Self-repairing cements

Abstract

A self-adaptive cement formulation includes cement, water and thermoplastic block-polymer particles. The set cement demonstrates self-healing properties when exposed to methane, and is particularly suited for well-cementing applications. After placement and curing, the self healing properties help maintain zonal isolation should bonding be disrupted between the set cement and the formation or a casing string, should cracks or defects appear in the set-cement matrix, or both.

Claims

1. A cement slurry, comprising: thermoplastic block-polymer particles selected from the group consisting of styrene-isoprene-styrene polymer particles, styrene-butadiene-styrene polymer particles, and mixtures thereof; wherein the thermoplastic block-polymer particles have a particle size between 100 m and 900 m, and a tensile strength between 1.5 MPa and 40 MPa, wherein the slurry further comprises an aqueous inverse emulsion of particles comprising a betaine group, poly-2, 2, 1-bicyclo heptene (polynorbornene), alkylstyrene, crosslinked substituted vinyl acrylate copolymers, diatomaceous earth, vinyl acetate rubber, polychloroprene rubber, acrylonitrile butadiene rubber, hydrogenated acrylonitrile butadiene rubber, ethylene propylene diene monomer, ethylene propylene monomer rubber, styrene/propylene/diene monomer, brominated poly(isobutylene-co-4-methylstyrene), chlorosulphonated polyethylenes, brominated butyl rubber, chlorinated butyl rubber, chlorinated polyethylene, epichlorohydrin ethylene oxide copolymer, ethylene acrylate rubber, ethylene propylene diene terpolymer rubber, sulphonated polyethylene or substituted styrene acrylate copolymers or combinations thereof; the cement slurry to be pumped in a well with a borehole penetrating a methane-containing formation, wherein methane is present at a concentration higher than 91 mol % and at a pressure higher than 3.5 MPa; and wherein the thermoplastic block-polymer particles swell when in contact with the methane, after microannuli, cracks or defects occur in a cement sheath.

2. The cement slurry of claim 1, wherein the concentration of the particles is between about 10% and 55% by volume of cement-slurry solids.

3. A cement slurry for maintaining zonal isolation in a subterranean well in which a borehole penetrates one or more methane-containing formations, comprising: thermoplastic block-polymer particles selected from the group consisting of styrene-isoprene-styrene polymer particles, styrene-butadiene-styrene polymer particles, and a mixtures thereof; wherein the slurry further comprises an aqueous inverse emulsion of particles comprising a betaine group, poly-2, 2, 1-bicyclo heptene (polynorbornene), alkylstyrene, crosslinked substituted vinyl acrylate copolymers, diatomaceous earth, vinyl acetate rubber, polychloroprene rubber, acrylonitrile butadiene rubber, hydrogenated acrylonitrile butadiene rubber, ethylene propylene diene monomer, ethylene propylene monomer rubber, styrene/propylene/diene monomer, brominated poly(isobutylene-co-4-methylstyrene), chlorosulphonated polyethylenes, brominated butyl rubber, chlorinated butyl rubber, chlorinated polyethylene, epichlorohydrin ethylene oxide copolymer, ethylene acrylate rubber, ethylene propylene diene terpolymer rubber, sulphonated polyethylene or substituted styrene acrylate copolymers or combinations thereof; wherein the particles have a particle size between 100 m and 900 m, and a tensile strength between 1.5 MPa and 40 MPa.

4. The cement slurry of claim 3, wherein the concentration of the particles is between about 10% and 55% by volume of cement-slurry solids.

5. The cement slurry of claim 3, wherein the particles swell in response to contact with the methane.

6. The cement slurry of claim 3, wherein the methane in the methane-containing formation is present at a concentration higher than 91 mol % and at a pressure higher than 3.5 MPa.

Description

DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a plot showing the swelling characteristics of styrene-isoprene-styrene (SIS) and styrene-butadiene-styrene (SBS) particles in the presence of methane at various temperatures and pressures.

(2) FIG. 2 is a schematic diagram of an experimental apparatus for measuring the self-healing ability of fractured cement samples.

(3) FIG. 3 presents normalized flow-rate reductions for set cements containing SIS and SBS particles exposed to methane.

(4) FIG. 4 presents the effect of slurry density on normalized flow-rate reductions for set cements containing SIS and SBS particles exposed to methane.

(5) FIG. 5 presents normalized flow-rate reductions for set cements containing SIS and SBS particles exposed to methane at various pressures.

DETAILED DESCRIPTION

(6) At the outset, it should be noted that in the development of any such actual embodiment, numerous implementationsspecific decisions must be made to achieve the developer's specific goals, such as compliance with system related and business related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort might be complex and time consuming but would nevertheless be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure. In addition, the composition used/disclosed herein can also comprise some components other than those cited. In the summary and this detailed description, each numerical value should be read once as modified by the term about (unless already expressly so modified), and then read again as not so modified unless otherwise indicated in context. Also, in the summary and this detailed description, it should be understood that a concentration range listed or described as being useful, suitable, or the like, is intended that any and every concentration within the range, including the end points, is to be considered as having been stated. For example, a range of from 1 to 10 is to be read as indicating each and every possible number along the continuum between about 1 and about 10. Thus, even if specific data points within the range, or even no data points within the range, are explicitly identified or refer to only a few specific points, it is to be understood that inventors appreciate and understand that any and all data points within the range are to be considered to have been specified, and that inventors possessed knowledge of the entire range and all points within the range.

(7) This disclosure concerns compositions for cementing subterranean wells, comprising a settable material, water and at least one Additive that swells in the event of structural failure of or damage to the set material (i.e., the cement sheath). Such behavior restores and maintains a physical and hydraulic barrier in the failure zone. As a result, zonal isolation in the subterranean well is preserved. Such set cements are said to be self-healing or self-repairing. In this application, both terms are used indifferently, and are to be understood as the capacity of a cement sheath to restore hydraulic isolation after suffering a matrix-permeability increase, structural defects such as cracks or fissures, or debonding from casing or formation surfaces (i.e., microannuli).

(8) Examples of settable materials include (but are not limited to) Portland cement, microcement, geopolymers, mixtures of cement and geopolymer, plaster, lime-silica mixtures, resins, phosphomagnesium cements or chemically bonded phosphate ceramics (CBPCs).

(9) As stated earlier, there is a need for self-healing set cements that operate in an environment containing high concentrations of gaseous hydrocarbons, methane in particular. Surprisingly, the inventors have discovered that self-healing properties may be achieved in this environment by incorporating thermoplastic block-polymer particles in the cement formulation. Typical block polymers comprise alternating sections of one chemical compound separated by sections of a different chemical compound, or a coupling group of low molecular weight. For example, block polymers can have the structure (A-b-B-b-A), wherein A represents a block that is glassy or semi-crystalline and B is a block that is elastomeric. In principle, A can be any polymer that is normally regarded as thermoplastic (e.g., polystyrene, polymethylmethacrylate, isotactic polypropylene, polyurethane, etc.), and B can be any polymer that is normally regarded as elastomeric (e.g., polyisoprene, polybutadiene, polyethers, polyesters, etc.).

(10) Further embodiments relate to methods for maintaining zonal isolation in a subterranean well having a borehole that penetrates one or more hydrocarbon-containing formations. The method comprises pumping a cement slurry comprising thermoplastic block-polymer particles into the well, and allowing the cement slurry to form a cement sheath. Those skilled in the art will recognize that a cement slurry is generally considered to be pumpable when its viscosity is less than or equal to 1000 mPa-s at a shear rate of 100 s.sup.1, throughout the temperature range the slurry will experience during placement in the well. The cement sheath may be located between the well casing and the borehole wall, or between the casing and another casing string. If microannuli, cracks or defects occur in the cement sheath, the casing-cement interface or the cement-borehole wall interface, the particles will be exposed to formation hydrocarbons, causing them to swell and enabling the cement sheath to have self-healing properties.

(11) Yet further embodiments aim at uses of thermoplastic block-polymer particles to impart self-healing properties to a set cement sheath in a subterranean well that penetrates one or more hydrocarbon-containing formations. The particles swell when contacted by hydrocarbons from the formation, in particular gaseous hydrocarbons.

(12) For all aspects, the tensile strength of the block polymer may be varied between (but is not limited to) about 1.5 MPa and 40 MPa, preferably between 3.4 to 34 MPa. Even more preferred tensile-strength may be between 2 MPa and 3.45 MPa or between 28 MPa and 34 MPa.

(13) Preferred thermoplastic block polymers include styrene-isoprene-styrene (SIS), styrene-butadiene-styrene (SBS) and mixtures thereof. The block-polymer-additive may be in one or more shapes, including (but not limited to) spherical, ovoid, fibrous, ribbon-like and in the form of a mesh.

(14) The concentration of the block-polymer particles is preferably between about 10% and 55% by volume of solids in the cement slurry, also known as percentage by volume of blend (BVOB). A more preferred particle concentration lies between about 20% and 50% BVOB. The particle-size range is preferably between about 100 m and 900 m, and more preferably between about 200 m and 800 m.

(15) One of the current challenge that the industry is facing is the presence in some wells of high concentration of gaseous hydrocarbons such as methane, propane and/or ethane. Such gaseous hydrocarbons being much more volatile than hydrocarbons in liquid form have the tendency to penetrate the failures and/or microannuli that can be present and the cement sheath and thus modifying the pressure and safety conditions of the well as the integrity is diminished. The inventors have determined that the present compositions can solve this problem up to very high concentration of gaseous hydrocarbon. In a preferred embodiment, the gaseous concentration of hydrocarbon fluid is greater than about 91 mol %, and more preferably above about 95 mol %. In addition, the hydrocarbon pressure to which the cement sheath is exposed is preferably above about 3.5 MPa, more preferably above about 6.9 MPa and most preferably above about 13.7 MPa.

(16) The block-polymer particles may be further encapsulated by a protective layer. The layer may rupture or degrade upon exposure to one or more triggers, including (but not limited to) contact with a hydrocarbon, propagation of a crack within the set-cement matrix, time and/or temperature.

(17) In addition to the block-polymer particles, the cement slurries may also comprise customary additives such as retarders, accelerators, extenders, fluid-loss-control additives, lost-circulation additives, gas-migration additives and antifoam agents. Furthermore, the cement slurries may contain additives that enhance the flexibility and/or toughness of the set cement. Such additives include (but are not limited to) flexible particles having a Young's modulus below about 5000 MPa and a Poisson's ratio above about 0.3. Preferably, such particles would have a Young's modulus below about 2000 MPa. Examples include (but are not limited to) polypropylene, polyethylene, acrylonitrile butadiene, styrene butadiene and polyamide. Such additives may also include fibers selected from the list comprising polyamide, polyethylene and polyvinyl alcohol. Metallic microribbons may also be included.

(18) The block-polymer particles may also be used in engineered-particle-size cement formulations involving trimodal or quadrimodal blends of small, medium and coarse particles. Such as formulations exemplified in U.S. Pat. No. 5,518,996 and/or CA 2,117,276.

(19) The block-polymer particles may be further associated with one or more compounds from the list comprising an aqueous inverse emulsion of polymer comprising a betaine group, poly-2,2,1-bicyclo heptene (polynorbornene), alkylstyrene, crosslinked substituted vinyl acrylate copolymers, diatomaceous earth, natural rubber, vulcanized rubber, polyisoprene rubber, vinyl acetate rubber, polychloroprene rubber, acrylonitrile butadiene rubber, hydrogenated acrylonitrile butadiene rubber, ethylene propylene diene monomer, ethylene propylene monomer rubber, styrene-butadiene rubber, styrene/propylene/diene monomer, brominated poly(isobutylene-co-4-methylstyrene), butyl rubber, chlorosulphonated polyethylenes, polyacrylate rubber, polyurethane, silicone rubber, brominated butyl rubber, chlorinated butyl rubber, chlorinated polyethylene, epichlorohydrin ethylene oxide copolymer, ethylene acrylate rubber, ethylene propylene diene terpolymer rubber, sulphonated polyethylene, fluoro silicone rubbers, fluoroelastomer and substituted styrene acrylate copolymers.

(20) Those skilled in the art will appreciate that the disclosed method and use may not necessarily be applied throughout the entire length of the subterranean interval being cemented. In such cases, more than one cement-slurry composition is placed sequentially. The first slurry is called the lead, and the last slurry is called the tail. Under these circumstances, it is preferred that the inventive slurry be placed such that it resides in regions where hydrocarbons exist. In most cases, this will be at or near the bottom of the well; therefore, the inventive method and use would preferably apply to the tail. Those skilled in the art will also appreciate that the disclosed method and use would not only be useful for primary cementing, but also for remedial cementing operations such as squeeze cementing and plug cementing.

(21) Other and further objects, features and advantages will be readily apparent to those skilled in the art upon a reading of the description of the examples which follows, taken in conjunction with the accompanying drawings.

EXAMPLES

(22) The following examples serve to further illustrate the disclosure.

(23) Table 1 lists the styrene-isoprene-styrene (SIS) polymers and styrene-butadiene-styrene (SBS) polymers that were used in the examples.

(24) TABLE-US-00001 TABLE 1 Suppliers and Properties of SIS and SBS Polymers Employed in Examples.* Property SIS #1 SIS #2 SBS #1 SBS #2 SBS #3 SBS #4 Supplier ICO Kraton ICO ICO ICO Kraton Polymers Polymers Polymers Polymers Product Name ICO1 D1161 ICO 3 ICO 4 ICO 5 D1192 EM PTM Melt Index 13 13.5 <1 23-37 <1 <1 (200 C./5 kg) (g/10 min) Density (kg/m.sup.3) 963 920 940 940 981 940 Tensile strength 17 21 16 10 33 at break (MPa) Hardness, 24 32 72 70 Shore A (30 s) Elongation at 1400 1300 680 900 880 break (%) *Test methods: ISO 1133 (Melt Index measurement) ISO 37 (Tensile Strength at Break and Elongation at Break measurements) ISO 2781 (Density measurement) ISO 868 (ICO Polymers) and ASTM 2240 (Kraton) (Hardness measurement)

Example 1

(25) Several polymer particles were placed inside a pressure cell equipped with a window that allows one to observe the behavior of materials within the cell. The cell supplier was Temco Inc., Houston, Tex. (USA). The cell temperature was also adjustable. A camera captured images from inside the pressure cell, and image-analysis software was employed to interpret the behavior of materials inside the cell. For particle-size measurements, the software examined the cross-sectional area of the particles in the cell.

(26) After the polymer particles were introduced into the cell, the cell was sealed. The cell was then heated to the desired temperature. The initial particle sizes were measured.

(27) A methane-gas line was then connected to the cell, and the methane pressure was raised to 21 MPa over a 3-min period. The cell pressure was maintained for 2 hr, after which the particle sizes were measured again.

(28) Tests were performed at 22 C. and 42 C. with an SIS polymer (SIS #1 from Table 1) and an SBS polymer (SBS #3). The results are presented in FIG. 1. At both temperatures, both SIS and SBS polymer demonstrated good performance.

Example 2

(29) The properties of cement slurries containing SIS or SBS particles were measured. The tests conformed to standard methods published by the International Organization for Standards (ISO): Petroleum and natural gas industriesCements and materials for well cementingPart 2: Testing of well cements, International Organization for Standards Publication No. ISO 10426-2. Two cement slurries were testedone containing SIS particles (SIS #1), and the other containing SBS particles (SBS #3). The test conditions were as followsbottomhole static temperature: 53 C.; bottomhole circulating temperature: 44 C.; bottomhole pressure: 21 MPa (3000 psi).

(30) The composition of the slurry containing SBS is given in Table 2, and the test results are presented in Tables 3 and 4. The slurry density was 1606 kg/m.sup.3, and the solid volume fraction (SVF) of the slurry was 51.8%.

(31) TABLE-US-00002 TABLE 2 Composition of Test Cement Slurry Containing SBS as Self-Healing Particle. Quantity Component Type (kg/m.sup.3) Cement Class G Portland cement 696 Self-healing particle SBS #3 214.5 Silica 200 mesh (74 m) 200.5 Water Fresh 395 Lightweight particle Acrylonitrile-butadiene copolymer 5 Antifoam Polypropylene glycol 4 Dispersant Polymelamine sulfonate 9 Antisettling 90% crystalline silica; 10% 1 polysaccharide biopolymer Fluid-loss additive RHODOFLAC, available from 72 Rhodia Nederland Retarder Calcium Lignosulfonate 2.5

(32) TABLE-US-00003 TABLE 3 Rheological Properties of Test Cement Slurry Containing SBS as Self-Healing Particle. Mixing 20-min Conditioning PV: 233 cP PV: 219 cP Ty: 4.3 kPa (9 lbf/100 ft.sup.2) Ty: 8.1 kPa (17 lbf/100 ft.sup.2)

(33) TABLE-US-00004 TABLE 4 Additional Properties of Test Cement Slurry Containing SBS as Self-Healing Particle. Measurement Results Free fluid 0.8% Fluid loss 13 mL Thickening time 8:53 (to 70 Bc) Compressive 500 psi [3.4 MPa] (UCA) after 23:42 strength 1000 psi [7 MPa] (UCA) after 72:58 development 783 psi [5.4 MPa] (crush); 512 psi [3.5 MPa] (UCA) after 24:00 1316 psi [9 MPa] crush (996 psi [6.9 MPa] UCA) after 72:00 Tensile strength* 1.9 MPa *Cement was cured for 7 days at 53 C. and 20 MPa before measuring tensile strength.

(34) The composition of the slurry containing SIS is given in Table 5, and the test results are presented in Tables 6 and 7. The slurry density was 1606 kg/m.sup.3, and the solid volume fraction (SVF) of the slurry was 51.7%.

(35) TABLE-US-00005 TABLE 5 Composition of Test Cement Slurry Containing SIS as Self-Healing Particle. Quantity Component Type (kg/m.sup.3) Cement Class G Portland cement 694 Self-healing additive SIS #1 208 Antifoam Polypropylene Glycol 5 Silica 200 mesh (74 m) 219 Water Fresh 393 Dispersant Polymelamine Sulfonate 8 Antisettling Biopolymer 1 Fluid loss RHODOFLAC, available from 81 Rhodia Nederland

(36) TABLE-US-00006 TABLE 6 Rheological Properties of Test Cement Slurry Containing SIS as Self-Healing Particle. Mixing 20-min Conditioning PV: 119 cP PV: 107 cP Ty: 6.7 KPa (14 lbf/100 ft.sup.2) Ty: 9.1 KPa (19 lbf/100 ft.sup.2)

(37) TABLE-US-00007 TABLE 7 Additional Properties of Test Cement Slurry Containing SIS as Self-Healing Particle. Measurement Results Free water 0.3% Thickening time 4:13 (to 70 Bearden cconsistency) Compressive strength 500 psi [3.4 MPa] after 11:52 development (measured 1000 psi [7 MPa] after 32:00 by UCA) 867 psi [6 MPa] after 24:00 1260 psi [8.7 MPa] after 72:00

Example 3

(38) Various cement formulations containing SIS or SBS were evaluated for their self-healing properties. The slurry compositions are presented in Table 8. The formulation that contains acrylonitrile-butadiene copolymer rubber (ABCR) was included as a control with no self-healing capability.

(39) TABLE-US-00008 TABLE 8 Slurry Compositions for Self-Healing Tests. Particle type Unit ABCR SIS #1 SIS #2 SBS #1 SBS #2 SBS #3 SBS # 4 Density (kg/m.sup.3) 1571 1498 1606 1498 1498 1498 1606 SVF (%) 55 50.3 52.3 50 50.6 50 52 Particle (kg/m.sup.3) 286 240 210 243 239 243 213 Cement 616 560 645 555 563 553 641 Silica 219 199 281 197 200 196 279 Water 436 494 459 498 491 497 463 Antifoam* 3 4 3 4 4 6 3 Dispersant* 5 0 5 0 0 3 5 Antisettling* 1 1 1 1 1 1 1 Retarder* 5 0 0 0 0 0 0 *Antifoam Agent: polypropylene glycol; Dispersant: polymelamine sulfonate; Antisettling Agent: 90% crystalline silica, 10% polysaccharide biopolymer; Retarder: calcium lignosulfonate.

(40) Each cement slurry was prepared according to the method described in ISO Publication 10426-2, and samples were prepared in the manner required to perform a Brazilian tensile-strength test. This test is also described in ISO Publication 10426-2. The cement-core samples were 66 mm long and 22 mm in diameter. The samples were cured at room temperature and atmospheric pressure. The curing times are presented in Table 9. Columns with two numbers indicate that two tests were performed.

(41) TABLE-US-00009 TABLE 9 Curing times. Particle SIS SIS SBS SBS SBS SBS name ABCR #1 #2 #1 #2 #3 #4 Curing 40/121 48 104 101 79/77 78/105 100 time (days)

(42) The samples were fractured by the Brazilian method, then transferred to a steel tube and secured by a scaling cement. As shown in FIG. 2, the steel tube 101 is 180 mm long. There are two 90-mm sectionsone with an internal diameter of 31.5 mm in diameter, the other with an internal diameter of 29.5 mm. The fractured cement sample 102 is placed inside the tube and the sealing cement 103 is applied around the sample. Midway along the cement sample, owing to the different tube diameters, there is an edge 104 to prevent the cement sample from sliding.

(43) The composition of the sealing cement was a 1.88-kg/m.sup.3 Portland cement slurry containing 2.7 mL/kg polynaphthalene sulfonate dispersant, 2.7 mL/kg polysiloxane antifoam agent, 178 mL/kg styrene butidiene latex and 2.1% by weight of cement calcium chloride accelerator.

(44) Pure methane was then injected through the fractured samples for 24 hours at 21 MPa backpressure and at ambient temperature (20-23 C.). Flow-rate and pressure variations were recorded, and normalized flow rates were calculated. The results are shown in FIG. 3.

(45) The cement matrices incorporating SIS particles demonstrated normalized flow-rate reductions greater than 98%. The performance of cement matrices incorporating SBS particles demonstrated flow-rate reductions between 49% and 97%. The control did not show a flow-rate reduction.

Example 4

(46) Using the methods described in Example 3, the effect of slurry density on the performance of set cements containing SIS#1 or SBS#3 was investigated. The slurry compositions are shown in Table 10.

(47) TABLE-US-00010 TABLE 10 Slurry Compositions for Self-Healing Tests Density (kg/m.sup.3) 1606 1606 1498 1498 SVF (%) 52 51.5 50.3 50.7 Particle type SIS#1 SBS#3 SIS#1 SBS#3 Particle (kg/m.sup.3) 213 216 240 242.5 Class G cement 641.5 635.5 560 554.3 Silica 280 277 199 196 Water 462.5 467.5 494 496.5 Antifoam 5 5 4 4 Dispersant 3 3 0 3 Antisettling 1 1 1 1

(48) The cement slurries were cured for 7 days at 53 C. and 20 MPa. The self-healing test results are presented in FIG. 4. For both cement matrices, density variation does not affect performance in terms of flow-rate reduction.

Example 5

(49) Using the methods described in Example 3, the effect of pressure on the performance of set cements containing SIS#1 or SBS#3 was investigated. The 1606-kg/m.sup.3 formulations from Table 9 were tested.

(50) The samples were cured for 7 days at 53 C. and 20 MPa. Flow-rate-reduction measurements were performed at four methane pressures: 3.5 MPa, 7 MPa, 13.7 MPa and 20 MPa. The results, presented in FIG. 5, indicate that flow-rate reduction was achieved at 3.5 MPa for the set cement containing SIS, and at 7 MPa for the set cement containing SBS.