl substituted aryl group.
5. A water soluble copolymer as claimed in any one of claims 1 to 4 in which theethylenically unsaturated polar monomer is an amide of an unsaturated carboxylicacid.
6. A water soluble copolymer as claimed in claim 5 in which the ethylenically unsaturated polar monomer is acrylamide,
7. A composition as claimed in any one of claims 1 to 6 in which the copolymer contains from 5-15% mol of structural units from said ester and 95-85% mol of structural units from said polar monomer.
8. A water soluble copolymer as claimed in any one of claims 1 to 7 in which thecopolymer is a regular or random copolymer or a graft copolymer.
9. A water soluble copolymer as claimed in claim 8 in which the copolymer is a graft copolymer in which ester units are grafted onto a polyacrylamide.
10. A water soluble copolymer as claimed in any one of claims 1 to 9 in which the copolymer is soluble in water to an extent of at least 10g/1.
11. A water soluble copolymer as claimed in claim any one of claims 1 to 10 in which the copolymer has a weight average molecular weight of at least 50,000.
12. A water soluble copolymer composition as claimed in claim 11 which the copolymer has a weight average molecular weight of 1-10 million.
13. A composition comprising a water soluble copolymer as claimed in any one of claims 1 to 12 and a polyvalent metal ion gelling agent.
14. A composition as claimed in claim 13 in which the metal ion is 3 or 4 valentmetal ion.
15. A composition as claimed in claim 14 in which the metal ion is selected fromtransition metals and aluminium
16. A composition as claimed in claim 15 in which the metal ion is chromium.
17. A composition as claimed in claim 15 in which the metal ion is zirconium.
18. A composition as claimed in any one of claims 13 to 17 in which the weight ratio of the metal to copolymer is 1:1-100
19. A composition as claimed in any one of claims 13 to 18 in which the metal ispresent as a salt.
20. A composition as claimed in claim 19 in which the metal salt is an inorganicsalt or a caboxylate.
21. A composition as claimed in claim 19 in which the metal salt is a halide.
22. A composition as claimed in claim 19 in which the metal salt is a hydrocarbyl monocarboxylate
23. A composition as claimed in claim 22 in which the metal salt is an acetate.
24. A method for conformance control of a reservoir, which comprises:
(a) injecting into the formation an aqueous solution of a composition as claimedin any one of claims 13 to 23 (b) allowing the solution to flow through at least one zone of high permeability in said formation under increasing temperature conditions (c) allowing the composition to gel under said conditions.
(a) injecting into the formation an aqueous solution of a composition as claimedin any one of claims 13 to 23 (b) allowing the solution to flow through at least one zone of high permeability in said formation under increasing temperature conditions (c) allowing the composition to gel under said conditions.
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| GB9426025.4 | 1994-12-22 | ||
| GBGB9426025.4A GB9426025D0 (en) | 1994-12-22 | 1994-12-22 | Oil and gas field chemicals |
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| CA2208440A1 true CA2208440A1 (en) | 1996-06-27 |
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| US (1) | US5836392A (en) |
| EP (1) | EP0799364B1 (en) |
| AU (1) | AU699103B2 (en) |
| BR (1) | BR9510465A (en) |
| CA (1) | CA2208440A1 (en) |
| DE (1) | DE69522710T2 (en) |
| DK (1) | DK0799364T3 (en) |
| GB (1) | GB9426025D0 (en) |
| NO (1) | NO313252B1 (en) |
| WO (1) | WO1996019636A1 (en) |
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| US4785028A (en) * | 1986-12-22 | 1988-11-15 | Mobil Oil Corporation | Gels for profile control in enhanced oil recovery under harsh conditions |
| US5043364A (en) * | 1990-03-15 | 1991-08-27 | Phillips Petroleum Company | Gelation of acrylamide-containing polymers with furfuryl alcohol and water dispersible aldehydes |
| US5133408A (en) * | 1991-05-31 | 1992-07-28 | Marathon Oil Company | Rate controllable gel for conformance improvement treatment in a subterranean hydrocarbon-bearing formation |
| US5465792A (en) * | 1994-07-20 | 1995-11-14 | Bj Services Company | Method of controlling production of excess water in oil and gas wells |
| US5543446A (en) * | 1994-11-23 | 1996-08-06 | Hercules Incorporated | Water-soluble acrylamide/acrylic acid polymers and their use as dry strength additives for paper |
-
1994
- 1994-12-22 GB GBGB9426025.4A patent/GB9426025D0/en active Pending
-
1995
- 1995-12-22 DE DE69522710T patent/DE69522710T2/en not_active Expired - Fee Related
- 1995-12-22 WO PCT/GB1995/003019 patent/WO1996019636A1/en active IP Right Grant
- 1995-12-22 DK DK95941790T patent/DK0799364T3/en active
- 1995-12-22 BR BR9510465-8A patent/BR9510465A/en not_active IP Right Cessation
- 1995-12-22 CA CA002208440A patent/CA2208440A1/en not_active Abandoned
- 1995-12-22 AU AU43093/96A patent/AU699103B2/en not_active Ceased
- 1995-12-22 US US08/849,904 patent/US5836392A/en not_active Expired - Lifetime
- 1995-12-22 EP EP95941790A patent/EP0799364B1/en not_active Expired - Lifetime
-
1997
- 1997-06-17 NO NO19972795A patent/NO313252B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| NO972795D0 (en) | 1997-06-17 |
| MX9704615A (en) | 1998-05-31 |
| DE69522710D1 (en) | 2001-10-18 |
| EP0799364B1 (en) | 2001-09-12 |
| EP0799364A1 (en) | 1997-10-08 |
| DE69522710T2 (en) | 2002-02-07 |
| DK0799364T3 (en) | 2001-12-17 |
| US5836392A (en) | 1998-11-17 |
| BR9510465A (en) | 1999-09-14 |
| AU699103B2 (en) | 1998-11-19 |
| WO1996019636A1 (en) | 1996-06-27 |
| GB9426025D0 (en) | 1995-02-22 |
| NO972795L (en) | 1997-06-17 |
| NO313252B1 (en) | 2002-09-02 |
| AU4309396A (en) | 1996-07-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |