CN101595196A - Use the method for stable hydrocarbon foams - Google Patents
Use the method for stable hydrocarbon foams Download PDFInfo
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- CN101595196A CN101595196A CNA2008800026080A CN200880002608A CN101595196A CN 101595196 A CN101595196 A CN 101595196A CN A2008800026080 A CNA2008800026080 A CN A2008800026080A CN 200880002608 A CN200880002608 A CN 200880002608A CN 101595196 A CN101595196 A CN 101595196A
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- 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
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
- C09K8/703—Foams
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- 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
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- 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
- C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
- C08F220/68—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
- C09K8/518—Foams
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- 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
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/536—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning characterised by their form or by the form of their components, e.g. encapsulated material
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Abstract
A kind of method of subsurface geology rock stratum of pack processing hydrocarbonaceous comprises to be enough to open in the stratum at least one fissured speed and pressure foam is injected wherein; And a kind of in the subsurface geology rock stratum that well is passed the method for completion, comprise and introduce foam in the well of described subsurface geology rock stratum and in the well of described subsurface geology rock stratum, implement well completion operations.Described foam comprises liquid hydrocarbon and contains the non-ionic polymers type tensio-active agent of fluorinated repeating units, wherein said fluorinated repeating units has maximum 5 perfluoro-carbon atoms, and the 1 weight % solution of wherein said non-ionic polymers type tensio-active agent in kerosene is at least 10 minutes at 22 ℃ half foam life period.
Description
Background technology
Pressure break give birth to the hydrocarbon well (as, oil or gasser) be a common technology, this technology is designed to lead the crack or groove increases well yield by generation height in the livings hydrocarbon geological formations around the well.This type of pressure break is normally finished by generating crack (being waterfrac treatment) with high speed and high-pressure injection fluid.
The various operations (as, cleaning well, gravel packed well and consolidate well) that are commonly referred to well completion operations are used to prepare the living hydrocarbon well that is used to produce.The fluid that is used for well completion operations is commonly referred to well completion fluid.
It is known using aerated fluid in pressure break or well completion operations.The more non-foam fluid of aerated fluid can have multiple advantage.For example, the liquid volume in the aerated fluid is less than the liquid volume in the non-foam fluid, and therefore when using foam, the fluid loss that permeable formation causes is less.In addition, after pressure break or well completion operations, aerated fluid is easier to remove from geological formations than non-foam fluid usually.Aerated fluid (comprising multiviscosisty fluid or non-multiviscosisty fluid) has the ability bigger than its non-foam counterpart toward contact and suspends and be transmitted in pressure break or the well completion operations particulate matter (as the particulate of propping agent, gravel and release) that uses or produce.
The liquid that is used as liquid phase in the foam that pressure break or well completion operations adopted comprises water, hydrocarbon and aqueous alcohol solutions.When the stratum was responsive to the intrusion of this stratum extraneous water, it was favourable that one or more hydrocarbon in the use aerated fluid liquid phase carry out the stratum processing.This type of water sensitive layer comprises clay usually, behind these clay contacting extraneous waters because clay swelling and/or the particulate migration that causes thus cause the infringement that can't repair.
In foam, bubble is separated from one another by thin liquid film.Usually, tensio-active agent is by in the absorption of the contact surface place of bubble and liquid film and hinder that bubble is coalescent to come stable foam.Form the hydrocarbon foam and have more challenge than forming resistance aqueous foam usually.Different with the water with high surface tension and solubilized charge species, hydrocarbon does not generally have the coalescent characteristic of the bubble of obstruction.
Some fluorinated surfactants that produce stable hydrocarbon foams are known.Traditionally, much the fluorinated surfactant that can extensively adopt comprises the long-chain perfluoroalkyl, for example the PFO sulfoamido.Yet, having recently to break away from the industry trends of using the PFO fluorinated surfactant, this has caused can producing (for example) demand of hydrocarbon foamy novel surfactant.
It is a kind of that to have the perfluorinated butane of containing sulfoamido repeating unit and weight-average molecular weight be that the non-ionic polymers type fluorinated surfactants of every mole of about 15,000 gram have been used as drilling fluid and have added the hydrocarbon blowing agent of the raising oil recovery factor fluid that injects well to.
Summary of the invention
In one aspect, the invention provides the method for the subsurface geology rock stratum of pack processing hydrocarbonaceous, this method comprises:
Foam is injected the subsurface geology rock stratum that comprises hydrocarbon to be enough to open in the subsurface geology rock stratum at least one fissured speed and pressure, wherein foam comprises liquid hydrocarbon and the non-ionic polymers type tensio-active agent that contains fluorinated repeating units, wherein fluorinated repeating units has maximum 5 perfluoro-carbon atoms, and wherein the 1 weight % solution of non-ionic polymers type tensio-active agent in kerosene is at least 10 minutes at 22 ℃ half foam life period.In certain embodiments, the weight-average molecular weight of non-ionic polymers type tensio-active agent is every mole of at least 45,000 gram.In certain embodiments, based on the foamy gross weight, the content of non-ionic polymers type tensio-active agent is in the scope of 0.1 weight % to 5 weight %.In certain embodiments, this method also comprises a plurality of proppant particles injections crack.In certain embodiments, foam also comprises jelling agent.
On the other hand, the invention provides the completion method in the subsurface geology rock stratum that well is passed, this method comprises:
A kind of foam is provided, this foam comprises liquid hydrocarbon and contains the non-ionic polymers type tensio-active agent of fluorinated repeating units, wherein fluorinated repeating units has maximum 5 perfluoro-carbon atoms, and wherein the 1 weight % solution of non-ionic polymers type tensio-active agent in kerosene is at least 10 minutes at 22 ℃ half foam life period;
Foam is introduced in the well of described subsurface geology rock stratum; And
In the well of subsurface geology rock stratum, carry out well completion operations.In certain embodiments, well completion operations is the gravpack well, cleans well or consolidate at least a in the well.
Among some embodiment aspect above-mentioned, non-ionic polymers type tensio-active agent comprises:
At least one is by the divalent unit of represented by formula I:
The divalent unit that at least one is represented by Formulae II:
Wherein
Rf is the perfluoroalkyl with 3 to 4 carbon atoms;
R and R
2Be the alkyl of hydrogen or 1 to 4 carbon atom independently of one another;
R
1It is the alkyl of 16 to 24 carbon atoms; And
N is 2 to 11 integer.
In some these embodiment, R
1It is the alkyl of 18 to 22 carbon atoms.In certain embodiments, non-ionic polymers type tensio-active agent comprises the divalent unit by represented by formula I, and based on the gross weight of non-ionic polymers type tensio-active agent, the content of this divalent unit is in the scope of 45 to 75 weight %.
Among some embodiment aspect above-mentioned, liquid hydrocarbon is at least a in kerosene, diesel oil, gasoline, pentane, hexane, heptane, mineral oil or the cycloalkanes.
On the other hand, the invention provides a kind of method for preparing non-ionic polymers type tensio-active agent, this method comprises:
Mix each component, component comprises:
At least a compound by following chemical formulation:
At least a compound by following chemical formulation:
Wherein
Rf is independently for having the perfluoroalkyl of 3 to 4 carbon atoms;
R and R
2Be the alkyl of hydrogen or 1 to 4 carbon atom independently of one another,
R
1Be the alkyl of 16 to 24 carbon atoms independently; And
N is 2 to 11 integer independently;
Chain-transfer agent;
Radical initiator; With
Solvent; And
Heat contents under maximum 70 ℃ temperature.
Handle the subsurface geology rock stratum according to the present invention and will use non-ionic polymers type tensio-active agent with the method for carrying out completion, this non-ionic polymers type tensio-active agent produces stable hydrocarbon foams (foam that promptly has the long transformation period) usually.Among some embodiment aspect above-mentioned, the 1 weight % solution of non-ionic polymers type tensio-active agent in kerosene is at least 12,14,16,18,20,22,24,26,28 or even at least 30 minutes at 22 ℃ half foam life period.In certain embodiments, the 1 weight % solution of non-ionic polymers type tensio-active agent in kerosene at 22 ℃ half foam life period greater than 20 minutes.In some embodiment of the method according to this invention, foam is stable under conditions down-hole, and in certain embodiments, foam is stable between entire method (promptly handling or finish the subsurface geology rock stratum) effective date.Can be used for implementing non-ionic polymers type tensio-active agent of the present invention provides such hydrocarbon foam, and this hydrocarbon foam is usually and to a miracle than before this at drilling fluid with to improve the non-ionic polymers type tensio-active agent that contains the perfluorinated butane sulfoamido that uses in the oil recovery factor operation more stable.In certain embodiments, can be used for implementing non-ionic polymers type tensio-active agent of the present invention provides at least and comprises the same stable hydrocarbon foam of similar non-ionic polymers type tensio-active agent that contains the PFO sulfoamido.
In this application:
" alkyl " and prefix " alkane " had both comprised straight chain and branched group, also comprised cyclic group.Cyclic group can be monocycle or polycyclic, and in certain embodiments, has 3 to 10 ring carbon atoms.
Term " perfluoroalkyl " comprises all c h bonds all by C-F key metathetical straight chain, side chain and/or cyclic alkyl, and the group that has hydrogen or chlorine atom rather than fluorine atom (precondition is that per two carbon atoms have maximum hydrogen atoms or chlorine atom).In some embodiment of perfluoroalkyl, when having at least one hydrogen or chlorine, perfluoroalkyl comprises at least one trifluoromethyl.
Term " hydrocarbon " refers to the compound be made up of carbon and hydrogen, and comprises and can be saturated or undersaturated straight chain, side chain and cyclic group.
Term " nonionic " refers to not contain ionic group (as salt) or is not contained in and is easy to Ionized group in the water (as-CO
2H ,-SO
3H ,-OSO
3H ,-P (=O) (OH)
2).
Term " foam " refers to the mixture of gas (as nitrogen, carbonic acid gas, air and Sweet natural gas) and liquid (comprising liquid hydrocarbon in this application).
Except as otherwise noted, otherwise all numerical ranges include its end value.
Embodiment
Can be used for implementing foamy stability of the present invention (being half foam life period) and other character (as the foam expansion rate) can use technology known in the art to measure; (referring to (for example) Alm, people such as R.R., Chemical Times ﹠amp; Trends, April, 1986, the 40-48 pages or leaves (people such as Alm, " chemistry epoch and trend " in April, 1986,40-48 page or leaf)).In present patent application, half foam life period is determined in the following manner: will the 1 weight % solution of about 200ml non-ionic polymers type tensio-active agent in kerosene place the food mixer (can be available from Hobart (Troy, OH), model is N-50) a mixing bowl in, down mixed this solution three minutes with middling speed (300rpm) at 22 ℃ then with the wire whisk annex.Then immediately the gained foam is poured in the graduated cylinder of 2000mL to measure foam expansion rate and half foam life period, this graduated cylinder (can be available from VWR International (West Chester, PA)) made by " NALGENE " high density poly propylene, internal diameter is about 8 centimetres, highly is about 52 centimetres.Measuring a semiliquid discharges (the original liquid volume that promptly obtains half) time necessary and obtains half foam life period from foam.The foam expansion rate is meant the volume of liquid before the volume that reaches after the foaming is divided by foaming.Multiply by half foam life period with the foam expansion rate and calculate foam index.
Can be used for implementing foam of the present invention and comprise non-ionic polymers type tensio-active agent.In certain embodiments, non-ionic polymers type tensio-active agent comprises the fluorinated repeating units of (3 in certain embodiments,, 2 or even 1) the perfluoro-carbon atom that has 4.In certain embodiments, can be used for implementing non-ionic polymers type tensio-active agent of the present invention and comprise at least one divalent unit by represented by formula I:
In certain embodiments, can be used for implementing non-ionic polymers type tensio-active agent of the present invention and comprise the divalent unit that at least one is represented by Formula I a:
In Formula I or Ia, Rf is the perfluoroalkyl (as perfluor normal-butyl, perfluor isobutyl-, perfluor sec-butyl, the perfluor tertiary butyl, perfluor n-propyl or perfluor sec.-propyl) with 3 to 4 carbon atoms.In some embodiment of Formula I or Ia, Rf is the perfluor normal-butyl.
In Formula I or Ia, R is the alkyl (as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or sec-butyl) of hydrogen or 1 to 4 carbon atom.In some embodiment of Formula I or Ia, R is methyl or ethyl.
In Formula I or Ia, n is that value is 2 to 11 integer (promptly 2,3,4,5,6,7,8,9,10 or 11).
In certain embodiments, can be used for implementing non-ionic polymers type tensio-active agent of the present invention and have the divalent unit that at least one is represented by Formula I b:
In certain embodiments, can be used for implementing the repeating unit that non-ionic polymers type tensio-active agent of the present invention comprises and have 14 to 24 the side chain alkyl of (16 to 24, or even 18 to 22 in certain embodiments) carbon atom.In certain embodiments, can be used for implementing non-ionic polymers type tensio-active agent of the present invention and comprise the divalent unit that at least one is represented by Formulae II:
R
2Alkyl (as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or sec-butyl) for hydrogen or 1 to 4 carbon atom.In some embodiment of Formulae II, R
2Be hydrogen.In some embodiment of Formulae II, R
2Be methyl.
R
1It is the alkyl of 16 to 24 (in certain embodiments, being 18 to 22) carbon atoms.
In certain embodiments, non-ionic polymers type tensio-active agent comprises the divalent unit that at least one is represented by Formulae II, wherein R
1Be the alkyl of 16 to 24 (or even 18 to 22) carbon atom, its foam that provides is unexpectedly represented by Formulae II and R wherein than comprising at least one
1For the non-ionic polymers type tensio-active agent of the divalent unit of the alkyl that is less than 14 carbon atoms has the more long lifetime.
In certain embodiments, the non-ionic polymers type tensio-active agent that can be used for implementing among the present invention comprises at least one divalent unit by represented by formula I, gross weight based on non-ionic polymers type tensio-active agent, the content of this divalent unit is in the scope of 45 to 75 weight % (50 to 70 weight % or even 55 to 65 weight % in certain embodiments).
In certain embodiments, can be used for implementing non-ionic polymers type tensio-active agent of the present invention and comprise the divalent unit that at least one is represented by Formula I a, gross weight based on non-ionic polymers type tensio-active agent, the content of this divalent unit is in the scope of 30 to 65 weight % (35 weight % to 60 weight % or even 45 to 55 weight % in certain embodiments).
In certain embodiments, can be used for implementing non-ionic polymers type tensio-active agent of the present invention and comprise the divalent unit that at least one is represented by Formulae II, gross weight based on non-ionic polymers type tensio-active agent, the content of this divalent unit at 25 to 55 weight % (in certain embodiments, 30 to 50 weight % or even 35 to 45 weight %) scope in, or in the scope of 35 to 70 weight % (40 to 65 weight % or even 45 to 55 weight % in certain embodiments).
In some embodiment that can be used for non-ionic polymers type tensio-active agent of the present invention, independently by the divalent group of at least one expression among Formula I or the Formula I a and the divalent group generation random copolymerization of representing by Formulae II independently.
Can be used for implementing non-ionic polymers type tensio-active agent of the present invention can (for example) by usually under the situation that has chain-transfer agent and initiator, make and contain at least the first and second monomeric mixture copolymerization and prepare.Term " copolymerization " expression forms polymkeric substance or the oligopolymer that comprises by first and second each caused at least a discernible structural unit of monomer.Usually, formed polymkeric substance or oligopolymer have the distribution of molecular weight and composition.
In certain embodiments, first monomer is fluoridized at least one of free radical polymerizable monomer for what represented by Formulae II I, IIIa or IIIb:
Wherein Rf, R and n as above regard to the unit that Formula I and Ia represent and define.
In certain embodiments, second monomer is the monomer of the aliphatic free redical polymerization represented by Formula I V:
R wherein
1And R
2As above the divalent unit in the face of Formulae II defines.
The free radical polymerizable monomer and preparation method thereof of fluoridizing that Formulae II I, IIIa and IIIb represent is as known in the art; (referring to (for example) U.S. Patent No. 2,803,615 (people such as Albrecht) and 6,664,354 (people such as Savu), the part that relates to free radical polymerizable monomer and preparation method thereof in its disclosure is incorporated this paper by reference into).The method of describing in the above-mentioned reference that is used to prepare the structure that comprises nine fluorine butane sulfoamidos can be used to prepare the heptafluoro-propane sulfoamido with the heptafluoro-propane sulfonic acid fluoride as initiator, the heptafluoro-propane sulfonic acid fluoride can be according to (for example) U.S. Patent No. 2,732, the method preparation of describing in the example 2 and 3 of 398 people such as () Brice, the disclosure of this patent is incorporated this paper by reference into.
The compound of Formula I V (as methacrylic acid cetyl ester, methacrylic acid stearyl, stearyl acrylate base ester, methacrylic acid docosyl ester) can derive from (for example) a plurality of chemical supplier (as Sigma-Aldrich Company (Milwaukee, WI); VWR International (West Chester, PA); Monomer-Polymer ﹠amp; Dajac Labs (Festerville, PA); Avocado Organics (Ward Hill, MA); And CibaSpecialty Chemicals (Basel, Switzerland)) maybe can be synthetic by ordinary method.The individual isomer (as the straight chain isomer) that some compound of Formula I V can be used as the simplification compound provides.Other compounds that Formula I V represents can be used as the mixture of (for example) isomer (as straight chain and branched chain isomer), the mixture of compound (as vinylformic acid cetyl ester and vinylformic acid stearyl) and their combination and provide.
In certain embodiments, can use more than one first monomer and/or more than one second monomeric mixture.In other embodiments, can use a kind of first monomer and a kind of second monomer.
At least a first monomer and at least a second monomeric polymerization are carried out under the situation that has the radical initiator that adds usually.Can use the polymerization that causes component such as those radical initiators that are widely known by the people in this area and use.The example of radical initiator comprises that azo-compound is (as 2; 2 '-azobis isobutyronitrile (AIBN), 2,2 '-azo two (2-methylbutyronitrile) or azo-2-cyanopentanoic acids), hydroperoxide (as isopropyl benzene, the tertiary butyl or t-amyl peroxy hydrogen), dialkyl peroxide (as di-t-butyl or dicumyl peroxide), peroxyester (as t-butylperoxyl benzoate or peroxide phthalic acid di tert butyl carbonate), diacyl peroxide (as benzoyl peroxide or lauryl peroxide).The available light trigger comprises benzoin ether (as benzoin methyl ether or benzoin isobutyl ether); Acetophenone derivs (as 2,2-dimethoxy-2-phenyl methyl phenyl ketone or 2,2-diethoxy acetophenone); And acylphosphine oxide derivative and acyl phosphonic acid ester derivative (as phenylbenzene-2,4,6-trimethylbenzoyl phosphine oxide, isopropyl phenyl-2,4,6-trimethylbenzoyl phosphine oxide or pivaloyl group dimethyl phosphonate).When being heated or during photodissociation, this radical initiator fracture produces free radical, free radical addition is to the ethylenic unsaturated link(age) and initiated polymerization.
Polyreaction can be carried out in being applicable to any solvent of organic free radical polymeric.Component in solvent can for any suitable concentration (as, count about 5 weight % to about 90 weight % with the gross weight of reaction mixture).The illustrative examples of suitable solvent comprises that aliphatic series and clicyclic hydrocarbon are (as hexane, heptane and hexanaphthene), aromatic solvent is (as benzene, toluene and dimethylbenzene), ether is (as Anaesthetie Ether, glyme, diglyme and Di Iso Propyl Ether), ester (as ethyl acetate and butylacetate), alcohol (as ethanol and Virahol), ketone is (as acetone, methylethylketone and methyl iso-butyl ketone (MIBK)), sulfoxide (as dimethyl sulfoxide (DMSO)), acid amides is (as N, dinethylformamide and N, the N-N,N-DIMETHYLACETAMIDE), halogenated solvent is (as trichloroethane, 1,1,2-three chloro-1,2, the 2-Halothane, trieline and trichlorotoluene zotrichloride), and their mixture.
Polymerization can be carried out under any temperature that is suitable for carrying out the organic free radical reaction.Those skilled in the art according to such as the agent dissolves degree, use the consideration of aspects such as required temperature of particular initiator and desired molecule amount can select concrete temperature and the solvent that uses.Though it is unrealistic to list the actual temp that is applicable to all initiators and all solvents, but suitable in general temperature at about 30 ℃ extremely about 200 ℃ (in certain embodiments, at about 40 ℃ to about 100 ℃, or even at about 50 ℃ to about 80 ℃) scope in.For preparation according to for some embodiment of the method for non-ionic polymers type tensio-active agent of the present invention, can be (in certain embodiments at about 30 ℃ extremely about 70 ℃, at about 40 ℃ to about 70 ℃, or even about 50 ℃ to about 70 ℃) scope in temperature under heat contents.
Can carry out radical polymerization under the situation of chain-transfer agent existing.Can be used for preparing the mercaptan that the typical chain transfer agent that can be used for implementing non-ionic polymers type tensio-active agent of the present invention comprises that hydroxyl replaces (as, 2 mercapto ethanol, 3-sulfydryl-2-butanols, 3-sulfydryl-2-propyl alcohol, 3-sulfydryl-1-propyl alcohol and 3-Mercapto-1 (being thioglycerol)); The amino mercaptan (as the 2-mercaptoethylamine) that replaces; Difunctionality mercaptan is (as two (2-mercaptoethyl) thioether; And aliphatic mercaptan (as spicy thioalcohol and Dodecyl Mercaptan).
Adjust the concentration of (for example) initiator concentration and activity, each monomeric concentration, temperature, chain-transfer agent and use the solvent of technology known in the art, can control the molecular weight of acrylate copolymer.
In certain embodiments, can be used for implementing and/or the weight-average molecular weight of non-ionic polymers type tensio-active agent prepared in accordance with the present invention is that at least 45,000 (is at least 50 in certain embodiments,, 000,55,000,60,000,65,000,70,000,75,000,80,000,85,000,90,000,95,000,100,000,105,000,110,000,115,000,120,000,125,000,130,000,135,000 or even at least 140,000) gram is every mole.In certain embodiments, the weight-average molecular weight that can be used for implementing non-ionic polymers type tensio-active agent of the present invention up to 250,000 (in certain embodiments, up to 245,000,240,000,235,000,230,000,225,000,220,000,215,000,210,000,205,000,200,000,195,000,190,000,185,000,180,000,175,000,170,000,165,000 or even up to 160,000) gram every mole.Unexpectedly, in certain embodiments, weight-average molecular weight is at least 45 according to observations, it is in longer life-span of the non-ionic polymers type tensio-active agent of every mole of 20,000 gram or the higher foam expansion rate at least one that every mole non-ionic polymers type tensio-active agent of 000 gram can provide more maximum than weight-average molecular weight.Non-ionic polymers type tensio-active agent has the distribution of molecular weight and composition usually.Can adopt technology known in the art to measure weight-average molecular weight by (for example) gel permeation chromatography (being size exclusion chromatography).
Usually, for the method for handling subsurface geology rock stratum and completion according to the present invention, based on the foamy gross weight, foam comprises at least 0.01 weight %, 0.015 weight %, 0.02 weight %, 0.025 weight %, 0.03 weight %, 0.035 weight %, 0.04 weight %, 0.045 weight %, 0.05 weight %, 0.055 weight %, 0.06 weight %, 0.065 weight %, 0.07 weight %, 0.075 weight %, 0.08 weight %, 0.085 weight %, 0.09 weight %, 0.095 weight %, 0.1 weight %, 0.15 weight %, 0.2 weight %, 0.25 weight %, 0.5 weight %, 1 weight %, 1.5 weight %, 2 weight %, 3 weight %, 4 weight % or 5 weight %, maximum 5 weight %, 6 weight %, 7 weight %, 8 weight %, the non-ionic polymers type tensio-active agent of 9 weight % or 10 weight %.For example, based on the foamy gross weight, the amount of non-ionic polymers type tensio-active agent can be in the scope of 0.01 weight % to 10 weight %, 0.1 weight % to 10 weight %, 0.1 weight % to 5 weight %, 1 weight % to 10 weight % in the foam, or even in the scope of 1 weight % to 5 weight %.In certain embodiments, based on the foamy gross weight, the content of non-ionic polymers type tensio-active agent is in the scope of 0.3 weight % to 0.5 weight %.Also can use non-ionic polymers type tensio-active agent lower or more a large amount in the composition may be that some application is required.
Employed foam comprises liquid hydrocarbon in the method for handling subsurface geology rock stratum and completion according to the present invention.Be suitable for implementing liquid hydrocarbon of the present invention and comprise crude oil; Refining hydrocarbon (as gasoline, kerosene and diesel oil); Paraffinic hydrocarbon and isoparaffin (as, derive from Total Fina (Paris with trade(brand)name " ISANE IP 130 " and " ISANEIP 175 ", France), and derive from Exxon Mobil Chemicals (Houston, pentane TX), hexane, heptane, higher alkane and isoparaffic solvent) with trade(brand)name " ISOPAR "; Mineral oil; V.M.. naphtha; Naphthene; Aromatic hydrocarbons (as dimethylbenzene and toluene); Natural gas condensate; With their composition (mixable or immiscible composition).In certain embodiments, liquid hydrocarbon is a kerosene.In certain embodiments, liquid hydrocarbon is a diesel oil.Be suitable for use as the liquid hydrocarbon of fracturing fluid can (for example) with trade(brand)name " PLATINUM ", " TG-740 ", " SF-770 ", " SF-800 ", " SF-830 " and " SF-840 " derive from SynOil (Calgary, Alberta, Canada).
Can utilize multiple mechanism (as machinery and chemism) to implement to form bubble (as nitrogen, carbonic acid gas and air) in the composition of non-ion fluorin fluidized polymer type tensio-active agent of the present invention comprising liquid hydrocarbon and can be used for.Available mechanical foaming mechanism comprises: vibrate (as shake, stir and stir) composition, inject air (as nozzle is inserted under the surface of composition, then air being blown into composition) and their combination in composition.Available chemical foaming mechanism comprises: the component (as liquefied gas, and the pressure by reducing composition or heating combination make the gaseous volatilization in the composition) that generates gas, evaporation composition by the decomposition original position of chemical reaction, composition component (as discharging the component of gas after the thermolysis).Can utilize in this area wherein a kind of in the known several different methods bubble to be sneaked into liquid hydrocarbon to form foam at (for example) well location (or even at well head).These class methods comprise and are described in U.S. Patent No. 3,463, and those among 231 people such as () Hutchison and 3,819,519 people such as () Sharman relate to the part that generates the foamy method and incorporate this paper by reference in its disclosure.Can be used for implementing foam of the present invention and comprise 10% to 90% the gas that the volume fraction scope is total lather volume usually.
At least one fissured technology is well known in the art so that open wherein in the subsurface geology rock stratum of pack processing hydrocarbonaceous.The crack that fracturing fluid (as foam) injects and opens rock with the high pressure that surpasses rock strength usually.Can use the multiple pumping system (as positive displacement pump and impeller pump) that adopts multiple driving mechanism (as motor, turbine and generator).The method according to this invention can be used for improving hydrocarbon in naturally occurring oil bearing reservoir or the artificial storage tank farm (as, oil and gas) extraction.
By foam being introduced the subsurface geology rock stratum to the subsurface geology rock stratum that well is passed carry out completion technology (as, the gravpack well, clean well and consolidate well) be known in the art (referring to for example U.S. Patent No. 7,066,262 (Funkhouser), the disclosure of this patent is incorporated this paper by reference into).Term " well " and " well " comprise recovery well, non-producing well, injection well, fluid handling well, experiment well and prospect pit.That well and well can be is vertical, level, angled-off and their combination between vertical and horizontal (as, have the perpendicular hole of non-perpendicular component).Term " introducing " comprises pumping, injects, pours, discharges, replaces, scatters, circulates, or otherwise utilizes any suitable mode as known in the art that foam is placed in well, well or the subsurface geology rock stratum.
In certain embodiments, the method for the subsurface geology rock stratum of pack processing hydrocarbonaceous also comprises according to the present invention: at least one fissured speed and pressure in the stratum are injected foam in the stratum and a plurality of proppant particles are injected in the crack that forms to be enough to open.The proppant particles that injects stops the crack closure that forms like this, thereby the hydrocarbon in the maintenance stratum can be from its conduction groove that flows through.The technology of proppant particles being injected the subsurface geology rock stratum of pressure break is well known in the art.In certain embodiments, injecting a plurality of proppant particles carries out simultaneously with the injection foam.Proppant particles can be before injecting the stratum and foams mix.In certain embodiments, inject a plurality of proppant particles that reinject after the foam.
Carry out among some embodiment of method of completion in the subsurface geology rock stratum that well is passed, foam also comprises a plurality of gravel particles.The foam that contains the suspension gravel particle can be used to gravel particle be sent to desired zone in the well (as, near the not fixed or weak fixed reservoir sand), thereby form gravpack to strengthen sand control.
Can be used for putting into practice proper supporting agent of the present invention and gravel particle comprises: sand, sintering alum clay, granular stupalith, glass bead and the particulate thermoplastic material of the nut-shell of grating nut-shell, other grating nutshells, resin-coating, the nutshell of other resin-coating, graded sand and stone, resin-coating.The sandstone particle can derive from (for example) Badger Mining company (Berlin, WI); Borden Chemical (Columbus, OH); Fairmont Minerals (Chardon, OH).The thermoplastics particle can derive from (for example) Dow Chemical company (Midland, MI); With BJ Services (Houston, TX).The clay-based particle can derive from (for example) CarboCeramics (Irving, TX); And Saint-Gobain (Courbevoie, France).Sintering alum clay ceramic particle can derive from (for example) Borovichi Refractories (Borovichi, Russia); 3M company (St.Paul, MN); CarboCeramics; With Saint Gobain.Glass bead can derive from (for example) Diversified Industries (Sidney, British Columbia, Canada); With 3M company.The particle size that is adopted can be depending on the characteristic on (for example) stratum.In general, suitable particle size can change to the scope of about 200 orders (U.S.mesh series) about 2.
In certain embodiments, can be used for implementing foam of the present invention and also comprise jelling agent (as phosphoric acid ester).In some these embodiment, this foam also comprises the activator (as the polyvalent metal ion source) of jelling agent.Usually, in the embodiment that uses jelling agent, to can be used for implementing liquid hydrocarbon of the present invention and mix, and the gained mixture will be changed into the foam that can inject the subsurface geology rock stratum with jelling agent (as phosphoric acid ester), activator (as ferric sulfate, iron(ic) chloride, aluminum chloride, sodium aluminate and aluminum isopropylate) and non-ionic polymers type tensio-active agent.Can be used for implementing jelling agent of the present invention and activator at (for example) U.S. Patent No. 4,622,155 people such as () Harris and No.5, describe to some extent among 846,915 people such as () Smith, the disclosure of these patents is incorporated this paper by reference into.Use therein among some embodiment of jelling agent, suitable gel breaker can be included in or be added in the foam, handles foamy viscosity thereby can finally reduce, for example in order at required time it is reclaimed from the stratum.Suitable gel breaker comprise (for example) those in U.S. Patent No. 7,066, the gel breaker of describing among 262 (Funkhouser), the disclosure of this patent is incorporated this paper by reference into.
Following limiting examples further illustrates embodiments of the invention and advantage, but concrete material and amount thereof that these examples are mentioned, and other conditions and details, should not be understood that improper restriction of the present invention.
Except as otherwise noted, otherwise all umbers in example and specification sheets rest part, percentage ratio, ratio etc. all by weight.
Example
Weight-average molecular weight is measured
Example 1,3 and 18 weight-average molecular weight compare definite by adopting gel permeation chromatography (GPC) and linear polystyrene polymkeric substance standard.(derive from (Milford of Waters company in Waters Alliance 2695 systems, MA)) on, use 5 microns SDVB copolymer pellets (to derive from Polymer Laboratories (Shropshire with trade(brand)name " PLGEL ", UK)) four apertures are that 300 millimeters (mm) of 10,000,1000,500 and 100 dusts take advantage of the linear chromatography post of 7.8mm to carry out gpc measurement.Under 40 ℃ temperature, use the RI-detector that derives from Waters company (model 410).Use 10 milliliters of (mL) tetrahydrofuran (THF)s (suppressing with the BHT of 250ppm) that the oligopolymer solids content is accounted for 50 milligrams of (mg) samples of 40% in ethyl acetate and dilute, the syringe filter by 0.45 micron filters then.The sample of 100 microlitre volumes is injected on the distillation column, and the distillation column temperature is 40 ℃.Adopt 1mL/ minute flow velocity, moving phase is tetrahydrofuran (THF).Adopting the peak averaging molecular weight is 3.8 * 10
5Restrain every mole of narrow dispersity polystyrene standard sample and carry out molecular weight calibration to every mole of 580 gram.Adopt suitable GPC software, utilize three rank polynomial fitting of molecular weight calibration curve to proofread and correct and the calculating of molecular weight distribution.Each record result is the mean value that repeats to inject.
Example 1
(300mmHg (4 * 10 in vacuum
4Pa)) under, 50% solution of 340 pounds of (154 kilograms (kg)) N-methyl perfluorinated butane sulfoamido ethyl-methyl acrylate (MeFBSEMA) in ethyl acetate is added in the stainless steel reactor of 75 gallons (284 liters) that jacket temperature is set to 70 (21 ℃), stirs this solution with 80rpm then.Recover vacuum, and 113 pounds of (51kg) methacrylic acid stearyl (are derived from Rohm ﹠amp; Haas (Philadelphia, PA)) is added in the reactor.Recover vacuum, and (premixed solution that derives from Evans Chemetics (Iselin, NJ)) and 2 pounds of (0.9kg) ethyl acetate is added in the reactor, then 229 pounds of (104kg) ethyl acetate is added in the reactor with 276 gram (g) thioglycerols.Reactor is placed nitrogen pressure, and (50psi (3.4 * 10
5Pa)) under, and reactor jacket temperature risen to 149 °F (65 ℃).Continuing under the stirring condition with 80rpm, add 5.7 pounds of (2.6kg) peroxide-2-ethyl hexanoic acid tert-butyls and (derive from the premixed solution of Atofina (Philadephia, 50% solution that is dissolved in solvent oil PA)) and 4 pounds of (1.8kg) ethyl acetate with trade(brand)name " LUPEROX 26M50 ".Stirred reaction mixture also heats reaction mixture about 27 hours under the temperature of 149 (65 ℃), makes it be cooled to about 90 °F (32 ℃), then it is entered in the tube and the pail of 5 gallons (19 liters) of two 55 gallons (208 liters).The weight of products obtained therefrom solution is 645 pounds (292kg).Sample was heated 1 hour under 105 ℃ temperature, and monomer and solvent volatilize fully with this understanding, and definite sample is 41% solid.Utilize the said determination method, weight-average molecular weight is defined as 1.36 * 10
5(number-average molecular weight is 4.0 * 10 to restrain every mole
4Restrain every mole).
MeFBSEA is according to U.S. Patent No. 6,664, method preparation in the A of the example 2 of 354 (Savu) and the B part, this content is incorporated this paper by reference into, and different is to have used 3420kg N-methyl perfluorinated butane sulfoamido ethanol, 1.6kg thiodiphenylamine, 2.7kg methoxyl group quinhydrones, 1400kg heptane, 980kg methacrylic acid (replacement vinylformic acid), 63kg methanesulfonic (replacement trifluoromethanesulfonic acid) and 7590kg water in the B part.
The foam stabilization property testing
By with kerosene (can be the solution that 41% solution dilutes the example 1 for preparing 1 weight % to solids content in the ethyl acetate available from Alfa Aesar (Ward Hill, MA)), thus the solution of preparation 188mL.Place the food mixer of being furnished with wire whisk (in can a mixing bowl, under room temperature (22 ℃), to stir this solution 3 minutes then this solution with 300rpm available from Hobart (Troy, OH), model is N-50).With the gained foam be transferred to immediately make by " NALGENE " high density poly propylene, internal diameter be about 8 centimetres, highly for about 52 centimetres 2000mL graduated cylinder (can be available from the VWR International (West Chester, PA)).With mL is that lather volume is measured by unit, and record foam expansion rate (promptly using lather volume divided by 188).Pass in time and observe lather volume, the time when the recording liquid volume is 94mL (half foam life period).Calculate foam index (being the product of foam expansion rate and half foam life period).Half foam life period, lather volume and foam index are recorded in the following table 1.
Table 1
| Fluorinated monomer (g) | Non-fluorinated monomer (g) | Half foam life period, minute | Lather volume, mL | Foam index | |
| Example 1 | MeFBSEMA (77,000) | Methacrylic acid stearyl (51,000) | 25 | 1380 | 183 |
| Example 2 | MeFBSEA (50) | Methacrylic acid stearyl (50) | 55 | 1500 | 438 |
| Example 3 | MeFBSEA (250) | Methacrylic acid stearyl (250) | 51.5 | 1450 | 389 |
| Example 4 | MeFBSEA (50) | Stearyl acrylate base ester (50) | 43 | 1450 | 331 |
| Example 5 | MeFBSEA (40) | Methacrylic acid stearyl (60) | 41 | 1550 | 337 |
| Example 6 | MeFBSEA (60) | Methacrylic acid stearyl (40) | 28.5 | 1300 | 197 |
| Example 7 | MeFBSEA (40) | Methacrylic acid docosyl ester (60) | 40.5 | 1350 | 290 |
| Example 8 | MeFBSEA (50) | Methacrylic acid docosyl ester (50) | 34.5 | 1150 | 211 |
| Example 9 | MeFBSEMA (55) | Methacrylic acid stearyl (45) | 23.5 | 1300 | 162 |
| Example 10 | MeFBSEMA (60) | Methacrylic acid stearyl (40) | 23 | 1360 | 166 |
| Example 11 | MeFBSEMA (65) | Methacrylic acid stearyl (35) | 24 | 1300 | 165 |
| Example 12 | MeFBSEMA (412) | Methacrylic acid docosyl ester (275) | 30.5 | 1275 | 207 |
| Example 13 | MeFBSEMA (70) | Methacrylic acid stearyl (30) | 16.5 | 1060 | 93 |
| Example 14 | MeFBSEA (60) | Methacrylic acid decyl ester (40) | 13 | 1250 | 86 |
| Example 15 | MeFBSEA (70) | Lauryl methacrylate (30) | 17.5 | 1350 | 125.7 |
| Example 16 | FBMA (60) | Methacrylic acid stearyl (40) | 12.5 | 2100 | 139.6 |
| Example 17 | MeFBSEMA (50) | Methacrylic acid stearyl (50) | 14.5 | 1100 | 85 |
| Example 18 | MeFBSEA (250) | Methacrylic acid stearyl (250) | 13 a | 1570 a | 109 a |
| Illustrative examples 1 | FBMA(50) | Methacrylic acid cetyl ester (50) | 0.5 | 1050 | 2.75 |
| Illustrative examples 2 | MeFBSEMA (40) | Methacrylic acid stearyl (60) | 2 | 960 | 10 |
| Illustrative examples 3 | FBMA(60) | Stearyl acrylate base ester (40) | 9 | 1600 | 76.5 |
| Illustrative examples 4 | MeFBSEMA (60) | Methacrylic acid decyl ester (40) | Insoluble b | Insoluble b | Insoluble b |
| Illustrative examples 5 | MeFBSEMA (60) | Lauryl methacrylate (40) | 5.5 | 940 | 28 |
| C.E. cA | FOMA(30) | Lauryl methacrylate (70) | 0.25 | 600 | 0.8 |
| C.E. cB | EtFOSEA(60) | Lauryl methacrylate (40) | 19 | 1500 | 152 |
| C.E. cC | NFA(10) | Lauryl methacrylate (6.7) | 0.25 | 500 | 0.66 |
| C.E. cD | NFA(10) | Lauryl methacrylate (30) | 0 | 500 | 0 |
| C.E. cE | NFMA(10) | Lauryl methacrylate (23) | 8.5 | 2250 | 102 |
| C.E. cF | NFMA(10) | Lauryl methacrylate (6.7) | 9 | 1400 | 67 |
aThe mean value of twice measurement.
bPolymkeric substance is insoluble to kerosene; Therefore, the preparation foam is impossible.
cComparative example.
Example 2
Under nitrogen gas stream, 50g N-methyl perfluorinated butane sulfoamido ethyl propylene acid esters (MeFBSEA), 50g octadecyl methyl acrylate (are derived from TCI (Tokyo, Japan), purity is 95%), (derive from Sigma-Aldrich (Milwaukee, WI)) and 143g ethyl acetate is added in the 1L flask of being furnished with overhead type agitator, thermopair and reflux exchanger the 0.2g thioglycerol.After the adding, the content of flask is remained under the nitrogen pressure of malleation a little.(derive from VWR International (West Chester, PA)) temperature set points is risen to 65 ℃, and add 50/50 mixture of 2.0g solvent oil/peroxide-2-ethyl hexanoic acid tert-butyl (" LUPEROX 26M50 ") with the J-Kem temperature regulator.Observing response 15 minutes rises to 70 ℃ with temperature regulator with temperature set points then.This is reflected at heated overnight under 70 ℃ the temperature, makes it be cooled to room temperature then.The mensuration of froth stability is by example 1 described carrying out, and outcome record is in last table 1.
MeFBSEA is according to U.S. Patent No. 6,664, method preparation in the A of the example 2 of 354 (Savu) and the B part, this content is incorporated this paper by reference into, and different is to use 4270kg N-methyl perfluorinated butane sulfoamido ethanol, 1.6kg thiodiphenylamine, 2.7kg methoxyl group quinhydrones, 1590kg heptane, 1030kg vinylformic acid, 89kg methanesulfonic (replacement trifluoromethanesulfonic acid) and 7590kg water in the B part.
Example 3
Method with example 2 prepares example 3, different be to use 250g MeFBSEA, 250g methacrylic acid stearyl (derive from 50/50 mixture and the 715g ethyl acetate of Sigma-Aldrich (Milwaukee, WI)), 1.0g thioglycerol, 10.0g solvent oil/peroxide-2-ethyl hexanoic acid tert-butyl (" LUPEROX26M50 ").Utilize the said determination method, weight-average molecular weight is defined as 1.28 * 10
5(number-average molecular weight is 6.8 * 10 to restrain every mole
4Restrain every mole).The mensuration of froth stability is by example 1 described carrying out, and outcome record is in last table 1.
Example 4-17, illustrative examples 1-5 and Comparative examples A-B
Utilize the method for example 2 to prepare and measure example 4-17, illustrative examples 1-5 and Comparative examples A-B, different monomer shown in the last table 1 and the amounts of being to use.
Stearyl acrylate base ester derives from VWR International.
Methacrylic acid docosyl ester with trade(brand)name " CIBA AGEFLEX FM22 " derive from Ciba Specialty Chemicals (Basel, Switzerland).
Methacrylic acid decyl ester and methacrylic acid cetyl ester derive from Monomer-Polymer ﹠amp; Dajac Labs (Feasterville, PA).
Lauryl methacrylate derive from Avocado Organics (Ward Hill, MA).2,2,3,3,4,4,4-seven fluorine butyl-2-methacrylic ester (FBMA) is according to preparation described in the 47th section of the EP1311637 that announced on April 5th, 2006 people such as () Savu, and this patent is incorporated this paper by reference into.
2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-15 fluorine octyl group-2-methacrylic ester (FOMA) with trade(brand)name " L-9179 " derive from 3M company (St.Paul, MN).
N-ethyl PFO sulfoamido ethyl propylene acid esters (EtFOSEA) derives from 3M company with trade(brand)name " FX-13 ".
Measure by the example 1 described froth stability of carrying out.The brbble test result of example 4-17, illustrative examples 1-5 and Comparative examples A-B provides in last table 1.
Comparative example C
Under nitrogen gas stream, with 10g 3,3,4,4,5,5,6,6, (deriving from Daikin Chemical Sales (Osaka, Japan)), 6.7g lauryl methacrylate (deriving from Avocado Organics), 0.03g thioglycerol and 33g ethyl acetate, to be added into the capacity of being furnished with overhead type agitator, thermopair and reflux exchanger be in the flask of 1L to 6-nine fluorine ethylhexyl acrylates (NFA).After the adding, the content of flask is remained under the nitrogen pressure of malleation a little.With J-Kem temperature regulator (deriving from VWR International) temperature set points is risen to 65 ℃, add 50/50 mixture of 0.33g solvent oil/peroxide-2-ethyl hexanoic acid tert-butyl (" LUPEROX 26M50 ") then.Observing response 15 minutes rises to 70 ℃ with temperature regulator with temperature set points then.This is reflected at heated overnight under 70 ℃ the temperature, makes it be cooled to room temperature then.The mensuration of froth stability is by example 1 described carrying out, and outcome record is in last table 1.
Comparative Example D-F
Utilize the method for comparative example C to prepare and measure Comparative Example D-F, different monomer shown in the last table 1 and the amounts of being to use.3,3,4,4,5,5,6,6,6-nine fluorine hexyl-2-methacrylic ester (NFMA) derive from Indofine Chemical company (Hillsborough, NJ).
Example 18
Utilize the method for example 3 to prepare and measure example 18, different is that polyreaction is carried out in hexane.Utilize the said determination method, the weight-average molecular weight of resulting polymers is defined as 8.9 * 10
4(number-average molecular weight is 5.7 * 10 to restrain every mole
4Restrain every mole).Foam characteristic provides in last table 1.
Comparative example G
Under nitrogen gas stream, it is in the flask of 5L that 840g MeFBSEMA, 560g methacrylic acid stearyl (deriving from Sigma-Aldrich), 14.0g thioglycerol and 2000g ethyl acetate are added into the capacity of being furnished with overhead type agitator, thermopair and reflux exchanger.After the adding, the content of flask is remained under the nitrogen pressure of malleation a little.With J-Kem temperature regulator (deriving from VWR International) temperature set points is risen to 73 ℃, add 50/50 mixture of 84g solvent oil/peroxide-2-ethyl hexanoic acid tert-butyl (" LUPEROX 26M50 ") then.Observing response 15 minutes rises to 78 ℃ with temperature regulator with temperature set points then.This is reflected at 78 ℃ heated 6 hours 20 minutes down, make it be cooled to room temperature then.Utilize the said determination method, the weight-average molecular weight of resulting polymers is defined as 1.5 * 10
4(number-average molecular weight is 9.1 * 10 to restrain every mole
3Restrain every mole), different is is dissolved in the sample of 125mg in the tetrahydrofuran (THF), and chromatographic column is under the room temperature, uses light scattering detector (deriving from PolymerLaboratories), and to adopt the peak averaging molecular weight be 1.1 * 10
6Restrain every mole of narrow dispersity polystyrene standard and carry out molecular weight calibration to every mole of 168 gram.By example 1 described mensuration of carrying out froth stability.Lather volume is 1120mL, and half foam life period is 8.5 minutes, and foam index is 51.
Comparative Example H
Non-ionic polymers type tensio-active agent (the solution that comprises 1 weight % of fluorinated repeating units according to the method preparation of example 1 as 50% with 8 perfluorinated carbon atoms, derive from 3M company (St.Paul, MN)) solution and make its foaming with trade(brand)name " FC-740 ".Lather volume is 1660mL, and half foam life period is 32 minutes, and foam index is 282.
Comparative Example I
Utilize the method for example 2 to prepare Comparative Example I, different be to use 60gMeFBSEMA, 20g methacrylic acid stearyl and 20g (derive from Union Carbide (Danbury with trade(brand)name " CARBOWAX 750 " from the end capped polyoxyethylene alcohol of methoxyl group, CT)) Zhi Bei acrylate monomer, this acrylate monomer uses U.S. Patent No. 3,728, step described in 151 (people such as Sherman) example 17, the disclosure of this patent is incorporated this paper into way of reference.This polymkeric substance is insoluble to kerosene; Therefore, the preparation foam is impossible.
Comparative Example J
The method of use-case 2 prepares and measures Comparative Example J, and different is to have used 55g MeFBSEMA, 40g methacrylic acid stearyl and 5g vinylformic acid (deriving from Sigma-Aldrich) in preparation.By example 1 described mensuration of carrying out froth stability.Lather volume is 1240mL, and half foam life period is 4.5 minutes, and foam index is 29.9.
Example 19
(deriving from Sunoco Service Station (London, Ontario)) is incorporated with in the vial of metal blind nut with the diesel oil of 100g automotive grade.Adding is according to the tensio-active agent of example 1 preparation, with 0.5% surfactant soln in the preparation diesel oil.With the bottle cap upper cover and with hand rolling 30 seconds.Visual inspection bottle when 5 seconds, 30 seconds, 1 minute, 5 minutes, 15 minutes, 30 minutes and 60 minutes, and when each the detection, all observe foamy and exist.
Example 20
Come embodiment 20 according to example 19 is described, different is the surfactant soln of preparation 0.3%.All observing foamy when each the detection exists.
Example 21
Come embodiment 21 according to example 19 is described, different is the surfactant soln of preparation 0.1%.Observing foamy when 5 seconds, 30 seconds, 1 minute, 5 minutes and 15 minutes exists.In the time of 30 minutes, do not observe foam.
Example 22
Method according to comparative example G prepares example 22, different is before the temperature of reaction mixture to be risen to 60 ℃ at interpolation peroxide-2-ethyl hexanoic acid tert-butyl " LUPEROX 26M50 " initiator, after adding initiator, 70 ℃ of following reaction stirred 18 hours.Utilize the said determination method, weight-average molecular weight is defined as 1.6 * 10
4(number-average molecular weight is 1.0 * 10 to restrain every mole
4Restrain every mole).By example 1 described mensuration of carrying out froth stability.Foam height is 1120, and half foam life period is 20 minutes, and foam index is 119.
Example 23
Method according to example 1 prepares example 23, different is to add 85g initiator " LUPEROX 26M50 " before in the 60g ethyl acetate, and 2520g MeFBSEMA, 1680g methacrylic acid stearyl, 9g thioglycerol and 5940g ethyl acetate are added in 22 liters of reactors.Utilize the said determination method, weight-average molecular weight is defined as 5.3 * 10
4(number-average molecular weight is 1.6 * 10 to restrain every mole
4Restrain every mole).By example 1 described mensuration of carrying out froth stability.Foam height is 1290, and half foam life period is 25 minutes, and foam index is 172.
Example 24 to 27
Method according to example 2 prepares example 24 to 27, different monomer shown in the following table 2 and the amounts of being to use, and when reaction finishes, add extra 122g ethyl acetate, be cooled to room temperature afterwards.Method according to example 1 provides in following table 2 result that example 24 and 27 carries out brbble test.
Table 2
| Fluorinated monomer (g) | Non-fluorinated monomer (g) | Non-fluorinated monomer (g) | Half foam life period, minute | Lather volume, mL | Foam index | |
| Example 24 | MeFBSEA (50) | Methacrylic acid stearyl (40) | Methacrylic acid docosyl ester (10) | 15 | 1360 | 115 |
| Example 25 | MeFBSEA (56) | Methacrylic acid stearyl (22) | Methacrylic acid docosyl ester (22) | 33 | 1500 | 263 |
| Example 26 | MeFBSEA (50) | Methacrylic acid stearyl (25) | Methacrylic acid docosyl ester (25) | 37 | 1500 | 295 |
| Example 27 | MeFBSEA (50) | Methacrylic acid stearyl (10) | Methacrylic acid docosyl ester (40) | 50 | 1500 | 402 |
Under the prerequisite that does not depart from the scope of the present invention with spirit, those skilled in the art can make various modifications and change to the present invention, and should be appreciated that the present invention should not be subject to the exemplary embodiment shown in this paper undeservedly.
Claims (11)
1. method of in the subsurface geology rock stratum that well is passed, carrying out completion, described method comprises:
The foam that comprises liquid hydrocarbon and contain the non-ionic polymers type tensio-active agent of fluorinated repeating units is provided, wherein said fluorinated repeating units has maximum 5 perfluoro-carbon atoms, and the solution of the 1 weight % of wherein said non-ionic polymers type tensio-active agent in kerosene is at least 10 minutes at 22 ℃ half foam life period;
Described foam is introduced in the well of described subsurface geology rock stratum; And
In the well of described subsurface geology rock stratum, carry out well completion operations.
2. method according to claim 1, wherein said well completion operations are the described well of gravpack, the described well of cleaning or consolidate at least a in the described well.
3. method according to claim 1 and 2, wherein said non-ionic polymers type tensio-active agent comprises:
At least one is by the divalent unit of represented by formula I:
The divalent unit that at least one is represented by Formulae II:
Wherein
Rf is the perfluoroalkyl with 3 to 4 carbon atoms;
R and R
2Be the alkyl of hydrogen or 1 to 4 carbon atom independently of one another;
R
1It is the alkyl of 16 to 24 carbon atoms; And
N is 2 to 11 integer.
4. method according to claim 3, wherein R
1It is the alkyl of 18 to 22 carbon atoms.
5. according to claim 3 or 4 described methods, wherein said non-ionic polymers type tensio-active agent comprises the divalent unit by represented by formula I, based on the gross weight of described non-ionic polymers type tensio-active agent, the content of described divalent unit is in the scope of 45 to 75 weight %.
6. according to each described method of aforementioned claim, the weight-average molecular weight of wherein said non-ionic polymers type tensio-active agent is every mole of at least 45,000 gram.
7. according to each described method of aforementioned claim, the 1 weight % solution of wherein said non-ionic polymers type tensio-active agent in kerosene is at least 20 minutes at 22 ℃ half foam life period.
8. according to each described method of aforementioned claim, wherein based on described foamy gross weight, the content of described non-ionic polymers type tensio-active agent is in the scope of 0.1 weight % to 5 weight %.
9. according to each described method of aforementioned claim, wherein said liquid hydrocarbon is at least a in kerosene, diesel oil, gasoline, pentane, hexane, heptane, mineral oil or the cycloalkanes.
10. according to each described method of aforementioned claim, wherein said foam also comprises a plurality of gravel particles.
11. a method for preparing non-ionic polymers type tensio-active agent, described method comprises:
Mix each component, described component comprises:
At least a compound by following chemical formulation:
At least a compound by following chemical formulation:
Wherein
Rf is independently for having the perfluoroalkyl of 3 to 4 carbon atoms;
R and R
2Be the alkyl of hydrogen or 1 to 4 carbon atom independently of one another;
R
1Be the alkyl of 16 to 24 carbon atoms independently; And
N is 2 to 11 integer independently,
Chain-transfer agent,
Radical initiator and
Solvent; And
The described component of heating under the highest 70 ℃ temperature.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62509307A | 2007-01-19 | 2007-01-19 | |
| US11/625,093 | 2007-01-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101595196A true CN101595196A (en) | 2009-12-02 |
Family
ID=39512638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008800026080A Pending CN101595196A (en) | 2007-01-19 | 2008-01-18 | Use the method for stable hydrocarbon foams |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2111432A2 (en) |
| CN (1) | CN101595196A (en) |
| CA (1) | CA2675349A1 (en) |
| WO (1) | WO2008089386A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942910A (en) * | 2012-11-27 | 2013-02-27 | 唐山市金沙工贸有限公司 | Surfactant for enhancing oil recovery factor |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2841573A (en) * | 1955-12-29 | 1958-07-01 | Minnesota Mining & Mfg | Fluorocarbon vinyl-type esters and polymers |
| US4557837A (en) * | 1980-09-15 | 1985-12-10 | Minnesota Mining And Manufacturing Company | Simulation and cleanup of oil- and/or gas-producing wells |
| US4432882A (en) * | 1981-12-17 | 1984-02-21 | E. I. Du Pont De Nemours And Company | Hydrocarbon foams |
| EP0624710A1 (en) * | 1993-05-05 | 1994-11-17 | Minnesota Mining And Manufacturing Company | A foamable oil well-treatment-fluid |
| DE60042561D1 (en) * | 1999-10-27 | 2009-08-27 | 3M Innovative Properties Co | FLUOROCHEMICAL SULPHONAMIDE TENSIDES |
| ATE421564T1 (en) * | 2002-05-24 | 2009-02-15 | 3M Innovative Properties Co | USE OF SURFACE-MODIFIED NANOPARTICLES FOR OIL EXTRACTION |
| DE602004032231D1 (en) * | 2004-09-02 | 2011-05-26 | 3M Innovative Properties Co | A method of treating porous stone using a fluorochemical composition |
-
2008
- 2008-01-18 CA CA002675349A patent/CA2675349A1/en not_active Abandoned
- 2008-01-18 EP EP08727885A patent/EP2111432A2/en not_active Withdrawn
- 2008-01-18 WO PCT/US2008/051403 patent/WO2008089386A2/en active Application Filing
- 2008-01-18 CN CNA2008800026080A patent/CN101595196A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942910A (en) * | 2012-11-27 | 2013-02-27 | 唐山市金沙工贸有限公司 | Surfactant for enhancing oil recovery factor |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2675349A1 (en) | 2008-07-24 |
| EP2111432A2 (en) | 2009-10-28 |
| WO2008089386A3 (en) | 2008-09-12 |
| WO2008089386A2 (en) | 2008-07-24 |
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Application publication date: 20091202 |