CN101146888B

CN101146888B - Soluble deverting agents

Info

Publication number: CN101146888B
Application number: CN2006800093692A
Authority: CN
Inventors: A·R·辛克莱尔; S·阿克巴; P·R·奥克尔
Original assignee: Fairmount Minerals Ltd
Current assignee: Fairmount Minerals Ltd
Priority date: 2005-01-21
Filing date: 2006-01-20
Publication date: 2012-08-08
Anticipated expiration: 2026-01-20
Also published as: WO2006088603A1; MX2007008850A; RU2433157C2; RU2007131659A; US20060175059A1; NO20074239L; CA2595686C; GB2437869A; GB2437869B; CA2595686A1; CN101146888A; GB0714796D0

Abstract

Methods and compositions for stimulating single and multiple intervals in subterranean wells by diverting well treatment fluids into a particular direction or into multiple intervals using water soluble coated diverting agents are described. The water soluble coating of the diverting material is preferably a collagen, poly(alkylene) oxide, poly(lactic acid), polyvinylacetate, polyvinylalcohol, polyvinylacetate/polyvinylalcohol polymer or a mixture thereof applied as a coating on any number of proppants. The method allows for the diverting of the flow of fluids in a downhole formation during a well treatment, such as during a fracturing process. Following completion of a treatment such as a hydraulic stimulation, the soluble diverting agent can be dissolved and removed by the water component of the well production.

Description

Soluble deverting agents

The application requires the right of priority of the U.S. Provisional Application SN 60/646,231 of submission on January 21st, 2005, and the full content of this application is attached to this paper by reference.

Invention field

The invention provides the method and composition of handling missile silo, more particularly, the method and composition that makes a plurality of well section raising the output in the missile silo is provided.Specifically; The invention provides through introducing and be coated with propping material or its of water-soluble polymers (for example collagen protein, Yodo Sol VC 400/Z 150PH, gather trialkylphosphine oxide, gather the silicate polymer of (lactic acid), periodic table of elements I or II family (basic metal or earth alkali metal)) and redirect the combination that flows to the slow water-soluble material of ground environment from the stimulation fluid of tubing string, make the well treat fluid redirect to the method and composition of a plurality of well sections.

Technical background

Well is handled the RF that (the for example acid on stratum and fracture treatment) is generally used for improving or increasing hydro carbons.Under many circumstances, the stratum can comprise two or more well sections with different permeability and/or injectability.Some well sections are owing to reasons such as low relatively, former terrestrial stress height of perviousness and/or formation damage possibly have low relatively injectability, or the fluidic ability is injected in acceptance.This type well section can be come completion and/or can come completion through hole completion method through preparation in the running casing well.In some cases, this type subterranean wells section can be present in the high inclination or horizontal section of well, for example in the effluent open hole section.Under any circumstance, when processing has a plurality of well section of different injectabilities, promptly whether all, also often be that well treat fluid that great majority are introduced will be transferred in the well section with the highest injectability one or a few.Even under the situation that a pending well section is only arranged, also possibly grow up or down in the crack.This perviousness that depends on original place reservoir stress and stratum changes.Maybe the water leg below the man-made fracture.If man-made fracture is expanded into this district, then maybe be because of there be too many water in well and be damaged because of the petroleum component of recovery well section blocks.On the man-made fracture district, possibly there is pneumatic jack, because the petroleum liquid component of gas shunting well, so pneumatic jack will cause damage to well production.

Be used for making treat fluid to redirect to the method and the material of the lower well section of perviousness and/or injectability in order the recovery well treat fluid to be assigned in each in a plurality of pending well sections more equably, to have developed.Yet routine turns to technology possibility costliness and/or possibly only obtain very limited achievement.In this, the mechanical steering technology is complicated and expensive usually.In addition, the mechanical steering method is confined to the situation of cased well and depends on enough being used to realize the cement and the equipment spacer that turn to usually.

Therefore, in the well stimulation treatment, be difficult to handle effectively extension vertical section and the processing simultaneously eyelets of organizing for many years all the time more.Many processing forward methods (FLAX-2 of for example oil soluble calcium soap, sulfuric acid and Dowell " Fixafrac " (mixture of lime, kerosene, classification chlorination calcium soap and jelling agent) and Dowell ^TM(like the summary of Harrison at his Journal of PetroleumTechnology, described in the pp.593-598 (1972)) is used to handle a plurality of districts with different efficient.Many kinds of chemotype diversion agents have been attempted being used to stop up the stratum opening and making treat fluid redirect to other districts on stratum.For example, used the wax pearl as diversion agent.Yet; The wax pearl has limited fusing point: about 138

to about 192

, this makes it when FT surpasses its fusing point, lose efficacy.

Also describe naphthalene (naphthalene ball (moth ball)) and sodium chloride particle and can be used as effective diversion agent.The naphthalene particle is soluble in the oil; And about 180

down fusion, therefore limited its application in the lesser temps stratum.The fusing point of sodium-chlor is about 1; 470

; Can at high temperature use; But need be handling stratum water or diluted acid cleaning well afterwards, so that remove sodium chloride particle fully.In addition, bring certain problem owing to the formation insoluble precipitate possibly stop well, sodium-chlor can not be used to handle missile silo with hydrofluoric acid.

Perhaps, when handling a plurality of well section with different injectabilities at the same time, used diversion agent, for example polymkeric substance, suspended solid material and/or foams.Usually before pumping well treat fluid, this type diversion agent is pumped in the stratum, so that the higher well section of shutoff perviousness and make the well treat fluid redirect to the lower well section of perviousness.Yet the steering-effecting of this type diversion agent often is difficult to prediction and monitoring, and treat fluid is redirect in all desired well sections.These problems particularly have in the high inclination completion of big area to the stratum of well opening especially serious at open hole completion.The existence of natural fracture also can make and turn to difficulty more.

Carried out the effort of the problem of different permeability zones in many solution wells for many years.The USP of authorizing Hower provides the infiltrative method on the stratum that a kind of increase has several different permeability zones for the 2nd, 803, No. 306.Described step comprises introduces the treat fluid that contains hydrochloric acid in well, the oil soluble particles dispersed is in said treat fluid, and this material is selected from stellar coal, naphthalene, santochlor, anthracene and β-Nai Fen.When handling, particle partly stops up the high permeability area on stratum, lets treat fluid get into low permeability areas.

The USP that transfers Halliburton discloses for the 3rd, 797, No. 575 by being dissolved in turning to that relative water insoluble solid material in the solvent (for example methyl alcohol or Virahol) forms and has formed additive.When this additive and aqueous treatment fluid were mixed, the solid material that is dissolved in the additive precipitate formation form in small, broken bits in the aqueous treatment fluid, and it serves as diversion agent subsequently.The USP that transfers Halliburton has equally been described for the 3rd, 724, No. 549 and a kind ofly has been used for making the aqueous treatment fluid to redirect to the diversion agent material on the gradually poor stratum of perviousness.This material by carrier fluid and fusing point be about 200

have about 20 and form to the ring-type of about 1,400 carbon atom or the resinoid graded particies of straight chain hydrocarbon.This material is described to water insoluble basically and sour, but oil-soluble makes resin after accomplishing the oil treatment operation, to be removed by output oil.

Knight etc. are at USP the 3rd, 872, have described in No. 923 and have used radiation-induced type polymkeric substance as temporary transient or permanent diversion agent.According to this specification sheets; Infiltrative temporary transient or permanent reduction can obtain through the aqueous solution that injects water-soluble polymers, and said water-soluble polymers obtains through the radiation-induced polymerization of an alkali metal salt of acrylic amide and/or USAF RH-1 and vinylformic acid, methylacrylic acid and/or this type acid.The resulting polymers diversion agent has for example temperature and the stable character of pH, so that reduce the porous medium perviousness effectively.Perviousness in the stratum can be recovered with decomposing copolymer through using chemical (for example hypochlorous acid hydrazine solution or strong inorganic acid) to handle subsequently.

The USP of Scheffel etc. provides polymer diverter for the 3rd, 954, No. 629 and the 4th, 005, No. 753 and has handled the method on stratum respectively with this base polymer diversion agent.Comprise Vilaterm, vinyl-vinyl acetate copolymer, polymeric amide and the for example solid particulate of the homogenizing mixture of the tenderizer of long chain aliphatic diamide according to describing said polymer compsn.It is reported this polymer diverter be applicable to FT be equal to or greater than 350

the stratum in.

Dill etc. are at USP the 4th, 527, have described the method that diverting material that uses to comprise aqueous carrier solution and the diversion agent that comprises solid azo component and methylene radical (methylenic) component temporarily stop up the stratum in No. 628.Diversion agent is preferably Hansa Yellow G (Fanchon YellowYH-5707 pigment) or Fast Yellow 4RLF dyestuff; The both have azo component and methylene radical component and have fusing point at least 332.6

, about 200 to about 425

temperature under in water, have certain solubility and about 200

to about 425

temperature under in kerosene, have the characteristic of certain solubility.

Purvis etc. are at USP the 6th, 367, have described in No. 548 through the well treat fluid being redirect to make in a plurality of well sections the method and composition of a plurality of well sections raising the output in the missile silo.According to this specification sheets, this is through alternately realizing to the stratum to the stratum and from tubing string transfer processing fluid from the annular zone transfer diversion agent of well.

The additive method that fracture treatment is turned to comprises LaGrone etc.; SPE 530; Limit discharge method (limited-entry technique) that pp.695-702 (1963) describes and Dingxiang etc., SPE 30816, many Splitting Method of use diversion agent (TMFUD) pressure break that 80-86 page or leaf (1988) proposes; The latter shows that the average petroleum production of each well improves 15.0t/d, and ultimate production improves 340.3 * 10 ⁴Ton.Diversion agent (the Alleman based on viscoelastic surfactant that is used for acid stimulation has also been described; D. etc.; SPE 80222 (2003)); It is VES gel (polyQuat), it is characterized in that under high pH stable and about 250

heat-staple unique vesicle structure.Usually, before pumping well stimulation fluid, this gel-type diversion agent is pumped in the stratum so that the high well section of shutoff perviousness and make the well treat fluid redirect to the low well section of perviousness.

According to all these progress and new technology, the steering-effecting of diversion agent often is difficult to prediction and monitoring, and treat fluid is redirect in all desired well sections, therefore fails farthest to bring into play the advantage of fracturing process.These problems are at open hole completion, particularly have can advance in the high inclination completion of big area to the stratum of well opening especially serious.The natural fracture that exists in the stratum also can make to turn to and have more challenge.Therefore, exist for making the well treat fluid redirect to novel composition and the needs of method in the well section of a plurality of different permeabilities in the stratum.

Summary of the invention

The invention provides a kind of in the stratum, the use and have the method for the particle of solubility top coating as diversion agent.Under type well in the presence of fracturing fluid and the gel breaker compsn, under downhole temperature and pressure through want the time after, the solubility top coating will dissolve.The instance of solubility top coating comprises collagen protein, gathers (alkylidene group) oxide compound, the silicate polymer that gathers (lactic acid), Yodo Sol VC 400, Z 150PH, Yodo Sol VC 400/Z 150PH, polylactone, polyacrylic ester, latex, polyester, I or II family or its mixture.

The invention provides water-soluble polymers propping agent that applies and the method for using this type diversion agent processing stratum as diversion agent.Diversion agent and carrier fluid are introduced in the stratum together.Carrier fluid flows in the crack and/or well section in the stratum.These cracks or well segment table be in various degree perviousness at present.According to the method for the invention, carrier fluid at first flows to the highest well section of perviousness with diversion agent.The temperature on stratum will cause the softening and swelling of the water-soluble polymers coating of diversion agent, stop up the crack thus.

In one embodiment, described and be suitable for making the well treat fluid to redirect to the diversion agent in single or a plurality of well sections, wherein this diversion agent is made up of particulate matrix and water soluble outer.The instance of this type water soluble outer polymkeric substance has (being not limited to) collagen protein, gathers (alkylidene group) oxide compound, gathers (lactic acid), the silicate polymer of Yodo Sol VC 400, Z 150PH, Yodo Sol VC 400/Z 150PH, polymerization lactone, water-soluble acrylic, latex, polyester, I or II family and composition thereof.

In another embodiment, described and be suitable for making the well treat fluid to redirect to the diversion agent in single or a plurality of well sections, wherein this diversion agent is formed by particulate matrix, middle water-insoluble layer and water-soluble polymers are outer.The instance of water soluble outer polymkeric substance has (being not limited to) collagen protein, gathers (alkylidene group) oxide compound, gathers (lactic acid), the silicate polymer of Yodo Sol VC 400, Z 150PH, Yodo Sol VC 400/Z 150PH, polymerization lactone, water-soluble acrylic, latex, polyester, I family or II family and composition thereof.The instance in water-insoluble middle layer has solvable fusible novolac polymer and solvable novolac polymer.

In another embodiment, described and be suitable for making the well treat fluid to redirect to the diversion agent in the single or a plurality of well sections in the well, wherein this diversion agent is mainly water-soluble polymer particles, for example the collagen protein pearl; Or gather (alkylidene group) oxide compound, gather (lactic acid), Yodo Sol VC 400, Z 150PH, Yodo Sol VC 400/Z 150PH, polymerization lactone, water-soluble acrylic, latex, polyester, I or the silicate polymer of II family or the granular particle of its mixture.

In another embodiment, disclose the method for the single well section raising the output that makes the stratum, this method may further comprise the steps: in pipe in the diversion agent that has water soluble ingredient on its skin and low viscosity fluid or the fracturing fluid combination introducing well; Diversion agent and fracturing fluid are transferred in the stratum, let the diversion agent blocking portion stratum of just handling gradually; Repeat this process as required, during fracturing operation, diversion agent is added in the carrier fluid in the slug.

The accompanying drawing summary

Following accompanying drawing becomes the part of this specification sheets and consults these accompanying drawings to further specify some aspect of the present invention.Detailed description with reference to the specific embodiments that one or more accompanying drawing and this paper provided can be understood the present invention better.

Fig. 1 shows the front section view of the down-hole part on the stratum with vertical pipes and single processing well section, wherein just according to the diversion agent injection hydrocarbon-containifirst stratum of an aspect disclosed by the invention with multiple coating.

The front section view on the stratum of Fig. 2 explanatory view 1 wherein just injects the hydrocarbon-containifirst stratum of having injected diversion agent of the present invention with propping agent.

Fig. 3 shows the well with vertical pipes and a plurality of

processing well section

58,60 and 62, and just injects according to the diversion agent of an aspect disclosed by the invention with multiple coating.

Definition

Provide to give a definition to help those skilled in the art to understand the detailed description of invention.

The term " carrier fluid " that this paper uses is meant the liquid based on oil or water of the particle (for example propping agent) that can move suspended state.The LV carrier fluid has less current capacity and particle possibly receive influence of gravity, if therefore pellet density little then particle rises than liquid, if or pellet density big then particle sinks than fluid density.High viscosity liquid can deliver sedimentation or rising degree smaller particles, because viscosity has overcome gravitational effect.

The term " linking agent (crosslinker; cross-linking agent) " that this paper uses is meant that those are used for the compound of covalent modified protein (for example collagen protein), and comprises the same bifunctional cross-linker of containing two identical reactive groups and the Heterobifunctional linking agent that contains two different activities groups.

Term " diversion agent " meaning that this paper uses refers to and typically refers in order to temporarily or for good and all to prevent liquid-flow to the reagent that is usually located at the specific position in the stratum that wherein this reagent is used for sealing this position, and cause liquid " turns to " different positions thus.

The term " propping agent " that this paper uses is meant that those are used for well well workover and the fixed size particle of processing (for example waterfrac treatment operation) with maintenance crack openings after processing.This type fixed size particle often mixes with fracturing fluid after waterfrac treatment processing or the processing of similar down-hole well, to keep crack openings.Except that naturally occurring sand grains and nutshell, term " propping agent " also comprises the propping agent of artificial or concrete design, and the for example sand grains of resin-coated or high-intensity stupalith are like sintered bauxite.The propping agent of resin-coated is representative with the propping agent that is coated with solvable fusible novolac polymer or solvable novolac polymer.Usually, but not inevitable ground, proppant material is produced the effective pipeline of fluid from the reservoir to the well by size and spherical careful classification to be provided for making.

In described herein and disclosed embodiment, the term of use " introducing " comprises the pumping in well, well or stratum of use any suitable method as known in the art, injection, impouring, release, transfer, application of sample, circulation or places fluid or material in addition.Equally, the term that uses of this paper " mixes ", " contact " and " applying " comprise to be enough to make and exist at least partial reaction or other interactional modes to make two or more materials, compound or component mix, contact between material, compound or the component or make its any known appropriate method together.

The term " water-soluble " that this paper uses is meant stable (not dissolving) under the ground environment condition but is being placed in behind given time (usually through several hours or a couple of days), become in the underground environment soluble resin, polymkeric substance or coating.

The term " processings " that this paper uses be meant on down-hole, well or reservoir or the multiple operation in down-hole, well or the reservoir in any, include but not limited to the processing of well workover type; Yield increasing type is handled, for example waterfrac treatment processing or s.t.; Isolation processing; The control reservoir fluid is handled or other are performed to improve the type of the remedying processing of overall well operation and yield-power.

The term " raising the output " that this paper uses be meant as with so that well yield-power or life-span increase and/or reach that maximum waterfrac treatment, acid fracturing splits, matrix acidizing, sand grains is handled or the well yield-power of other types process result improves or regenerative operation, this often realizes through generation highly conc reservoir flowing-path.

Detailed Description Of The Invention

In the embodiment of disclosed diversion agent; Single and a plurality of well sections on stratum can be come staging treating or raising the output through continue introducing the diversion agent that comprises particulate matrix and slowly water-soluble top coating, and wherein said slowly water-soluble top coating comprises collagen protein or collagen protein and slow water-soluble NCP mixtures of material.

The invention provides particulate compsn that comprises the soluble material coating that contains collagen protein and the method for preparing this based composition.This based composition can be used in the stratum turning to turn in single well section in waterfrac treatment working life chien shih well treat fluid to increase fracture length or to have in a plurality of well sections on stratum of different permeability and/or injectability.Use in the process of diversion agent of the present invention at fracturing process; The propping agent (or particulate matrix) that is coated with slowly water-soluble coating (matrix of for example independent collagen protein or collagen protein and NCP water-soluble plastic coating material mixture) with so that the crack turn to because the coating on the propping agent is served as the limited boundary of incipient crack.After fracture treatment, because the slow dissolution characteristics of coating, coating can be removed, and remaining hypertonicity propping agent flows in the crack, brings into play the effect of its propping agent.

Though with " comprising/comprise " various components or step compsn and method are described, compsn and method also can be basically by various components or step is formed or be made up of various components or step.

A. Matrix

Be applicable to that microparticle material of the present invention (also being called body material among this paper) comprises the multiple microparticle material that can be used for the suitable or possible proper supporting agent of being known as of downhole operations.According to the present invention, spendable microparticle material (or body material) comprises any propping agent that is suitable for waterfrac treatment known in the art.The instance of this based fine particles material includes but not limited to natural materials, silicon-dioxide propping agent, ceramic proppant, metallic propping agent, synthetic organic propping agent, its mixture etc.

The natural product that is suitable as propping agent includes but not limited to nutshell, for example English walnut, brazilnut and Queensland nut; And fruit stone, for example peach-pit, almond, Nux Canarii albi; And any resin impregnation of these products or the pattern of resin-coated.Typical resin coating or macerate comprise bis-phenol; The bis-phenol homopolymer; The blend of bis-phenol homopolymer and phenol-aldehyde polymer; Bis-phenol-urea formaldehyde and/or polymkeric substance; Phenol-aldehyde polymer and homopolymer; Modification and unmodified soluble phenolic resin; Aldehydes matter (comprises aryl phenol; Alkylphenol; Alkoxyl group phenol and aryloxy phenol); Resorcinol resin; Epoxy resin; Solvable fusible novolac polymer resin; The Procuring of solvable fusible bis-phenol-aldehyde polymer and wax and this resinoid coating or curing pattern.

Be applicable to that silicon-dioxide propping agent of the present invention includes but not limited to glass sphere and glass microsphere, granulated glass sphere, silicon-dioxide silica sand and all types of sand grains, the for example sand grains of white or brown.The typical silicon-dioxide sand grains that is fit to use comprises Northern White Sands (Fairmount Minerals; Chardon, OH), the pattern of any resin-coated of Ottawa, Jordan, Brady, Hickory, Arizona, St.Peter, Wonowoc and Chalfort and these sand grains.Under the situation of using silicon oxide fibre, fiber can be straight line, curve, curling or spiral helicine, and can have any grade, for example E-level, S-level and AR-level.The instance that is used for the silicon-dioxide propping agent of appropriate resin coating of the present invention comprises deformable propping agent, for example FLEXSAND LS ^TMWith FLEXSAND MS ^TM(from BJ Services, Inc., Houston, TX buys); With Tempered HS

, Tempered LC

, TemperedDC With Tempered TF

The tempering propping agent, all from Santrol, Fresno, TX buys.

The ceramic proppant that is applicable to method of the present invention includes but not limited to ceramic bead; Waste fluid-cracking catalyst (FCC), for example USP the 6th, 372, those catalyzer of describing in No. 378, this full patent texts is attached among this paper; Ultralight matter ceramic foam; Economical light ceramics, for example " ECONOPROP ^TM" (Carbo Ceramics, Inc., Irving, TX); Light ceramics, for example " CARBOLITE ^TM"; Medium tenacity pottery, for example " CARBOPROP ^TM" (from Carbo Ceramics, Inc., Irving, TX buys); High-strength ceramic, for example " CARBOHSP ^TM" and " Sintered Bauxite " (Carbo Ceramics, Inc., Irving TX) and HYPERPROP G2 ^TM, DYNAPROP G2 ^TMOr OPTIPROP G2 ^TMAny resin-coated of the curable ceramic proppant (from Santrol, Fresno, TX buys) of encapsulation and these ceramic proppants (for example the above) or the pattern of resin impregnation.

The metallic propping agent that is applicable to embodiment of the present invention includes but not limited to the pattern of any resin-coated of aluminum shot, aluminum shot, aluminium pin, aluminum steel, shot, shot etc. and these metallic propping agents.

Synthetic propping agent is equally applicable to the present invention.The instance of suitable synthetic propping agent includes but not limited to that plastic grain or pearl, nylon beads, nylon granule, SDVB (SDVB) pearl, thomel are (for example from Zoltek Corporation (Van Nuys, the PANEX that CA) buys ^TMThomel) and be similar to " FLEXSAND MS ^TM" (BJ Services Company, Houston, resin coalesced particle TX) and the pattern of resin-coated thereof.

In addition, envisioning the soluble material that is suitable as propping agent equally can be used in the method for the present invention.For example, place the solubility propping agent of the passage of the eyelet that is produced to include but not limited to the carbonate particulate that marble or race or any other are suitable.In addition, through with handle chemical and contact and become soluble or the fusible coating of endokinetic fissure backflow or uncoated wax, plastics or resin particle are suitable as propping agent of the present invention.

The common working concentration of proper supporting agent of the present invention is about 1 to about 18 pounds/gallon, and (it is about 2 that about 120g/L arrives, 160g/L) fracturing fluid compsn, but also can use higher or lower concentration on demand.

Equally, the particle diameter that is applicable to particulate matrix of the present invention is USS test screen number about 4 (that is, about 0.18 inch is arrived about 0.003 inch sieve aperture) in about 200 scope.More particularly, the size that is applicable to particulate matrix of the present invention comprises the size range of about 4 meshes (4750 microns) to about 200 meshes (75 microns).Being equally applicable to of the present invention is microparticle material or the propping agent with following dimension mark: 6/12,8/16,12/18,12/20,16/20,16/30,20/40,30/50,40/70 and 70/140; But can use any desired distribution of sizes; For example 10/40,14/20,14/30,14/40,18/40 etc.; With and any combination (for example, 10/40 and 14/40 mixture).According to the present invention, preferred size of mesh is 20/40 mesh.

B. The solubility coating

Solubility coating used according to the invention can be through for some time slow many known soluble reagents of dissolved in down-hole, stratum.Can be used for soluble polymeric material of the present invention should under down-hole, formation condition, to dissolve in (that is to say and can be dissolved in) salt solution, water, oil, organic solvent, acid or acidic medium and/or pH be about 1 to about 14 fluid with and composition thereof in.

The solubility coating is preferably structural protein, for example collagen protein or remove to hold peptide collagen protein (atelocollagen); Vegetable-protein, the vegetable-protein that for example exists in wheat, corn, oat or the almond; Or derive from the collagen protein of ocean environment.The collagen protein of back one type can extract from fish, algae, planktonic organism, plankton micro-organism etc.The solubility coating is collagen protein more preferably, comprise type i collagen albumen, II collagen type, III collagen type, IV type or collagen type v albumen with and the combination.According to the present invention, the solubility coating most preferably is type i collagen albumen or removes to hold the peptide collagen protein.

Be suitable as the type i collagen albumen of solubility coating according to the present invention or go to hold the peptide collagen protein to contain the collagen protein of at least one Ls-hydroxyproline residue for those.This type type i collagen albumen or go is held the peptide collagen protein to comprise the collagen protein (for example tropocollagen) that exists in tendon, skin, bone, the scar tissue etc. and is derived from controlled, the enzymatic of collagen protein or the product of chemical reduction.The molecular weight of this type collagen protein is preferably about 10,000 dalton to about 500,000 dalton, and more preferably about 100,000 dalton are to about 300,000 dalton.Suitable molecular weight is about 100,000 dalton, 125,000 dalton, 150,000 dalton, 175; 000 dalton, 200,000 dalton, 225,000 dalton, 250; Molecular weight between any two in 000 dalton, 275,000 dalton, 300,000 dalton and these values; For example molecular weight is about 225,000 to about 275,000 daltonian collagen proteins.For example, be applicable to that preferred type i collagen albumen of the present invention is Milligans and Higgins, (Johnstown, NY) molecular weight of supply is about 250,000 tropocollagen to Inc..

The Bo Lumu intensity (Bloom strength) that is applicable to collagen protein of the present invention arrives about 900psi for about 100psi, and more preferably about 300psi is to about 700psi.The Bo Lumu intensity that is applicable to collagen protein of the present invention arrives about 600psi for about 400psi.According to the present invention; Suitable Bo Lumu intensity be about 400psi, about 410psi, about 420psi, about 430psi, about 440psi, about 450psi, about 460psi, about 470psi, about 480psi, about 490psi, about 500psi, about 510psi, about 520psi, about 530psi, about 540psi, about 550psi, about 560psi, about 570psi, about 580psi, about 590psi and about 600psi and these the value in any two between Bo Lumu intensity; For example about 400psi is to about 520psi, for example 512psi.

The Bo Lumu intensity that this paper uses is meant according to stdn Bo Lumu TP (BS757:1975 for example; GMIA Testing Standard B5757; Be used to test viscosity gelatin International Standard ISO9665 or as " Official Methods of Analysis ofAOAC INTERNATIONAL (OMA) " described in similar standard) measure the intensity of the gelatinous mass (for example collagen protein) that forms by the standardized solution that under steady temperature, keeps definite concentration of specified time and/or the observed value of rigidity.The unit of Bo Lumu intensity level is generally " pound/square inch " (psi) or gram, has reflected the distance required power that reduces the sample surfaces favored area 4mm of institute.In typical method, jel product (for example collagen protein or gelatin) forms with concrete denseness (for example 6 and 2/3% solution) and under the constant temperature of 10 ℃ of thermostatic baths, kept 18 hours.Adopt subsequently and be called texture analysis appearance (TA.XT2i texture analysis appearance for example; Scarsdale; NY) measurement device; Standard A OAC [Associateion of OfficialAnalytical Chemists (the analytical chemistry Shi Xiehui of official)] the gelometer piston that will have a sharp lower rim reduce 4mm in gel or the BS piston with feather edge that will can be used as piston turn to the required weight of 0.4mm radius (gram) (or pressure, psi).For example, if this method needs 200 grams to reduce piston, the Bo Lumu intensity of gelatin is 200 so.

Be applicable to the proteic sieve aperture distribution/dimension mark of type i collagen of the present invention be 6/12,8/16,12/18,12/20,16/20,16/30,20/40,30/50,40/70 and 70/140 and in these marks any two between sieve aperture distribute; But can use any desired distribution of sizes, for example 8/40,10/40,14/20,14/30,14/40,18/40 etc. with and any combination (for example 10/40 and 14/40 mixture).According to the present invention, preferred size of mesh is 8/40 mesh.

This paper can be crosslinked, uncrosslinked or both combination as the collagen protein of solubility coating, and crosslinked type and degree depend on the concrete application based on the solubility coating of collagen protein.There are 4 kinds of fixedly elementary tactics of collagen material and the material built by the collagen protein of collagen fabric or the purifying of processing.It is crosslinked that these strategies comprise that the reagent that uses the goal response property part utilize in the collagen fabric system and the covalent coupling of corsslinking molecular own to be close to collagen fabric carries out exogenous chemical; Through the physical chemistry crosslinking technological of the covalently bound collagen fabric of naturally occurring reactive amino acid side chain, for example photoxidation, microwave irradiation, dehydration and dehydrogenation thermal treatment; Chemical catalysis intramolecular crosslinking between the amino acid side chain on the collagen fabric; Also form not non-covalent or covalent interaction [Koob, T.J., " Collagen Fixation " with polymerization and collagen protein assembling blended compound with the polymerization of collagen fabric chemical reaction; In Encyclopedia of Biomaterials andBiomedical Engineering, Wnek, G.E.; Bowlin; G.L., Eds., 2004].According to the present invention, the collagen protein that is used as the solubility coating preferably uses the chemically crosslinked technology crosslinked.These technology include but not limited to based on aldehyde crosslinking technological, based on the crosslinking technological of polyepoxy compound, use isocyanic ester, carbodiimide is crosslinked and crosslinked based on acid azide.Collagen protein more preferably uses based on the crosslinking technological of aldehyde crosslinked, for example uses LUTARALDEHYDE or formaldehyde crosslinking.

Crosslinking technological based on aldehyde comprises that those uses contain two technology [Khor in order to the reagent of the reactive aldehyde groups of formation covalent cross-linking between contiguous collagen protein (the particularly epsilon-amino of lysine residue in the collagen protein); E.; Biomaterials, Vol.18:pp.95-105 (1997)].Be applicable to that aldehyde of the present invention includes but not limited to LUTARALDEHYDE, formaldehyde, propionic aldehyde and butyraldehyde.

Comprise based on the crosslinking technological of poly epoxide and reagent and to use for example with the compound of reactive epoxide functional group as the short-chain branch polymkeric substance of end group.The polyepoxy compound that is suitable as linking agent of the present invention includes but not limited to glyceryl ether, terepthaloyl moietie and glycerine polyglycidyl ether.

Isocyanic ester is suitable as linking agent of the present invention equally.Usually, make isocyanic ester (R-NCO) and primary amine reaction to form urea key (R-H-CO-NH-R); Therefore the bifunctional isocyanate can pass through its lysine side-chain and collagen cross-linking.The isocyanic ester that is suitable as linking agent of the present invention is preferably vulcabond; Comprise xenyl vulcabond, dimethoxy-4 '; 4 '-xenyl vulcabond, dimethyl--4; 4 '-xenyl vulcabond, 1; Two (isocyano methyl) benzene of 3-, phenyl diisocyanate, tolylene diisocyanate (toluenediisocyanate), tolylene diisocyanate (tolylene diisocyanate), two isocyano hexanes, two isocyano octanes, two isocyano butane, isophorone diisocyanate, XDI,, 1,8-hot vulcabond, phenylene diisocyanate and gather (hexamethylene diisocyanate).The isocyanic ester that is used as the linking agent of collagen molecules of the present invention is preferably hexamethylene diisocyanate.

Also can use carbodiimide linking agent and technology within the scope of the invention.The carboxyl reaction that makes interior aspartic acid of this type reagent and collagen protein and L-glutamic acid side chain is to form different acyl urea derivatives/isopeptide bond [ibid for Khor, E.].The carbodiimide that is suitable as the linking agent of collagen protein of the present invention includes but not limited to N, N '-dicyclohexyl carbodiimide (DCC); N, N '-di-isopropyl carbodiimide (DIC); N, N '-di-t-butyl carbodiimide; 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC; EDAC); Water-soluble EDC (WSC); The 1-tertiary butyl-3-ethyl carbodiimide; 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide; Two (trimethyl silyl)-carbodiimide; 1, two (2,2-dimethyl--1, the 3-dioxolane-4-ylmethyl) carbodiimide (BDDC, like USP the 5th, 602, No. 264 are said) of 3-; N-cyclohexyl-N '-(2-morpholine-4-base ethyl) carbodiimide; N, N '-diethylammonium carbodiimide (DEC); 1-cyclohexyl-3-(2-morpholine-4-base ethyl) carbodiimide methyl-tosilate [for example, Sheehan, J.C. etc., J.Org.Chem., Vol.21:pp.439-441 (1956)]; Oligomeric alkyl-cyclohexyl carbodiimide, for example those oligomeric alkyl-cyclohexyl carbodiimide [J.Org.Chem., Vol.69:pp.8340-8344 (2004)] of describing such as Zhang; The DCC of polymer-bound; With the EDC of polymer-bound, for example JANDAJEL ^TMCrosslinked N-ethyl-N '-(3-dimethylaminopropyl) carbodiimide.In addition, N-hydroxy-succinamide (NHS), 1-hydroxyl-7-azepine benzotriazole (HOAt) or similar reagents can be used so that the internal rearrangement of the different acyl urea derivatives of activation minimizes and provide more effective crosslinked together with carbodiimide.

As carbodiimide is handled; The acid azide linking agent generates covalent linkage [Petit between the epsilon-amino of the Methionin of the carboxylic acid side chain of aspartic acid and L-glutamic acid and collagen protein; H. etc., J.Biomed.Mater.Res., Vol.24:pp.179-187 (1990)].At carboxyl esterification (wherein methyl being added in the acid) afterwards, biomaterial is handled to form corresponding hydrazides with hydrazine; Add sodium nitride subsequently, itself and hydrazides are reacted and the formation acid azide.Many hydrazines known in the art can be used in this method, comprise dimaleoyl imino propionyl hydrazine (MPH).

Be applicable to that the present invention includes but not limited to same bifunctional cross-linker with other chemical cross-linking agents of crosslinked with collagen protein molecular that the solubility coating of serving as on the proppant particles is provided, for example BMME, BSOCOES, DSP (linking agent of sulfo--cleavable), DSS, EGS, water-soluble EGS and SATA; And Heterobifunctional linking agent; Comprise GMB, MBS, PMPI, SMCC, SPDP and MPH (dimaleoyl imino propionyl hydrazine), MCH, EMCH (dimaleoyl imino caprinoyl hydrazine), KMUH (N-(k-dimaleoyl imino undecane) hydrazides) and MPBH (4-(4-N-dimaleoyl imino phenyl) daminozide); All (Cedex France) buys from Interchim.

Be suitable for that the other technologies that the crosslinked with collagen thiozell uses for solubility propping agent coating include but not limited to dewater, UV irradiation under 254nm, combine the glucose mediation crosslinked (glycosylation) of UV irradiation crosslinked with biology.Back one technology comprises the use natural product; For example genipin (genipin) and relevant iridoid thereof; Its fruit from Gardenia Ellis plant (cape jasmine (Gardenia jasminoides)) separates; It is the dialdehyde aqueous solution, therefore can react to provide crosslinked with the epsilon-amino on the lysine side-chain that is close to collagen molecules.Be applicable to that other biological cross-linking system of the present invention comprises from the isolating catechol of Wood creosote shrub-quinone tanning system; For example 3,4-dihydroxyl tyrasamine and nordihydroguaiaretic acid (NDGA), it serves as linking agent [Koob through two catechols on the NDGA; T.J.; Comp.Biochem.Physiol., PartA, Vol.133:pp.1171-1192 (2002)].

Open according to the present invention, the slow water-soluble coating on the particulate matrix also can be the NCP material, for example slow water-soluble synthetic polymer.This type NCP material includes but not limited to: polyethylene oxide, polypropyleneoxide, polycaprolactone; The grafts of polyethylene/polypropylene and polycaprolene; The grafts of Vilaterm/polypropyleneoxide and polycaprolactone; The reducible acrylic acid or the like of water soluble or water; The reducible phenoxy resin of water; Latex; Polyester; The solubility segmented copolymer; The grafts of Z 150PH (PVA) and Yodo Sol VC 400; The verivate of polylactide and POLYACTIC ACID; Sodium bromoacetate homopolymer, SRU (PGA); Sodium bromoacetate homopolymer, SRU lactic acid (polyglycoliclactic acid, PGLA).That also can be used for water-soluble coating is the silicate polymer of periodic table of elements I or II family (basic metal or earth alkali metal), for example SOLOSIL ^TM(Foseco International, Ltd., Great Britain), a kind of water glass polymkeric substance.

C. Method of use

In the embodiment of disclosed method, single or a plurality of well sections on stratum can be through continuing in the diversion agent introducing of the present invention stratum, then with coming staging treating or raising the output in the well treat fluid introducing stratum." well " that this paper uses comprises the cased section and/or the open hole section of well, should be appreciated that well can be vertical, level or its combination.Term " pipeline post " is meant and is suitable for placing and any pipeline of transporting fluid to well, includes but not limited to oil pipe, work string, drilling pipe, spiral oil pipe etc.In addition, should understand benefit disclosed by the invention and be that disclosed diversion agent and diversion treatments technology are applicable to the well treat fluid of any kind, include but not limited to s.t., condensed water processing, waterfrac treatment processing etc.In addition, should understand disclosed method and composition benefit can by at the frac pressure place on stratum, under frac pressure or the well that carries out more than the frac pressure handle to realize.

First: well purposes: in this aspect of the invention; Disclose complete water miscible particle in well (for example collagen protein or other water-soluble polymers plastics or its mixture) and made fluid flow redirect to another regional purposes from a zone, complete water miscible particle dissolves subsequently.Collagen protein (being uncrosslinked form and cross-linked form) and solubility plastics can be used for making fluidic to be flowing in the well turning to.This type diverting material should be in 1-100 size of mesh, in the scope of preferred 4-50 size of mesh and can use to improve performance through fluidic being flowed redirect to another zone from a zone with other additives or plastic material combinations.

These materials as turning to the obstruction ball, enter a zone and flow to the zone that another PP is higher or perviousness is lower with block fluid flow but this material of test displaying recently can be used as diversion agent.

The invention provides and a kind ofly handle the running casing well so that fluidic flows and to redirect to another regional method from a zone.This method relates to turning to fluid to be pumped in the well, and this turns to fluid to be made up of the aqueous carrier solution with the water-soluble polymers that is scattered in particulate form wherein, and wherein the density of microparticle polymer is greater than or less than the density of carrier fluid.When turning to fluid to be pumped in the well, microparticle polymer is deposited to the well zone, makes flowing of treat fluid redirect to another zone from a zone thus.Usually, treat fluid is turned to or stop that it flows in the zone that PP is higher or perviousness is lower.

In the method that the present invention uses about well, the water insoluble particulate polymkeric substance is collagen protein, gathers (alkylidene group) oxide compound, gathers silicate polymer or its mixture of (lactic acid), Yodo Sol VC 400, Z 150PH, Yodo Sol VC 400/Z 150PH, polylactone, polyacrylic ester, latex, polyester, periodic table of elements I or II family (basic metal or earth alkali metal).Usually, the amount that is present in the microparticle polymer in the carrier fluid be about 0.001 pound/gallon to about 10 pounds of/gallon carrier fluids.Advantageously microparticle polymer has the different densities that is greater than or less than carrier fluid density.Usually, carrier fluid is water, salt solution, aqueous acid or gel acid solution.

Second: the crack purposes of generation: in this aspect of the invention, can the various propping agents (being coated with the mixture of complete soluble collagen albumen or polymeric plastic material or solubility and soluble collagen protein or polymeric plastic material) that adopt coated particle be pumped in the pressure break stratum in case crack arrest is stitched from the production area, turns to.For example, the dense sintering bauxitic clay particle that has solubility or a part solubility coating will drop to Slit bottom and the crack is turned to from low rock stratum or water leg.Equally, the low density walnut shell that has solubility or part solubility coating will rise in the crack so that the crack contains gas or water leg from upwards growing to redirect to.Coating can have solubility wholly or in part, because propping agent places maintenance the crack and after frac job is accomplished, in the crack conductivity is provided.Some coatings on the propping agent should be dissolved, but advantageously the mixture of solubility and insolubility plastics or collagen protein moves in the crack to prevent propping agent.

The propping agent of the diversion agent that in the crack, uses for applying with solubility or part solubility coating (using any mixture of collagen protein and/or polymer plastic coated material or these materials).Through using these crack being turned to as the solubility coating on the propping agent of the limited boundary of incipient crack.After the fracture treatment, coating will disappear and the previous particle that applies will revert to normal propping agent, and it has hypertonicity.Coating on the multiple density proppant can produce crack boundary at the fracturing process initial stage; Because low viscosity fluid will make the proppants settle down of high-density coating or drop in the crack; Obtaining lower crack boundary and the crack is turned to from well, thereby make the crack elongated and increase the yield-power of well.Equally, the propping agent that low density applies will rise to the fissured top of growth with the formation top boundary, and the growth crack is turned to away from damaging the upper area that well is produced.Contain under the crannied situation at top and bottom, the crack can will be improved the potential productivity of well to outgrowth and contained longer crack.

The well that Fig. 1 explanation will be handled according to an embodiment disclosed by the invention with vertical running casing well section and single well section stratum.The well 10 of Fig. 1 has the sleeve pipe 12 that extends its at least a portion length from well head 11, externally uses cement sheath 14 bonding with fixed sleeving 12 on the spot, the stratum or the well section of isolating infiltration.Cement sheath 14 is outside sleeve pipe 12 and in the annulus between the well inwall, and artesian well eyeground portion extends up to and is higher than production rock stratum/18 places, hydrocarbon-containifirst stratum at least.The reason that comprises this sheath has many, but mainly is cement sheath 14 integrity that helps to guarantee well (that is, so it does not collapse) or isolates concrete different geological district (that is, isolating petroliferous province and (undesirable) exhalant region).Optional sleeve pipe or the liner shoe 16 of also being equipped with of well is so that help guide sleeves tubing string 12 during it places well, to cross cay or hamper.For the hydro carbons that in production rock stratum 18, remains to be produced, must between production rock stratum 18 and sleeve pipe 12 inside, set up the fluid channel.This realizes through bore the eyelet 15 that passes through sleeve pipe 12 and cement sheath 14 by instrument known to those skilled in the art.This kind tool includes but not limited to perforating gun, shaped charge device (shapedcharge device) and phase charge device, and for example USP the 6th, 755, No. 249, the 5th, 095, and No. 099 and the 5th, 816, those devices described in No. 343; Horizontal orientation perforation system (HOPS), for example those are by Owen Oil Tubes, Inc. (Ft.Worth, the system of TX) making; The machinery perforating system, for example transversely movable perforating device (USP the 2nd, 482, No. 913), acupuncture shot gun and gear shot gun (for example USP the 4th, 220, those shot guns of No. 201 descriptions); Fill in (for example USP the 4th, 498, person described in No. 543) with shearing.Eyelet 15 forms that fluids flow to sleeve pipe 12 from the stratum and flows to the path on stratum from sleeve pipe 12.

Flow out and flow to sleeve pipe 12 inner hydro carbons and can be transported to ground from production rock stratum 18 through eyelet 15 through production tubing 20.Production packer 22 can be chosen wantonly near the lower end that is installed in production tubing 20 and at the highest eyelet more than 15, so that realize the pressure sealing between production tubing 20 and the sleeve pipe 12.According to the present invention, optional and equally acceptably, and nonessential use production tubing 20, and under these circumstances, whole volumes of sleeve pipe 12 all are used to guide hydro carbons to top.

Handle operating period need turn to the time at well, use high specific gravity to support diversion agent 26a and/or low-gravity and support diversion agent 26b (both is mainly with solubility coating coating of the present invention) (promptly having the coating that contains collagen protein) and seal the last hypomere of production rock stratum 18 basically.During handling, at the fixed time with in temporary transient diversion agent 26a and/or the 26b lead-in bushing 12 time, there are this basic sealing or stratum, border.When with the fluid upper reaches of the perforation of diversion agent 26a and/or 26b lead-in bushing 12 part, it flows down production tubing 20 or sleeve pipe 12 through treat fluid 24 delivery of flowing.In case treat fluid 24 arrives the porose well section in the sleeve pipes, they will be from eyelet 15 surface current mistakes, and flow in the pending rock stratum 18.Flow through the treat fluid 24 temporary transient diversion agent 26a of delivery and/or the 26b of eyelet 15 through eyelet and get in the rock stratum 18.At this moment; Density supports the bottom (shown in arrow) that diversion agent 26a is deposited to man-made fracture greater than the high specific gravity of treat fluid 24, temporary transient " lower boundary " of formation between crack and for example sand grains, shale or clay seam 19 or other zones (need from the shutoff of production rock stratum).Equally, density supports the top (shown in arrow) that diversion agent 26a rises to man-made fracture less than the low-gravity of treat fluid 24, between crack and undesirable layer (the for example clay seam of shale or rock stratum), forms another temporary transient " coboundary " thus.

Fig. 2 explains next step of this aspect of the present invention.In case temporary transient diversion agent 26a and 26b drop on the top and/or the bottom of man-made fracture respectively, the fluid flow rate and the viscosity that contain the treat fluid 24 of regular proppant particles 28 will increase.By this way, the crack can be away from well (along the direction of arrow) to outgrowth, and in this case, fissured total length increases, and therefore helps to increase the raising the output and/or the life-span of well.Accomplish under the situation that well handles, temporary transient diversion agent 26a will dissolve with the solubility coating on the 26b, let remain proppant particles and remove through eyelet 15 with treat fluid 24, or reservation and in the process of rock stratum, crack is opened in support, serve as other propping agent.

Fig. 3 explains another embodiment of the invention.With shown in Figure 1 similar; Well 50 has vertical pipes well and cement sheath 56; Wherein said vertical pipes well has from well head 52 extends the sleeve pipe 54 of at least a portion borehole length, and artesian well eyeground portion extends up to and is higher than place, existing rock stratum at least in the annulus of said cement sheath 56 between sleeve pipe 54 outsides and well inwall.What in the open hole section of well, expose is the stratum with a plurality of processing well sections 58,60 and 62.Though 3 independent well sections have been described in Fig. 3, have been it should be understood that benefit disclosed by the invention is to use method and composition disclosed by the invention to handle any amount of well section from two processing well sections to many processing well sections.In addition, should understand these handles that well sections can be arranged continuously and is not must be to be separated by impermeable relatively zone (for example shaly bed).Though Fig. 3 has explained complete cased well, will also be understood that disclosed treatment process can be used for the whole situation of well of nearly all type.For example, disclosed method can be advantageously used in handles following well construction, includes but not limited to one or more well of vertical boreholes, complete running casing well, horizontal hole, the well with multiple wells and shared these characteristics.

In Fig. 3, handle definite well section that the stratum of processing has been confirmed in

well section

58,60 and 62 representatives.In this, can so confirm to be present in many well sections or its part only in the stratum.Perhaps, this type well Duan Haike represents the porose well section in the running casing well.As shown in Figure 3, eyelet 66 extends through sleeve pipe 54 and cement sheath 56 by instrument known in the art, forms in this case that fluid flows to sleeve pipe 54 from the stratum and flows to the path on stratum from sleeve pipe 54.

Flow out through eyelet 66 production rock stratum 18 from

handle well section

58,60 and 62 and the hydro carbons that flows to inside pipe casing can be transported to ground through production tubing 64.In addition, illustrated like Fig. 3, production packer 68 can be chosen wantonly and be installed in basically near the lower end of production tubing 64 and at the highest eyelet more than 66, so that realize the pressure sealing between production tubing 64 and the sleeve pipe 54.Be not always need use production tubing 64, under these circumstances, the totality volume of sleeve pipe 54 is used to guide hydro carbons to ground to well head 52.

In the time of during well is handled, need turning to, use diversion agent 72 basic some eyelets 66 of sealing.Basic sealing takes place when the flow through eyelet 66 significantly reduces, and stops that by diversion agent 72 increase of one or more eyelet 66 caused bottomhole wellbore pressures is indicated usually.According to this aspect of the invention, diversion agent 72 is preferably mainly spherical in shape, but can use other geometrical shapies.Use diversion agent 72 of the present invention to stop up some eyelets 66 through during handling, at the fixed time diversion agent 72 lead-in bushings 12 being realized.When with the fluid upper reaches of the meshed portion (66) of diversion agent 72 lead-in bushings 12, it flows down production tubing 64 or sleeve pipe 12 by fracturing fluid 70 deliveries of flowing.In case fracturing fluid 70 arrives the porose well section in the sleeve pipes, it will be from the surface current mistake of eyelet 66, and flows in the pending processing well section 58,60 and 62.Flow through the fracturing fluid 70 of eyelet 66 to eyelet 66 delivery diversion agents 72, diversion agent 72 is dropped on the eyelet 66.In case drop on the eyelet 66, diversion agent 72 just is fixed on the eyelet 66 by the fluid pressure difference that exists between the processing well section 58,60 and 62 in the inboard of sleeve pipe 54 and sleeve pipe 54 outsides.When diversion agent 72 drops on 66 last times of eyelet, the gravel size decision of diversion agent 72 seals eyelet 66 basically.Therefore, the diversion agent 72 that is located is in order to those eyelets 66 of effective sealing, up to the pressure reduction counter-rotating and diversion agent discharges or diversion agent 72 because its environment change (for example introducing water) and dissolving through for some time.

Diversion agent 72 will at first seal the eyelet 66 that fracturing fluid 70 flows through the most fast.Preferential sealing high flow rate eyelet 66 is with the

processing well section

58,60 and 62 on the whole porose well section of Balance Treatment.For diversion agent 72 is dropped on the eyelet 66 most effectively, under the temperature and pressure condition of down-hole hole area, the density of diversion agent 72 should be less than the density of treat fluid in the well 70.Usually, and according to this aspect of the invention, diversion agent 72 should have sizable outside surface of being made up of collagen protein or collagen protein mixture at least.The quantity of required diversion agent 72 depends on objective circumstances and the characteristic and the stimulation treatment to be used of individual well during well workover or well processing, and can be confirmed by those skilled in the art.

In implementing the process of disclosed method, employedly be suitable for realizing that the diversion agent or the medium that make fluid redirect to fixed processing well section are diversion agent of the present invention, it is outer with slowly water-soluble collagen protein that it comprises the particulate matrix.In one embodiment, can use this neutral buoyancy variant that contains the collagen protein diversion system, so that reduce diversion agent and the isolating chance of particulate diversion agent carrier fluid." neutral buoyancy " diversion system is following system, and wherein the particulate diversion agent is suspended in the carrier fluid with the enough sealing density that produces mixture or specific gravity, and solid ingredient not sedimentation or rising basically in system of diversion agent under quiescent conditions.This type segregation can cause that pile up the one or more positions of (for example) diversion agent in well and the pipeline post stops (sticking) in borehole segments.In addition, because diversion agent moves away from pending also section, segregation can cause the steering-effecting forfeiture.The neutral buoyancy diversion system can have peculiar advantage in high inclination or horizontal well; Wherein because for example diversion agent migration up or down in the high inclination of well or horizontal section, the gravity segregation of non-neutral buoyancy diversion system possibly hinder effective obstruction or reduction to be exposed to the perviousness of the stratal surface whole circumference in the well.

Spendable diversion agent comprise separately or with any well section that is suitable for that the subsequent disposal fluid is redirect to and has low injectability in the diversion agent of the present invention with slowly water-soluble top coating of diversion agent (for example oil soluble, solubility in acid etc.) combination.A kind of suitable diversion agent of the present invention is the diversion agent that is essentially collagen protein.Can include but not limited to that phenylformic acid thin slice, wax (" the Divert VI " that for example buy from BJ Services), cement level stellar coal or gilsonite, polymkeric substance (include but not limited to natural polymer, for example guar gum with the instance of the suitable diversion agent of diversion agent of the present invention combination; Or synthetic polymer, for example polyacrylic ester), halite etc.The suitable diversion agent of spendable other types includes but not limited to the solubility in acid diversion agent, and for example USP the 3rd, 353, those solubility in acid diversion agents of No. 874 descriptions; With the phthalimide particle, for example the U.S. the 4th, 444, those phthalimide particles of describing in No. 264.

In one embodiment of the invention; Can use carrier fluid, comprise natural or synthetic salt solution (for example KCl aqueous solution etc.) and comprise the carrier fluid of jelling agent (for example common or synthetic polymer) or other weighted material known in the art with any kind that is suitable for forming the neutral buoyancy diversion system.Cement level stellar coal (also claiming " Uintate ") is crushed and is divided into the pitch of the natural kind of particulate of multiple size.This diversion agent compsn can (include but not limited to salt, for example KCl, NH in the oil well position and in order to fresh water through the particular chemical modification (water that for example contains the about 1% wetted surface promoting agent of the 0.05%-that has an appointment) that disperses stellar coal and the weighting agent that randomly is used to adjust density and/or control stratum-clay ₄Cl, NaCl, CaCl ₂Deng) and the jelling agent (polymkeric substance, for example guar gum, hydroxypropyl guar gum, carboxyl methyl hydroxypropyl guar gum, carboxyl methyl hydroxyethylcellulose, XG 550, CMC 99.5 etc.) that is used to adjust viscosity and/or reduce resistance mix.

Diversion agent of the present invention preferably is present in the carrier fluid with about 0.001 pound of/gallon concentration to about 10 pounds of/gallon carrier fluids, but also can use the concentration that exceeds this scope.The most preferable concentrations of diversion agent is about 0.01 to about 6 pounds of/gallon carrier fluids.When using, will be difficult for stopping up the stratum less than about 0.001 pound/gallon diversion agent concentration with the carrier fluid volume that adopts usually in the oil well position.Concentration less than 0.001 pound/gallon situation under, the carrier fluid that needs is increased gradually volume is to produce enough reservoir choke.

Can not increase turning to of treat fluid significantly greater than about 10 pounds/gallon diversion agent concentration, therefore in the process of embodiment of the present invention, not cater to the need especially.

Carrier fluid is usually by water, salt solution, aqueous acid or gel acid solution composition.Acid solution usable fibers element, natural gum, polysaccharide, SEPIGEL 305, alkoxylated fats amine and composition thereof gelling.

Diversion agent can add when handling beginning in the carrier fluid, when treat fluid is pumped into well, adds in the carrier fluid continuously, or can during handling, add in the carrier fluid every now and then.For example, in acidization, can diversion agent be added in the acidizing fluid continuously.Therefore, diversion agent is the pending stratum of blocking portion gradually, stops acid only to flow to the trend in the perviousness the best part stratum thus, replaces and produces even acidifying stratum.When treat fluid segmentation pumping, the fs has the diverting material of being made up of carrier fluid (containing gelling or the emulsive water or the acid of bridging agent usually) in a large number at the back.The diversion agent shutoff is by the part stratum of fs treat fluid infiltration.Then the subordinate phase treat fluid is pumped in another part stratum.Alternately the treat fluid and the diverting material of amount can continue to provide even acidifying stratum.Though can use the same procedure of in carrier fluid, introducing diversion agent continuously for fracture treatment, during fracturing operation, diversion agent added in the carrier fluid in the slug usually.

Known fracturing liquid preferentially flows to and is easy to most accept in the part stratum of this liquid.The stratum can be added to bridging agent in the fracturing liquid by after the pressure break in this section, thereby it will stop up the part of pressure break on stratum.Because fracturing fluid preferential flow entrance pressure split plot, so it will deliver bridging agent.So the pressure break district is blocked and fracturing fluid redirect in the perviousness the best part of still accepting the fluidic stratum.

In one aspect of the invention, can repeat this pressure break and the method that turns to obtain a plurality of cracks.

Can be by making the diversion agent distillation or making the diversion agent dissolving and from the stratum, remove diversion agent with produced fluid.Increase FT and produce bigger diversion agent dissolving or rate of sublimation.For example; Have been found that about 250

under; The water-soluble a little collagen protein of about 80% weight distilled in 24 hours; And 300

under; About 95% weight distilled in 24 hours; About 400

temperature under, water-soluble a little collagen protein distillation/dissolving in about 24 hours of about 99%.Distillation/the dissolution rate that this shows diversion agent increases with the stratum temperature.

Comprise that following examples are with explanation the preferred embodiments of the invention.Therefore the technology that in embodiment of the present invention, has good result that the disclosed technology among the embodiment of it will be apparent to those skilled in the art that is still represented the inventor and found can think that these technology constitute optimal ways of embodiment of the present invention.Yet, according to the present invention, it be to be appreciated that those skilled in the art that and can carry out many changes to disclosed specific embodiments without departing from the scope of the invention that these changes still obtain similar or similar result.

Embodiment

Embodiment 1: predictive embodiment

Following predictive embodiment has described the solubility coating of the present invention on propping agent and can how to be used for crack growth being turned to and making the method for fracture propagation to the production area of oil or gas well.The main purpose of the propping agent that solubility applies is to produce in the vertically split at hydraulic pressure to limit up-and-down boundary, thereby makes the main direction of growth on away from the length direction of well, outwards continue to extend.The fissured extra length of this conduction helps the additional area of drainage productive zone, because fracture length is longer, lets oil, gas and/or water reclaim yield-power and improves and obtain bigger flow velocity.

The proppant material of using solubility of the present invention to apply can be followed following steps.

1. confirm the crack rate of injection with the LV fracturing fluid.

The propping agent that applies of solubility (walnut shell that for example applies, the bauxitic clay that applies with crosslinked collagen protein or both combinations) with crosslinked collagen protein at the mixing head place adding with formation fracturing fluid slurries.

3. the fracturing fluid that will contain the propping agent of solubility coating is pumped to the down-hole.First part's slurries get into to be accepted in most of fluidic initial crack.In this case, owing to use slowly softening and swollen soluble deverting agents (for example collagen protein) in this fluid, slurries slowly stop up the border of man-made fracture.

4. in case flow velocity slows down in first crackle or obviously reduces, pressure will increase, and begins to accept to contain the slurries of the propping agent that solubility applies until another flowing-path, crackle or zone.

5. all need contain under the situation of the propping agent that solubility applies in fissured top and bottom, preferably use two kinds of various supports agent density.For example, high-density bauxitic clay particle is applied its slowly softening and swelling when it falls the bottom of vertical man-made fracture in the crack with the soluble collagen protein coating.To slow down in order making in vertically split, upwards to grow, low-density second propping agent (the for example walnut shell of solubility coating) to be added and injects fluid.When injecting fluid entering stratum, the propping agent that the low density soluble material applies rises in vertically split and has slowed down and makes flow losses and the upwards growth of direction.

In the crack still when being higher than pressure break speed and pressure and making a bet into fluid, the crack continues to keep the control crack growth away from the well growth and through the flow velocity of control fracturing fluid.Continue to inject, up to the propping agent filling crack of rule, pressure reaches predetermined threshold or up to injecting the master plan amount.

7. in case the growth of top and bottom all reduces, then with the propping agent (for example Ottawa Sand (20/40)) of the insoluble coating of standard, the ceramic perhaps propping agent of many resin-coated) the injection stratum.Continuing pumping is in the man-made fracture up to the appointment propping agent of all amts.

8. shut-in well and remove pumping equipment.

9. well is resumed production, and the water in the stratum in time and during the solubility coating of dissolving on the propping agent, the soluble collagen protein coating on walnut shell or the bauxitic clay is removed.

Embodiment 2: confirm the dissolution rate of polymkeric substance and the method for solubleness

The sand grains matrix is applied with multiple water-soluble polymers:

Chemical name	Trade(brand)name	Supplier
			Polyethylene oxide	WSR80	?Dow?Chemicals
Polypropyleneoxide	WSRN750	?Dow?Chemicals
			Polypropyleneoxide	UCAR309	?Dow?Chemicals
Gather (lactic acid)	PLA6551-D	?E&M?specialties
			Gather (lactic acid)	PLA5600	?E&M?specialties
Gather (vinyl-acetic ester/alcohol)	PVA/Hydrolene	?Idroplax?Inc.
			Collagen protein 1	Glue?512	?Milligans?and?Higgins
Collagen protein 2	GM?Bond	?Hormel?foods

After this, use following TP to confirm dissolution rate and solubleness:

Confirm the total mass of polymkeric substance on the sand grains with regular LOI method.In 1 premium on currency, add the sand grains that 500 grams apply.Get 400mm filter paper and after on the analytical balance it being weighed into radix point 4.Through using 400mm filter paper, porose ceramic funnel, 2 liters of erlenmeyer flasks to prepare vacuum apparatus with the side opening that is connected with vacuum pump through rubber tubing.Each minute at interval after sand grains and water slurry through the coating of 400mm filter paper filtering.Must be with on the coating sand grains add-back filter paper in " filtration " water.After filtering completion, from porose funnel, shift out filter paper, and make its drying in the moisture eliminator through holding it in.Filter paper is weighed.This is the gross weight of dissolved polymers and filter paper, so it should be greater than the weight of filter paper before filter paper being used for filtration procedure.Through using following formula to calculate the % of dissolved polymkeric substance:

X＝((C-B)/A))×100

Wherein,

The per-cent of the dissolved polymkeric substance of X=

The quality (g) of the polymkeric substance of A=on sand grains

The quality (g) of B=filter paper before filtration procedure

The quality (g) of C=filter paper after filtration procedure

Swelling and dissolved particle subsequently	Dissolving and swollen particle not
		UCAR309	WSR80
Collagen protein 1	WSRN750
		Collagen protein 2	PLA6551-D
	PLA5600

The result of this TP is: polyethylene oxide (from the WSR 80 that Dow Chemical buys) 80

under in about 300 minutes, reach fully dissolving; 150 under; It needs about 180 minutes; 200

under, it needs about 90 minutes.

Use another polymkeric substance to carry out identical test.These results show polypropyleneoxide polymkeric substance (from the WSRN 750 that Dow Chemicals buys) 80

under in about 390 minutes, reach fully dissolving; 150

under; It needs about 320 minutes; 200 under, it needs to reach in about 245 minutes dissolving fully.

The swollen polymkeric substance was showed 100% solubleness in 30 minutes, but microscopical analysis is showed owing to swelling rather than dissolving are retained on the filter paper.Form remarkable the increasing of gum material and sand grains/water slurry volume and show polymers swell rather than polymer dissolution.

Open according to the present invention, can prepare or implement all compsns, method and/or technology disclosed herein and the requirement protection, and need not the over-drastic experiment.Though described the compositions and methods of the invention according to preferred embodiment; But those skilled in the art should can apply various variations to the step of compsn as herein described, method and/or technology and method or the order of step obviously under the situation that does not break away from principle of the present invention and scope.More particularly, some reagent that obvious available chemistry is relevant with physiology substitutes reagent as herein described, and will realize identical or similar result.Think that similar that all these it will be apparent to those skilled in the art that substitutes and revise all within scope of the present invention and principle.

Claims

1. one kind turns to fluid, said diverted flow body be used for through with said turn to fluid to pack into to limit with the well of handling the hole that well section fluid is communicated with come the top and the bottom of temporarily sealing processing well section, the said fluid that turns to comprises

(a) aqueous carrier solution of forming by water basically,

(b) be scattered in the first diversion agent particulate in the said aqueous carrier solution; The said first diversion agent particulate comprises the first support particulates matrix with water-soluble polymers coating; The density of the said first diversion agent particulate is greater than the density of said aqueous carrier solution; Said turn to fluid contain the first enough diversion agent particulate with the lower part of encapsulation process well section basically and

(c) be scattered in the second diversion agent particulate in the said aqueous carrier solution; The said second diversion agent particulate comprises the second support particulates matrix with water-soluble polymers coating; The density of the said second diversion agent particulate is less than the density of said aqueous carrier solution, and the said fluid that turns to contains the second enough diversion agent particulate with the upper section of encapsulation process well section basically.

2. claim 1 turns to fluid; The density of the wherein said first diversion agent particulate is sufficiently more than the density of said carrier fluid; Cause from the well first diversion agent particulate of handling the well section of packing into and can sink to the bottom of handling the well section; Thereby form temporary transient lower boundary, said lower boundary encapsulation process well section basically prevents that liquid flow from crossing this lower boundary; And

The density of the wherein said second diversion agent particulate is enough less than the density of said carrier fluid; Cause from the well second diversion agent particulate of handling the well section of packing into and can rise to the top of handling the well section simultaneously; Thereby form temporary transient coboundary, said coboundary when forming basically encapsulation process well section prevent that liquid flow from crossing this coboundary.

Claim 2 turn to fluid, wherein said carrier fluid is at least a in water, salt solution and aqueous acid and the gel acid solution.

4. claim 3 turns to fluid; The support particulates matrix of the wherein said first diversion agent particulate is selected from silicon-dioxide propping agent, density greater than the ceramic proppant of aqueous carrier solution density, metallic propping agent, marble chips, race, carbonate particulate and their mixture except that marble chips and race, and the support particulates matrix of the said second diversion agent particulate is selected from density less than the natural materials of aqueous carrier solution density, density ceramic proppant, plastic grain or pearl, thomel, resin coalesced particle and their mixture less than aqueous carrier solution density.

Claim 4 turn to fluid, wherein said natural materials is selected from nutshell, fruit stone and composition thereof.

Claim 5 turn to fluid, wherein at least a support particulates matrix in the first diversion agent particulate and the second diversion agent particulate is the propping agent of resin-coated.

Claim 6 turn to fluid, the propping agent of wherein said resin-coated is selected from following at least a water-insoluble resin-coated: bis-phenol homopolymer, phenol-aldehyde polymer, aryl phenol polymkeric substance, alkylphenol polymkeric substance, alkoxyl group phenol polymer, aryloxy phenol polymer, resorcinol resin, epoxy resin and wax.

Claim 4 turn to fluid, wherein the water-soluble polymers coating on the first diversion agent particulate and the second diversion agent particulate is independently selected from and comprises collagen protein, vegetable-protein, synthetic polymer, alkalimetal silicate polymkeric substance and the alkaline earth metal silicate polymkeric substance of holding the peptide collagen protein.

Claim 8 turn to fluid, wherein the water-soluble polymers coating on the first diversion agent particulate and the second diversion agent particulate is a collagen protein.

Claim 9 turn to fluid, wherein the collagen coating at least a in the first diversion agent particulate and the second diversion agent particulate is crosslinked.

11. claim 2 turn to fluid, wherein the water-soluble polymers coating on the first diversion agent particulate and the second diversion agent particulate is independently selected from and comprises collagen protein, vegetable-protein, synthetic polymer, alkalimetal silicate polymkeric substance and the alkaline earth metal silicate polymkeric substance of holding the peptide collagen protein.

12. claim 11 turn to fluid, wherein the water-soluble polymers coating on the first diversion agent particulate and the second diversion agent particulate is a collagen protein.

13. claim 12 turn to fluid, wherein the collagen coating at least a in the first diversion agent particulate and the second diversion agent particulate is crosslinked.

14. claim 7 turn to fluid, the propping agent of wherein said resin-coated is selected from following at least a resin-coated: solvable fusible novolac polymer resin and solvable novolac polymer resin.

15. during fracture treatment, handle the stratum so that make the method for stratum raising the output for one kind, said method comprises:

The fluid that turns to of claim 1 is pumped in the stratum;

Carrier fluid is penetrated in the stratum so that deliver diverting material in the stratum; With

Make diverting material stop up the porous part on stratum, the flow divert that therefore makes treat fluid is in the low part of the perviousness on stratum.

16. the method for claim 15, the wherein said fracture treatment that is treated on stratum, and wherein said raising the output be since the increase of fracture length due to.

17. the method for claim 15, the support particulates matrix of wherein said first and second diversion agents independently are selected from natural materials propping agent, silicon-dioxide propping agent, ceramic proppant, metallic propping agent, synthetic organic propping agent and composition thereof separately.

18. the method for claim 15, wherein the support particulates matrix of at least a diversion agent is the propping agent of resin-coated.

19. the method for claim 15, the water-soluble polymers of wherein said first and second diversion agents independently are selected from collagen protein separately, gather (alkylidene group) oxide compound, gather (lactic acid), the silicate polymer of Yodo Sol VC 400, Z 150PH, polylactone, polyacrylic ester, polyester, alkali-metal silicate polymer, earth alkali metal and composition thereof.

20. the method for claim 15, the support particulates matrix particle diameter separately of wherein said first and second diversion agents is that 3 meshes are to 200 meshes.

21. the method for claim 15, the water-soluble polymers of wherein said first and second diversion agents independently are selected from type i collagen albumen, II collagen type, III collagen type, IV collagen type, collagen type v albumen and composition thereof separately.

22. the method for claim 21, wherein the water-soluble collagen albumen of said at least first or second diversion agent adopts the linking agent that is selected from aldehyde, carbodiimide, isocyanic ester and acid azide to carry out crosslinked.

23. the method for claim 15, at least a non-soluble polymer that also comprises in said first and second diversion agents.

24. the method for claim 23, wherein said non-soluble polymer are solvable fusible novolac polymer and solvable novolac polymer.

25. the water-soluble polymers in the method for claim 15, at least a in wherein said first and second diversion agents for gather (alkylidene group) oxide compound, gather (lactic acid), Yodo Sol VC 400, Z 150PH, Yodo Sol VC 400/polyvinyl alcohol graft copolymerized polymkeric substance or its mixture.

26. the method for claim 25, wherein said gathering (alkylidene group) oxide compound be polyethylene oxide, polypropyleneoxide, gather (oxyethane)-gather (propylene oxide) segmented copolymer or its mixture.

27. the method for claim 15, the amount that wherein is present in the diverting material in the carrier fluid are 0.001 pound/gallon to 10 pounds/gallon carrier fluid.

28. the method for claim 15, wherein said carrier fluid are water, salt solution, aqueous acid or gel acid solution.