专利摘要:
The various embodiments disclosed relate to cement activation compositions for the treatment of subterranean formations. In various embodiments, the present invention provides a method for treating a subterranean formation which comprises placing in the subterranean formation a liquid cement activating composition comprising water, an alkali sulfate salt, a salt of polyphosphate and a stabilizer for polymer.
公开号:FR3040392A1
申请号:FR1656708
申请日:2016-07-12
公开日:2017-03-03
发明作者:Janelle Haydon；Sean William Riggio；Kyriacos Agapiou；Thomas Jason Pisklak；Samuel Lewis
申请人:Halliburton Energy Services Inc；
IPC主号:

专利说明:

CEMENT ACTIVATION COMPOSITION FOR THE TREATMENT OF
UNDERGROUND TRAINING
CONTEXT
[0001] Cements play an important role in the integrity of the wellbore. The cements can be used in primary cementing operations in which tube trains, such as tubing or liners, are cemented into the wellbore. In a typical primary cementing operation, a cement may be pumped into a ring between the outer surface of the tubing string placed therein and the walls of the wellbore (or a larger conduit in the wellbore). The cement can harden in the ring, thus forming an annular sheath of hardened, substantially impermeable material (eg, a cement sheath) that can support and position the string of tubes in the wellbore and can bond the outer surface from the tube train to the walls of the wellbore (or to a larger duct). The cements can also be used in cementing processes, such as pressure cementing to fill voids in a string of tubes, a cement sheath, a filter bed, an underground formation, and the like.
[0002] A wide variety of cement compositions has been used in underground cementing operations. In some cases, delayed hardening cement compositions have been used. The delayed hardening cement compositions are characterized in that they remain in a comparable fluid state for at least about one day (e.g., at least about 7 days, about 2 weeks or about 2 years or more) at room temperature. ambient temperature (eg around 20 to 30 ° C) during inactive storage. When needed, one must be able to activate delayed cure cement compositions which thereby develop reasonable compressive forces. For example, an activating composition may be added to a retarded cure cement composition which hardens the composition (eg, solidifies) into a solid mass.
A number of activating compositions can be used to activate or accelerate the curing of the cement composition. However, within 24 hours, several activating compositions demonstrate separation or form a gelled mass that can not be returned to a uniformly dispersed suspension even with the application of a shear force or agitation. Therefore, many activating compositions must be prepared immediately before use, which could have several disadvantages such as, for example, functional interruptions due to the need to prepare the material on site.
BRIEF DESCRIPTION OF THE FIGURES
The figures illustrate, by way of example, but not by way of limitation, various embodiments presented in this document.
[0005] Fig. 1 illustrates a system or apparatus for delivering a composition into an underground formation, in accordance with various embodiments.
[0006] FIG. 2 illustrates a photo of an activation system 7 days old, in accordance with various embodiments.
[0007] Figure 3 illustrates a photo of a 7-day old activation system comprising a 2-acrylamido-2-methylpropanesulphonic acid (AMPS) / dimethylacrylamide (DMA) copolymer, according to various embodiments.
[0008] FIG. 4 illustrates a photo of a 3 day old activation system comprising an AMPS / acrylamide / acrylonitrile copolymer and a viscosity agent, according to various embodiments.
[0009] Fig. 5 illustrates a photo of a 3 day old activation system comprising an AMPS / DMA copolymer and a viscosity agent, according to various embodiments.
FIG. 6 illustrates a photo of an activation system 4 days old, comprising an AMPS / DMA copolymer and a viscosity agent, according to various embodiments.
Figure 7 illustrates a photo of a 3 day old activation system comprising an AMPS / DMA copolymer and a viscosity agent, according to various embodiments.
Figure 8 illustrates a photo of an activation system 3 days old, according to various embodiments.
Figure 9 illustrates a photo of an activation system 3 days old, according to various embodiments.
Fig. 10 illustrates a photo of a 24 hr activation system comprising an AMPS / DMA copolymer according to various embodiments.
FIG. 11 illustrates a photo of a 24 hour old activation system comprising a polyvinyl alcohol polymer, according to various embodiments.
Figure 12 illustrates a photo of a 24 hour old activation system comprising an acrylamide-acrylic acid copolymer, according to various embodiments.
DETAILED DESCRIPTION OF THE INVENTION
Reference will now be made in detail to certain embodiments of the subject of the invention disclosed, examples of which are illustrated in part in the accompanying figures. While the object of the disclosed invention will be described in association with the enumerated claims, it will be understood that the object of the invention exemplified is not intended to limit the claims to the object of the invention. disclosed.
In this document, the values are expressed in a range format and should be interpreted flexibly to include not only the numerical values explicitly mentioned as the limits of the range, but should also include all the individual numerical values or sub-ranges encompassed by this range as if each numerical value or each sub-range is explicitly mentioned. For example, a range "from about 0.1% to about 5%" "from about 0.1% to 5%" should be interpreted to include not only about 0.1% to about 5%, but also individual values (eg, 1%, 2%, 3% and 4%) and sub-ranges (eg, 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The phrase "about X to Y" has the same meaning as "about X to approximately Y" unless otherwise indicated. Similarly, the statement "about X, Y or about Z" has the same meaning as "about X, about Y or about Z" unless otherwise indicated.
In this document, the terms "a", "a" or "the" are used to include one or more, unless the context clearly indicates otherwise. The term "or" is used to describe a non-exclusive "or" unless otherwise indicated. The statement "at least one of A and B" has the same meaning as "A, B or A and B". In addition, it should be understood that the phraseology or terminology used here, which is not defined, is given for descriptive and not limiting purposes. The use of section headers is intended to assist in reading the document and should not be construed as a limitation; information that is relevant to a section header can be inside or outside that given section. A comma can be used as a delimiter or delimiter of decimal points to the right or left of a decimal point; eg, "0.000.1" is equivalent to "0.0001".
In the methods described here, the actions can be performed in any order without departing from the principles of the invention except when a temporal or operational sequence is explicitly described. In addition, specific actions can be performed simultaneously unless specifically mentioned in the claims that they must be performed separately. For example, an action claimed to perform X and a claim claimed to be made Y may be made in a single operation, and the resulting process will be literally within the scope of the claimed process.
The term "about" as used herein may allow a degree of variability in value or range, eg, within 10%, within 5% in 1% of the value. mentioned or a specified range of limits, and includes the exact value or range mentioned.
The term "substantially" as used herein describes a majority of, or most of, as in at least about 50%, 60%, 70% 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%.
The term "organic group" as used herein describes any functional group containing carbon. For example, a group containing oxygen such as an alkoxy group, an aryloxy group, an aralkyloxy group, an oxo (carbonyl) group; a carboxyl group comprising a carboxylic acid, a carboxylate and a carboxylate ester; a group containing sulfur such as an alkyl or aryl sulfide; and other groups containing heteroatoms. Non-limiting examples of organic groups include OR, OOR, OC (O) N (R) 2, CN, CF 3, OCF 3, R, C (O), methylenedioxy, ethylenedioxy, N (R) 2, SR, SOR, SO 2 R , SO2N (R) 2, SO3R, C (O) R, C (O) C (O) R, C (O) CH2C (O) R, C (S) R, C (O) OR, OC (O) ) R, C (O) N (R) 2, OC (O) N (R) 2, C (S) N (R) 2, (CH2) 0-2N (R) C (O) R, (CH2) ) 0. 2N (R) N (R) 2, N (R) N (R) C (O) R, N (R) N (R) C (O) OR, N (R) N (R) CON (R) 2, N (R) SOaR, N (R) SO 2 N (R) 2, N (R) C (O) OR, N (R) C (O) R, N (R) C (S) R, N ( R) C (O) N (R) 2, N (R) C (S) N (R) 2, N (COR) COR, N (OR) R, C (-NH) N (R) 2, C (0) N (OR) R, C (= NOR) R, and the substituted or unsubstituted (C1-C10o) hydrocarbyl, wherein R may be a hydrogen atom (in the examples which include other carbon atoms ) or a carbon-based entity, and wherein the carbon-based entity can itself be substituted or not.
The term "substituted" as used herein in combination with a molecule or an organic group, as defined herein, describes the state in which one or more hydrogen atoms are in that These are replaced by one or more non-hydrogen atoms.
The term "functional group" or "substituent" as used herein refers to a group that can be or is substituted on a molecule or on an organic group. Examples of substituents or functional groups include, but are not limited to, halogen (eg, F, Cl, Br and I); an oxygen atom in groups such as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo (carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates and carboxylate esters; a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups and sulfonamide groups; a nitrogen atom in groups such as amines, hydroxyamines, nitriles, nitro groups, N-oxides, hydrazides, azides and enamines; and other heteroatoms in various other groups. Non-limiting examples of substituents which may be attached to a substituted carbon (or other) atom include F, Cl, Br, I, OR, OC (O) N (R) 2, CN, NO, NO 2, ONO 2 , azido, CF3, OCF3, R, O (oxo), S (thiono), C (O), S (O), methylenedioxy, ethylenedioxy, N (R) 2, SR, SOR, SO2R, SO2N (R) 2 , S03R, C (O) R, C (O) C (O) R, C (O) CH2C (O) R, C (S) R, C (O) OR, 0C (O) R, C (O) ) N (R) 2, OC (O) N (R) 2, C (S) N (R) 2, (CH 2) o-2N (R) C (O) R, (CH 2) o-2N (R) ) N (R) 2, N (R) N (R) C (O) R, N (R) N (R) C (O) OR, N (R) N (R) CON (R) 2, N (R) SO 2 R, N (R) SO 2 N (R) 2, N (R) C (O) OR, N (R) C (O) R, N (R) C (S) R, N (R) C (0) N (R) 2, N (R) C (S) N (R) 2, N (COR) COR, N (OR) R, C (= NH) N (R) 2, C (O) N (OR) R and C (= NOR) R, R being a hydrogen atom or a carbon-based entity; e.g., R can be hydrogen, (C 1 -C 10) hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl or heteroarylalkyl; or wherein the R group bonded to a nitrogen atom or adjacent nitrogen atoms may, together with the nitrogen atom (s), form a heterocyclyl.
The term "alkyl" as used herein describes linear or branched alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, from 1 to about 20 carbon atoms, from 1 to 12 carbon atoms. carbon or, in some embodiments, from 1 to 8 carbon atoms. Examples of straight chain alkyl groups include those having 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-pentyl, heptyl and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl and 2,2-dimethylpropyl groups. As used herein, the term "alkyl" includes n-alkyl, isoalkyl and anteisoalkyl as well as other branched-chain forms of alkyl. Representative substituted alkyl groups may be substituted one or more times with any of the groups listed herein, eg, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy and halogen.
The term "alkenyl" as used herein refers to cyclic, linear or branched alkyl groups as defined herein, except that there is at least one double bond between two carbon atoms. Thus, the alkenyl groups have from 2 to 40 carbon atoms, or from 2 to about 20 carbon atoms, or from 2 to 12 carbon atoms or, in some embodiments, from 2 to 8 carbon atoms. Examples include, without limitation, vinyl, -CH = CH (CH3), -CH = C (CH3) 2, -C (CH3) = CH2, -C (CH3) = CH (CH3), -C (CH2CH3) ) = CH2, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl and hexadienyl, among others.
The term "acyl" as used herein refers to a group containing a carbonyl moiety in which the moiety is bonded across the carbonyl carbon atom. The carbonyl carbon atom is bonded to a hydrogen atom forming a "formyl" group or bonded to another carbon atom, which may be part of an alkyl, aryl, aralkyl cycloalkyl, cycloalkylalkyl, heterocyclyl group heterocyclylalkyl, heteroaryl, heteroarylalkyl or etc. An acyl group may comprise from 0 to about 12, from 0 to about 20 or from 0 to about 40 additional carbon atoms bonded to the carbonyl group. An acyl group may contain double or triple bonds in the definition given herein. An acryloyl group is an example of an acyl group. An acyl group may also include heteroatoms in the definition given herein. A nicotinoyl (pyridyl-1-3-carbonyl) group is an example of an acyl group as defined herein. Other examples include acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl and acryloyl groups, and the like. When the group containing the carbon atom which is attached to the carbonyl carbon atom contains a halogen, the group is called a "haloacyl" group. An example is a trifluoroacetyl group.
The term "aryl" as used herein refers to cyclic aromatic hydrocarbon groups that do not contain heteroatoms in the ring. Thus, the aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthhacenyl, chrysenyl, biphenylenyl, anthracenyl and naphthyl groups. In some embodiments, the aryl groups contain about 6 to about 14 carbon atoms in the ring moiety of the groups. The aryl groups may be substituted or unsubstituted as defined herein. Representative substituted aryl groups may be monosubstituted or substituted more than once, for example, without limitation, a substituted phenyl group at any one or more of 2-, 3-, 4-, 5- or 6- phenyl ring, or a substituted naphthyl group at any one or more 2- to 8-positions thereof.
The term "heterocyclyl" as used herein refers to aromatic and nonaromatic ring compounds containing 3 or more members, one or more of which is a heteroatom such as, without limitation, N, O, and S Thus, a heterocyclyl or a cycloheteroalkyl, or a heteroaryl, or for a polycyclic, any combination thereof. In some embodiments, heterocyclyl moieties comprise from 3 to about 20 members, while other moieties have from 3 to about 15 members. A heterocyclyl group identified as C2-heterocyclyl may have 5 members with 2 carbon atoms and 3 heteroatoms, 6 members with 2 carbon atoms and 4 hetero atoms, etc. In the same way a C4-heterocyclyl may have 5 members with a heteroatom , 6-membered with 2 heteroatoms, etc. The number of carbon atoms plus the number of hetero atoms is equal to the total number of atoms in the ring. A heterocyclyl ring may also include one or more double bonds. A heteroaryl ring is an embodiment of a heterocyclyl group. The term "heterocyclyl group" includes fused ring entities including those that include aromatic and nonaromatic fused moieties.
The terms "halo", "halogen" or "halide" groups, as used herein, alone or as part of another substituent, mean, unless otherwise indicated, a fluorine atom. , chlorine, bromine or iodine.
The term "haloalkyl" group, as used herein, includes mono-halo alkyl groups, poly-halo alkyl groups in which all the halo atoms may be the same or different atoms, and alkyl groups. per-halo, in which all hydrogen atoms are replaced by halogen atoms, such as fluoro. Examples of haloalkyl include trifluoromethyl, 1,1-dichloroethyl, 1,2-dichloroethyl, 1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.
The term "hydrocarbon" or "hydrocarbyl" as used herein describes a molecule or functional group, respectively, which has carbon and hydrogen atoms. This term may also describe a molecule or functional group which normally has both carbon and hydrogen atoms but in which the hydrogen atoms are substituted by other functional groups. A hydrocarbyl group may be a functional group derived from a straight chain, branched or cyclic hydrocarbon, and may be alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl, or any combination thereof . The hydrocarbyl moieties may be exemplified as (Ca-Cb) hydrocarbyl, wherein a and b are positive integers and means that there may be any number of a to b carbon atoms. For example, (Ci-C4> hydrocarbyl means that the hydrocarbyl group may be methyl (Ci), ethyl (C2), propyl (C3) or butyl (C4), and (Co-Cb) hydrocarbyl say that there is no hydrocarbyl group in some embodiments.
The term "solvent" as used herein refers to a liquid that can dissolve a solid, a liquid or a gas. Non-limiting examples of solvents are silicones, organic compounds, water, alcohols, ionic liquids and supercritical fluids.
The term "number average molecular weight" (Mn) as used herein describes the ordinary arithmetic mean of the molecular weight of the individual molecules in a sample. It is defined as the total weight of all molecules in a sample divided by the total number of molecules in the sample. Experimentally, Mn is calculated by analyzing a sample divided into fractions of molecular weight of the species having n, molecules of molecular weight Mi through the formula Mn = ΣΜμ / Zrij. Mn can be measured by a variety of well-known methods such as exclusion chromatography, end-group analysis by spectroscopy and osmometry. In the absence of precision, the molecular weights of the polymers given herein are number average molecular weights.
The term "weight average molecular weight" as used herein describes an Mw, which is equal to ΣΜ2ηι / ΣΜίΠί, where nj represents the number of molecules having the molecular weight Mi. In various examples, the weight Weight average molecular weight can be determined using light diffraction, small angle neutron diffraction, X-ray diffraction, and sedimentation rate.
The term "room temperature" as used herein describes a temperature of about 15 to 28 ° C.
The term "standard temperature and pressure" as used herein describes a temperature of 20 ° C and a pressure of 101 kPa.
As used herein, the term "degree of polymerization" represents the number of repeating units in a polymer.
As used herein, the term "polymer" describes a molecule having at least one repeating unit and may include copolymers.
The term "copolymer" as used herein refers to a polymer that comprises at least two repeating units. A copolymer may comprise any suitable number of repeating units.
[0041] The term "bottom well" as used herein describes an underground location, such as a location within or connected to a wellbore fluid.
As used herein, the term "cementing fluid" describes fluids or suspensions used in cementing operations of a well. For example, a cementing fluid may comprise an aqueous mixture containing at least one of cement or cement kiln dust. In another example, a cementing fluid may comprise a curable resinous material such as a polymer that is at least partially in an uncured state.
As used herein, the term "water control material" describes a solid or liquid material that interacts with the aqueous material at the bottom of the well, so that the hydrophobic material can more easily travel to the water. the surface and so that a hydrophilic material (including water) can travel less easily to the surface. A water control material may be used to treat a well to cause a decrease in the proportion of the water produced and to cause an increase in the proportion of hydrocarbons produced, e.g. by selectively binding a material together. between subterranean formations producing water and the wellbore while still allowing production at the hydrocarbon producing formations.
As used herein, the term "fluid" describes liquids and gels, unless otherwise indicated.
As used herein, the term "subterranean material" or "subterranean formation" describes any material beneath the surface of the earth, including under the surface of the ocean floor. For example, an underground formation or subterranean material may represent any section of a wellbore and any section of a formation or sub-region producing oil or water in fluid contact with the well drilling. Placing a material in an underground formation may include contacting the material with any section of a wellbore or any subterranean region in fluid communication therewith. Underground materials may include any material placed in the wellbore such as cement, drill shafts, liners, tubes, casing or filters; placing a material in an underground formation may include contacting with such subterranean materials. In some examples, an underground formation or subterranean material may represent any subterranean region that can produce liquid or gaseous oil materials, water, or any section of an underground fluid in contact therewith. For example, an underground formation or subterranean material may be at least one of a desired fracturing zone, a fracture or an area surrounding a fracture, and a flow path or an area surrounding a flow path, in wherein a fracture or flow path may optionally be fluidly connected to an underground region producing oil or water directly through one or more fractures or flow paths.
As used herein, the term "treatment of an underground formation" may include any activity oriented toward the extraction of water or oil products from a region or formation. underground generating oil or water, eg, drilling, pacing, hydraulic fracture, cleaning, acidification, completion, cementing, remediation, abandonment, etc.
As used herein, the term "flow path" at the bottom of the well may include any suitable underground flow path through which two underground locations are in fluid connection. The flow path may be sufficient for oil or water to flow from an underground location to the wellbore or vice versa. A flow path may comprise at least one of a hydraulic fracture and a fluid connection through a filter, through a filter bed, through a support, including through a retaining structure bonded to a resin or a support deposited in a fracture, and through sand. A flow path may include a natural underground passageway through which fluids may flow. In some embodiments, a flow path may be water source and may include water. In some embodiments, a flow path may be from an oil source and may include oil. In some embodiments, a flow path may be sufficient to divert from a well, a fracture, or a flow path connected thereto at least one of water, a fluid downhole or hydrocarbon produced.
In various embodiments, the salts having a positively charged counterion may include any positively charged positively charged counterion. For example, the counterion may be ammonium (NH4 +), or an alkali metal such as sodium (Na +), potassium (K +) or lithium (Li +). In some embodiments, the counterions may have a positive charge greater than +1, which may in some embodiments complex with multiple ionized moieties, such as Zn2 +, Al3 +, or alkaline earth metals such as Ca2 + or Mg2 +.
In various embodiments, the salts having a negatively charged counter-ion may comprise any suitable negatively charged counter-ion. For example, contraction may be a halide, such as fluoride, chloride, iodide or bromide. In other examples, the counterion may be nitrate, hydrogen sulphate, dihydrogen phosphate, bicarbonate, nitrite, perchlorate, iodate, chlorate, bromate, chlorite, hypochlorite , hypobromite, cyanide, amide, cyanate, hydroxide, permanganate. The counterion may be a conjugate base of any carboxylic acid, such as acetate or formate. In some embodiments, a counterion may have a negative charge greater than -1, which may in some embodiments complex with multiple ionized moieties, such as oxide, sulfide, nitride, arsenate , phosphate, arsenite, hydrogen phosphate, sulphate, thiosulfate, sulphite, carbonate, chromate, dichromate, peroxide or oxalate.
The polymers described herein may terminate in any suitable manner. In some embodiments, the polymers may terminate in a terminal moiety that is independently selected from a suitable polymerization initiator, -H, -OH, substituted or unsubstituted (C1-C20) hydrocarbyl (e.g. C10) alkyl or (C6-C20) aryl) interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, substituted or non-NH-, and -S-, a poly (substituted or unsubstituted) (C1-C20) hydrocarbyloxy) and a poly (substituted or unsubstituted (Cr C2o) hydrocarbylamino).
In various embodiments, the present invention describes a method for treating a subterranean formation. The method comprises placing in a subterranean formation a liquid cement activating composition comprising water, an alkali sulfate salt, a polyphosphate salt and a polymer stabilizer. The polymer stabilizer comprises a repeating group which is ethylene substituted with a group selected from the group consisting of -C (O) OH, a salt thereof, a (C 1 -C 20) hydrocarbyl ester substituted or unsubstituted this one ; Wherein R 1 is independently selected from the group consisting of (C 1 -C 20) hydrocarbyl substituted or unsubstituted; -CN; and combinations thereof. In each case, the ethylene is independently also substituted or not. The polymer stabilizer also includes a repeating group that includes an anionic moiety.
In various embodiments, the present invention describes a method for treating a subterranean formation. The method comprises placing in the subterranean formation a composition comprising a liquid cement activating composition. The liquid cement activating composition comprises water, an alkali sulfate salt, a polyphosphate salt and a polymer stabilizer. The water is about 30% by weight to about 95% by weight of the liquid cement activating composition. The alkali sulfate salt is from about 0.001% by weight to about 40% by weight of the liquid cement activating composition. The polyphosphate salt is from about 0.001% by weight to about 30% by weight of the liquid cement activating composition. The polymer stabilizer is from about 0.001% by weight to about 30% by weight of the liquid cement activating composition. The polymer stabilizer comprises repeating groups having the structure:
Each time, the repetitive units are found independently in the illustrated direction or in the opposite direction. The repeating units have a block or random copolymer arrangement. The variables R2, R3, and R4 are independently selected from the group consisting of -H, and (C1-C5o) hydrocarbyl substituted or unsubstituted, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O -, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) ni-, and - (CH2-CH2-CH2-O) n-, where n1 is about 1 to about 10,000. R5 is independently selected from the group consisting of C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted or unsubstituted therefrom; -C (O) NR'2, wherein in each case R1 is independently selected from the group consisting of (C1-C20) hydrocarbyl substituted or unsubstituted; and -CN. Variable A is selected from the group consisting of -O- and -NR9-. The variables R6, R7, R8, R9 are independently selected from the group consisting of -H, and a (C1-C50) hydrocarbyl substituted or unsubstituted and interrupted by 0, 1,2 or 3 groups independently selected from the group consisting of: O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n2- and - (CH2-CH2-CH2-O) n2-, where n2 is about 1 to about 10,000. L1 is selected from the group consisting of a bond and a (C1-C5o) hydrocarbylene substituted or uninterrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH 2 -CH 2 -O) n 3 -, and - (CH 2 -CH 2 -CH 2 -O) n 3 -, where n 3 is about 1 to about 10,000. AG variable is an anionic group. Repetitive group A represents about 0.001 mol% to about 25 mol% of the polymer stabilizer. Repetitive group B represents about 25 mol% to about 99.999 mol% of the polymer stabilizer.
In various embodiments, the present invention describes a method for treating a subterranean formation. The method comprises placing in a subterranean formation a liquid cement activating composition comprising water, an alkali sulfate salt, a polyphosphate salt and a polymer stabilizer. The water is about 30% by weight to about 95% by weight of the liquid cement activating composition. The alkali sulfate salt is from about 0.001% by weight to about 40% by weight of the liquid cement activating composition. The polyphosphate salt is from about 0.001% by weight to about 30% by weight of the liquid cement activating composition. The polymer stabilizer is from about 0.001% by weight to about 30% by weight of the liquid cement activating composition. The polymer stabilizer comprises repeating groups having the structure:
Each time, the repetitive units are found independently in the illustrated direction or in the opposite direction. The repeating units have a block or random copolymer arrangement. The group -S (O) (O) OH is in the form of an acid or a salt thereof. Repetitive group A represents about 0.001 mol% to about 25 mol% of the polymer stabilizer. Repetitive group B represents about 25 mol% to about 99.999 mol% of the polymer stabilizer.
In various embodiments, the present invention describes a system comprising a tube placed in a subterranean formation. The system also includes a pump configured to pump an activation composition of the liquid cement into the subterranean formation through the tube. The cement activating composition comprises water, an alkali sulfate salt, a polyphosphate salt and a polymer stabilizer. The polymer stabilizer comprises a repeating group which is ethylene substituted by a group selected from the group consisting of -C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted or unsubstituted this one ; -C (O) NR'2, wherein in each case R1 is independently selected from the group consisting of (C1-C20) hydrocarbyl substituted or unsubstituted; -CN; and combinations thereof. In each case, the ethylene is independently also substituted or not. The polymer stabilizer also includes a repeating group that includes an anionic moiety.
In various embodiments, the present invention describes a liquid cement activating composition for the treatment of an underground formation. The cement activating composition comprises water, an alkali sulfate salt, a polyphosphate salt and a polymer stabilizer. The polymer stabilizer comprises a repeating group which is ethylene substituted by a group selected from the group consisting of -C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted or unsubstituted this one ; -C (O) NR12, wherein in each case R1 is independently selected from the group consisting of (C1-C20) hydrocarbyl substituted or unsubstituted; and -CN. In each case, the ethylene is independently also substituted or not. The polymer stabilizer also includes a repeating group that includes an anionic moiety.
In various embodiments, the present invention describes a liquid cement activation composition for the treatment of an underground formation. The cement activating composition comprises water, an alkali sulfate salt, a polyphosphate salt and a polymer stabilizer. The water is about 30% by weight to about 95% by weight of the liquid cement activating composition. The alkali sulfate salt is from about 0.001% by weight to about 40% by weight of the liquid cement activating composition. The polyphosphate salt is from about 0.001% by weight to about 30% by weight of the liquid cement activating composition. The polymer stabilizer is from about 0.001% by weight to about 30% by weight of the liquid cement activating composition. The polymer stabilizer comprises repeating groups having the structure:
Each time, the repetitive units are found independently in the illustrated direction or in the opposite direction. The repeating units have a block or random copolymer arrangement. The variables R2, R3, and R4 are independently selected from the group consisting of -H, and (C1-C5o) hydrocarbyl substituted or unsubstituted, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O -, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) ni-, and - (CH2-CH2-CH2-O) n-, where n1 is about 1 to about 10,000. R 5 is independently selected from the group consisting of C (O) OH, a salt thereof, a (C 1 -C 20) hydrocarbyl ester substituted or unsubstituted therefrom; -C (O) NR '2, where in each case R 1 is independently selected from the group consisting of (C 1 -C 20) hydrocarbyl substituted or unsubstituted; and -CN. Variable A is selected from the group consisting of -O- and -NR9-. The variables R6, R7, R8, R9 are independently selected from the group consisting of -H, and a (C1-C5o) hydrocarbyl substituted or unsubstituted and interrupted by 0, 1,2 or 3 groups independently selected from the group consisting of: O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n2- and - (CH2-CH2-CH2-O) n2-, where n2 is about 1 to about 10,000. L1 is selected from the group consisting of a bond and a substituted or unsubstituted (C1-C50) hydrocarbylene interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH - substituted or unsubstituted, - (CH2-CH2-O) n3-, and - (CH2-CH2-CH2-O) n3-, where n3 is about 1 to about 10,000. The variable AG is an anionic group. Repetitive group A represents about 0.001 mol% to about 99.999 mol% of the polymer stabilizer. Repetitive group B represents about 0.001 mol% to about 99.999 mol% of the polymer stabilizer.
In various embodiments, the present invention describes a process for preparing a composition for the treatment of an underground formation. The method comprises preparing a liquid cement activating composition for treating a subterranean formation (e.g., for mixing with and for activating a cement composition above the surface or at the bottom of the well, for hardening of the cement composition in the subterranean formation). The cement activating composition comprises water, an alkali sulfate salt, a polyphosphate salt and a polymer stabilizer. The polymer stabilizer comprises a repeating group which is ethylene substituted with a group selected from the group consisting of -C (O) OH, a salt thereof, a (C 1 -C 20) hydrocarbyl ester substituted or unsubstituted this one ; Wherein R1 is independently selected from the group consisting of (C1-C20) hydrocarbyl substituted or unsubstituted; and -CN. In each case, the ethylene is independently also substituted or not. The polymer stabilizer also includes a repeating group that includes an anionic moiety.
Various embodiments of the cement activating composition and method of use thereof have advantages over other cement activating compositions and methods of using same , at least some of them being unexpected. For example, in various embodiments, the cement activating composition can activate or accelerate the curing of a wide variety of cement compositions, such as Portland cement compositions and lime and pozzolan cement compositions. such as lime cement and delayed cure pozzolana compositions. In some embodiments, the activating composition may have better stability than the homogeneity of the composition, and less gelling, for longer periods, compared to other activating compositions. In various embodiments, the increased stability of the activating composition may be independent of the viscosity of the activating composition. In various embodiments, the improved stability of the activating composition may allow its advance preparation and storage for longer periods, the composition remaining homogeneous, non-gelled and ready for use. In various embodiments, the improved stability of the activating composition can enable the activation composition to be prepared in a suitable location and then transported to the site of use, which can reduce equipment costs given less need for bulk storage and on-site mixing equipment, such as in offshore cementing operations where space on board ships may be limited.
Due to the limitations associated with the reactivity due to the hydration of several delayed curing compositions, most cement activating compositions can only be used at temperatures above 60 ° C to allow Cement compositions activated to develop adequate strength. However, in various embodiments, the activating composition may allow low temperature activation (eg, below 60 ° C) of the cement compositions.
In some embodiments, the activating composition may have fluid loss control properties. Some cementitious compositions can not be prepared with fluid loss control agents either in a dry mix or in a storable paste state, or can be prepared only with a limited type and concentration of agents. control of fluid loss, eg because of the limitations imposed by the rheology of the dough during storage. For example, the addition of a fluid loss control agent to a retarded cure cement composition can cause undesirable dough effects of the cement composition during the storage period. In various embodiments, the activating composition can impart fluid loss control properties to an activated cement composition therein. In various embodiments, the fluid loss control properties imparted by the activating composition may prevent the on-site mixing of fluid pair control materials with the cement suspensions.
Method of treating an underground formation
In some embodiments, the present invention describes a method for treating a subterranean formation. The method comprises placing a liquid cement activating composition in a subterranean formation, such as any embodiment of the cement activating composition described herein. Placement of the cement activating composition into the subterranean formation may include contacting the cement activating composition with any suitable portion of the subterranean formation, or contacting the activating composition of the cement and underground material, as any suitable underground material. The underground formation may be any appropriate underground formation. In some examples, placing a cement activating composition in the subterranean formation comprises contacting the cement activating composition with or placing the cement activating composition in at least one a fracture, at least one of an area surrounding a fracture, a flow path, an area surrounding a flow path and a desired area to be fractured. The placement of the cement activating composition into the subterranean formation may be any placement and may include any contacting between the subterranean formation and the cement activating composition.
In some embodiments, the method comprises obtaining or using the cement activating composition. The obtaining or use of the cement activating composition can be at any convenient time and at any suitable location. The obtaining or use of the cement activating composition can be above the surface (eg, one or more components of the cement activating composition can be mixed above the surface ). The obtaining or use of the cement activating composition can be in the subterranean formation (eg, one or more components of the cement activating composition can be combined at the bottom of the well).
In various embodiments, the method may comprise mixing the cement activating composition with a cementitious composition. The mixing can be done above the surface, so that the placement of the cement activating composition in the subterranean formation includes placing a mixture of the cement activating composition and the cement composition. in the underground formation. The mixing can be done in the subterranean formation so that a mixture of the cement activating composition and the cement composition is formed in the subterranean formation. The mixture of the cementitious activating composition and the cementitious composition may be a curable composition that can harden and solidify. Any suitable amount of the mixture of the cement activating composition and the cement composition can form the cement activating composition, such as, for example, about 0.001% by weight to about 99.999% by weight of the mixture of the an activating composition of the cement and the cement composition, or about 10% by weight to about 50% by weight, or about 0.001% by weight or less, or, less than, equal to or greater than about 0.01% by weight % by weight, 0.1, 1, 2, 3, 4, 5, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99% by weight, or about 99.999% by weight or more. In the mixture of the cement activating composition and a cement composition containing pumice (eg, containing pozzolan), the amount of the cement activating composition may be any appropriate percentage of the weight total of the pumice in the cement composition, e.g., about 0.001% to about 99.999%, about 60% to about 95%, about 70% to about 90% or about 0.001% or less, or less than , equal to greater than about 0.01%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15,20,25, 30, 35,40,45, 50, 55, 60 ,,,,,, , 91, 92, 93, 94, 95, 93, 97, 98, 99, 99.9, 99.99%, or about 99.999% or more.
In various embodiments, the method may comprise curing (e.g., solidifying) a mixture that comprises the cement activating composition and a cement composition, such as a cement composition containing pumice stone (eg, containing pozzolana). Curing may occur for any suitable time, at any suitable temperature, and at any suitable pressure, such as temperatures and pressures experienced at the bottom of the well. Curing can be for less than, equal to or more than 10 minutes, 20, 30, 40, 50 minutes, 1 hour, 1.5, 2, 3, 4, 5, 6, 8, 10, 12, 14 , 16, 18, 20.22 h, 1 day, 1.5.2, 3.4, 5, 6 days, 1 week, 1.5, 2, 3 weeks, or approximately one month at most. Curing may be at about 0 ° C about 500 ° C, or about 20 ° C to about 400 ° C, or about 0 ° C or less, or less than, equal to or greater than about 10 ° C, , 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 275, 300, 350, 400, 450, or about 500 ° C or more.
The cured product of the mixture comprising the cement activating composition and the cement composition may have any suitable tensile strength, e.g. about 100 psi to about 10,000 psi, about 500 psi to about 1000 psi, or about 100 psi or less, or about 150 psi, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700 , 750, 800, 850, 900, 1,000, 1,500, 2,000, 2,500, 5,000, 7,500, or about 10,000 psi or more.
The cured product of the mixture comprising the cement activating composition and the cementitious composition may have any suitable compressive strength, e.g. about 50 psi to about 10,000 psi, about 300 psi to about 10,000 psi, about 1000 psi to about 3000 psi, about 100 psi to about 500 psi, or about 50 psi or less, or about 75 psi, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 450, 500, 600, 700, 800, 900, 1,000, 1,500, 2,000, 2,500, 3,000, 5,000, 7,500, or about 10,000 psi or more.
In various embodiments, the method includes cementing or repairing a wellbore in an underground formation. For example, the cement activating composition can be placed in a ring between a casing and the wellbore, or between two casings, mixed with a cementitious composition, and the mixture can then be cured. The mixture of the cement activating composition and the cement composition can be made prior to placing the cement activating composition in the ring, so that a mixture of the cement activating composition and the cement composition is placed in the ring. In another embodiment, a cement composition can be placed in the ring, and the cement activating composition can be added to the cement composition in the ring to form a mixture, which can then be cured. In some examples, the method may include placing a mixture of the cement activating composition and a cement composition in a damaged region of a wellbore and then curing the mixture of the composition of the activation of the cement and the cement composition. The cement composition may either be mixed with the cement activating composition prior to placement in the desired cure location, or the cement composition may already be in place at the bottom of the well and the cement activating composition may then be to be mixed inside of it.
In various embodiments, the method comprises consolidation of the bottom well particles. For example, the method may include placing a mixture of a cement activating composition and a cement composition in a region of the subterranean formation that includes fine particles, gravel, or other particles, and allowing the mixture to harden so that the particles are substantially fixed in place. In various embodiments, the method may include lost circulation management, eg, by placing a mixture of the cement activating composition and a cement composition in a subterranean region experiencing fluid loss and hardening. the composition. The cement composition may either be mixed with the cement activating composition prior to placement in the desired cure location, or the cement composition may already be in place at the bottom of the well and the cement activating composition may then be to be mixed inside of it.
Cement composition.
In various embodiments, the cement activating composition may be mixed with a cementitious composition. The cementitious composition may be any cement composition that can be cured to form a cured cement, eg, curing after mixing with the cement activating composition. The cement composition may comprise any type of suitable cement, eg, hydraulic cement. The cementitious composition may comprise a cement containing calcium, aluminum, silicone, oxygen, iron or sulfur, which may harden and solidify by reaction with water. The cement composition may contain Portland cement, pozzolan cement, gypsum cement, high alumina cement, dairy cement, silica cement, or a combination thereof. In some embodiments, the Portland cements that are suitable for use in the embodiments of the present invention are classified as Class A, C, H and G cement according to the American Petroleum Institute, API Specification for Materials. and Testingfor Well Cements, API Specification 10, 5th ed., July 1, 1990. The cement composition may comprise a pozzolan cement, such as lime-pozzolan cement. The cementitious composition may be a delayed hardening cement composition. The cement composition may comprise any amount of cement therein, e.g., about 10% by weight to about 100% by weight, or about 10% by weight or less, or less than, or equal to, greater than to about 12% by weight, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94 , 95, 96, 97, 98, or about 99% by weight or more. The cement composition may be a dry cement composition, or a paste (eg, containing water). A paste cement composition may contain any amount of water, e.g. about 10% by weight to about 95% by weight, or less than or equal to or greater than about 12% by weight, 14, 16 , 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94% by weight, or about 95% by weight or more.
A cement composition may comprise cement kiln dust. The cement kiln dust may be any cement kiln dust. Dust from the cement kiln may be formed during cement manufacture and may be from the partially calcined furnace feed which is removed from the gas stream and collected in a dust collector during the manufacturing process. The dust of the cement kiln can advantageously be used in a cost-effective manner since kiln dust is often considered a low value waste of the cement industry. Some embodiments of the cementitious composition may include cement kiln dust but no cement, cement kiln dust and cement or cement but no cement kiln dust. Cement kiln dust may be present in an amount of about 0.001% by weight to about 95% by weight, or about 0.001% by weight or less, or less than or equal to or greater than about 0.01% by weight. %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15,20, 25, 30, 35,40,45, 50, 55, 60, 65, 70, 75, 80, 85, 90% by weight, or about 95% by weight or more.
Optionally, other additives may be added to a cement composition or oven dust containing composition of the embodiments of the present invention as will be deemed appropriate by a subject matter expert, in light of this disclosure. disclosure. Any optional ingredient mentioned in this paragraph may be present or absent from the composition or a mixture comprising it. For example, the composition may include fly ash, metakaolin, shale, zeolite, curing retardant additive, surfactant, gas, accelerants, weight reduction additives, In some examples, the additives may include crystalline silica compounds, amorphous silica, magnesium silicates, salts, fibers, hydratable clays, microspheres, pozzolan lime, thixotropic additives, combinations thereof, etc .;
Cement activation composition.
[0072] The activating composition of the liquid cement (eg, a heterogeneous or homogeneous liquid) may be mixed with a cementitious composition to prepare a mixture which can harden and solidify into a cured material. The cement activating composition can be stable, substantially avoiding separation (eg, remaining substantially homogeneous) and substantially avoiding gelation (e.g., substantially avoiding an increase in viscosity), e.g. day to about 5 years or more, for about 1 day to about 5 months, for about 1 day to about 5 weeks or for at least about 1 day or less, or for at least about 2 days, 3, 4, 5, 6 days, 1 week, 1.5, 2, 2.5, 3 weeks, 1 month, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 months, 1 year, 1 , 5, 2, 3, 4, or for about 5 years or more.
The cement activating composition may contain water. The water may be any suitable water, such as fresh water, brine, produced water, return water, brackish water, seawater, or a combination thereof. The water may comprise any suitable proportion of the cement activating composition, e.g., from about 30% by weight to about 95% by weight of the cement activating composition, from 60% by weight to about 80% by weight. % by weight, or about 30% by weight or less, or less than or equal to or greater than about 35% by weight, 40, 45, 50, 55, 60, 62, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 82, 84, 86, 88, 90% by weight, or about 95% by weight or more of the composition cement activation. In a mixture comprising the cement activating composition and a cement composition comprising pumice, the water in the cement activating composition may be any appropriate percentage of the total weight of the pumice, e.g. about 10% to about 90%, about 40% to about 80%, or about 10% or less, or less than or equal to or greater than about 15%, 20, 25, 30, 35, 40, 42, 44, 46, 48, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 62, 64, 66, 68, 70, 75, 80, 85%, or about 90% or more. The activating composition of the liquid cement may be an aqueous composition, wherein the remaining part of the composition is water (eg, apart from the alkali sulfate salt, the polyphosphate salt, the polymer stabilizer, and any other components, the composition may be water).
The cement activating composition may comprise an alkaline sulfate salt. The activating composition may comprise an alkali sulfate salt, or a plurality of alkali sulfate salts. The alkali sulfate salt may be any alkali sulfate salt, so that the cement activating composition can be used as described herein, such as, for example, potassium sulfate, calcium sulfate, lithium sulfate, sodium sulfate, or a combination thereof. The alkali sulfate salt may be sodium sulfate. One or more alkali sulfate salts may be any suitable proportion of the cement activating composition, such as, eg, about 0.001% by weight to about 40% by weight of the cement activating composition about 1% by weight to about 15% by weight, or about 0.001% by weight less, or less than or equal to or greater than about 0.01% by weight, 0.1, 1, 2, 3, 4, 5, 5.5, 6, 6.5, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7, 9, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, or about 40% by weight or more of the cement activating composition . In a mixture comprising the cement activating composition and a cement composition comprising pumice, one or more alkali sulfate salts may be any suitable percentage of the total weight of the pumice, as, e.g. about 0.001% to about 20%, or about 0.1% to about 5%, or about 0.001% at least, or less than or equal to or greater than about 0.01%, 0.1%. , 2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5 , 1.6, 1.7, 1.8, 1.9, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3 , 8, 4, 4.5, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18%, or about 20% or more.
The cement activation composition may contain a polyphosphate salt. The cement activating composition may comprise a polyphosphate salt or a plurality of polyphosphate salts. The polyphosphate salt may be any suitable polyphosphate salt, so that the cement activating composition can be used as described herein. For example, the polyphosphate salt may be a polymeric metaphosphate salt, a phosphate salt, or a combination thereof. The polyphosphate salt may be sodium hexametaphosphate, sodium trimetaphosphate, sodium tetrametaphosphate, sodium pentametaphosphate, sodium heptametaphosphate, sodium octametaphosphate, and combinations thereof. The polyphosphate salt may be sodium hexametaphosphate. The one or more polyphosphate salts may be any suitable proportion of the cement activating composition, such as, eg, about 0.001 wt% to about 30 wt% of the cement activating composition, about 1 wt% to about 15 wt%, or about 0.001 wt% at least, or less than or equal to or greater than about 0.01 wt%, 0.1, 1, 1.5, 2, 2.5, 3, 3.5, 3.6, 3.8, 4, 4.1.4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4, 8, 4.9, 5, 5.2, 5.4, 5.6, 5.8, 6, 6.5, 7, 7.5, 8, 8.5, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, 22, 24, 26, 28, or about 30% by weight or more. In a mixture comprising the cement activating composition and a cement composition comprising pumice, one or more polyphosphate salts may be any appropriate percentage of the total weight of the pumice stone therein, such as , e.g., about 0.001% to about 20%, or about 0.01% to about 10%, or about 0.001% at least, or less than, or equal to, or greater than about 0.01%, 0, 05%, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1 , 3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.2, 2.4, 2.6, 2.8, 3.5 , 4, 4.5, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18%, or about 20% or more.
The cement activation composition may comprise an optional dispersing agent; in some embodiments, the cement activating composition comprises one or more dispersing agents, while in other embodiments, the cement activating composition contains no dispersing agent. The dispersing agent may be any suitable dispersing agent, so that the cement activating composition can be used as described herein. The dispersing agent can help maintain a desirable dough rheology when the cement composition is activated by the cement activating composition. The dispersing agent can influence the thickening time of the cement paste. The dispersing agent may be a superplasticizing dispersing agent, a sulfonated formaldehyde dispersing agent (eg CFR-3 ™ available from Halliburton), a polycarboxyl ether dispersing agent, or a combination thereof. this. The dispersing agent may be a polycarboxyl ether, such as, for example, Liquiment® 514L or 5581F available from BASF. The one or more dispersing agents may be any suitable proportion of the cement activating composition, such as, eg, about 0.001% by weight to about 40% by weight of the cement activating composition, about 1 wt% to about 25 wt%, or about 0.001 wt% at least, or less than or equal to or greater than about 0.01 wt%, 0.1, 1.2, 4.6, 7, 8, 8.5, 9, 9.5, 10, 10.2, 10.4, 10.6, 10.8, 11, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12, 12.2, 12.4, 12.6, 12.8, 13, 13.5, 14, 14.5, 15, 16, 17, 18, 19, 20, 22, 24, 26, 28, 30, 35, or about 40% by weight or more of the cement activating composition. In a mixture comprising the cement activating composition and a cement composition comprising pumice, the one or more dispersing agents may represent any suitable percentage of the weight of the pumice in it, such as e.g., about 0.001% to about 20%, about 0.01% to about 10%, or about 0.001% at least, or less than, or equal to, or greater than about 0.01%, 0.05% , 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.5 , 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2,2,2,3,2,4, 2,5, 2,6, 2,7, 2,8 , 2.9, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.5, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18%, or about 20% or more.
The cement activation composition may contain a polymer stabilizer. The cement activating composition may comprise a polymer stabilizer or a plurality of stabilizing polymers. The polymer stabilizer may comprise a repeating group which is ethylene substituted with a group selected from the group consisting of -C (O) OH, a salt thereof, a substituted or unsubstituted (C1-C20) hydrocarbyl ester of it; -C (O) NR'2, wherein in each case R1 is independently selected from the group consisting of (C1-C20) hydrocarbyl substituted or unsubstituted; and -CN. In each case, the ethylene may be independently also substituted or unsubstituted.
The polymer stabilizer may also include a repeating group that includes an anionic moiety. The one or more stabilizing polymers can be any suitable proportion of the cement activating composition, so that the cement activating composition can be used as described herein, such as, for example, about 0.001% by weight to about 30% by weight of the activating composition, about 0.1% by weight to about 10% by weight, or about 0.001% by weight or less, or less than, equal to, or greater to about 0.01% by weight, 0.1, 0.5, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.1, 2,2,2,3, 2 , 4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3 , 7, 3.8, 3.9, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.5, 6, 7, 8, 9, 10, 12, 14, 16 , 18, 20, 25, or about 30% by weight or more. In a mixture comprising the cement activator and a cement composition comprising pumice, one or more stabilizing polymers may represent any appropriate percentage of the weight of the pumice in it, such as, for example, , about 0.001% to about 20%, about 0.01% to about 10%, or about 0.1% to about 2.5%, or about 0.001% or less, or less than, or equal to, or greater than about 0.01%, 0.05%, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1 , 2, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7 2.8, 2.9, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.5, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, or about 20% or more.
Without being limited by a given mechanism of action, in various embodiments, the combination of alkali sulfate salt and polyphosphate salt can create a synergy that gives better results than the simple use of one. or the other component. The alkaline sulfated salt may produce an alkali hydroxide upon reaction with lime, which may result in an increase in the pH of the pulp and, therefore, an increase in the dissolution rate of the silicone dioxide. The rate of hydration of the cement has a direct relationship with the proportion of free silicates and / or aluminosilicates. The polyphosphate salt can interact through a chelation mechanism that contributes to the dissociation of retardants on cement surfaces, which can subsequently increase the dissolution rate of the inhibitory calcium complexes. However, in the absence of the polymer stabilizer described herein, the combination of the alkali sulfate salt and the polyphosphate salt can not maintain homogeneity in the activating composition over long periods.
The repeating group which is a substituted ethylene may be any suitable proportion of the polymer stabilizer, so that the activating composition can be used as described herein, such as, for example, about 0.001 mol%. to about 99.999 mol%, 0.001 mol% to about 25 mol%, or about 0.001 mol% less, or less than or equal to or greater than about 0.01 mol%, 0.1, 1 mol. , 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82 , 84, 86, 88, 90, 91.92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% by weight or more of the polymer stabilizer. The repetitive group that is substituted by ethylene can have the structure:
The variables R2, R3, and R4 may be independently selected from the group consisting of -H, and (C1-C5o) hydrocarbyl substituted or unsubstituted, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of: O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-O) n1-, and - (CH2-CH2-CH2-O) n1-, wherein ni is about 1 to about 10,000 ( e.g., about 1 to about 1000, about 1 to about 100, or about 1 to about 10, or about 2, 3, 4, 5, 6, 7, 8, 10, 15, 20, 25, 50, 75 , 100, 150, 200, 250, 500, 750, 1,000, 2,000, 5,000, 7,500, or about 10,000 or more). The variables R2, R3, and R4 may be the independently (C1-C20) hydrocarbyl unsubstituted. The variables R2, R3, and R4 can be independently (C1-C10) alkyl. Variables R2, R3, and R4 can be -H. The variable R5 may be independently selected from the group consisting of C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted or unsubstituted therefrom; Wherein R 1 is independently selected from the group consisting of (C 1 -C 20) hydrocarbyl substituted or unsubstituted; and -CN. The variable R5 can be ^ (OiNR ^, where R1 can be independently the unsubstituted (C1-C20) hydrocarbyl.) The variable R3 can be -C (O) NR'2, where each time R1 can be ( C1-C5) alkyl The variable R5 may be -C (O) NR12, where R1 may be methyl The repeating group which is substituted by ethylene may have the structure:
The repeating group which comprises an anionic group can represent any suitable proportion of the polymer stabilizer, so that the activating composition can be used as described herein, such as, for example, about 0.001 mol%. about 99.999 mol% of the polymer stabilizer, about 25 mol% to about 99.999 mol%, or about 0.001% or less, or less than or equal to or greater than about 0.01 mol%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91.92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% by weight or more of the stabilizer for polymer. The anionic group in the repeating group may be in the form of an acid or a salt thereof. The repetitive group that includes an anionic group can have the structure:
Variable A can be chosen from the group consisting of -O- and -NR9-. Variable A can be -NR9-. The variable R9 may be selected from the group consisting of -H and (C1-C10) alkyl. Variable A can be -NH-. The variables R6, R7, Rs, R9 can be independently selected from the group consisting of -H, and a (C1-C5o) hydrocarbyl substituted or unsubstituted, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-O) n2-, and - (CH2-CH2-CH2-O) n2-, wherein n2 is about 1 to about 10,000 (e.g., about 1 to about 1000, about 1 to about 100, or about 1 to about 10, or about 2, 3, 4, 5, 6, 7, 8, 10, 15, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750, 1,000, 2,000, 5,000, 7,500, or about 10,000 or more). The variables R6, R7, R8 may be independently selected from the group consisting of -H and unsubstituted (C1-C20) hydrocarbyl. The variables R6, R7, R8 may be independently selected from the group consisting of -H and unsubstituted (C1-C10) alkyl. The variables R6, R7, R8 can be -H. The variable L1 is selected from the group consisting of a linkage or (C1-C5o) hydrocarbylene substituted or uninterrupted by 0, 1,2 or 3 groups independently selected from the group consisting of -O-, -S-, - NH- unsubstituted or substituted, - (CH 2 -CH 2 -O) n 3 -, and - (CH 2 -CH 2 -CH 2 -O) n 3 -, where n 3 is about 1 to about 10,000 (e.g., about 1 to about 1000 from about 1 to about 100, or about 1 to about 10, or about 2, 3, 4, 5, 6, 7, 8, 10, 15,20, 25, 50, 75, 100, 150, 200, 250, 500, 750, 1,000, 2,000, 5,000, 7,500, or about 10,000 or more). The variable L1 may be the (C1-C20) hydrocarbylene which is substituted or unsubstituted by (C1-C10) alkyl or otherwise unsubstituted. The variable L1 may be a (C 1 -C 20) alkylene which is substituted or unsubstituted by a (C 1 -C 5) alkyl or otherwise unsubstituted. The variable L1 may be a (C1-C10) alkylene which is substituted or unsubstituted by methyl or else unsubstituted. The variable L1 can be prop-1, 2-ylene substituted with 2-methyl. The variable L1 can have the structure:
The variable AG can be the anionic group. The variable AG can be -S (O) (O) -OH or a salt thereof. The repetitive group that includes an anionic group can have the structure:
The -S (O) (O) OH may be in the form of an acid or a salt thereof.
In various embodiments, the polymer stabilizer may comprise repetitive groups having the structure:
Each time, the repeating units can be found independently in the illustrated direction or in the opposite direction. The repeating units may have a block or random copolymer arrangement. The variables R2, R3, and R4 can be independently selected from the group consisting of -H, and (C1-C50) substituted or unsubstituted hydrocarbyl, interrupted by 0, 1,2 or 3 groups independently selected from the group consisting of: O-, -S-, -N- substituted or unsubstituted, - (CH2-CH2-0) n [-, and - (CH2-CH2-CH2-O) nr, where n1 is about 1 to about 10,000 The variable R5 may be independently selected from the group consisting of C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted or unsubstituted therefrom; -CiCtyNR ^, where in each case R1 is independently selected from the group consisting of (C] -C20) substituted or unsubstituted hydrocarbyl; and -CN. Variable A can be chosen from the group consisting of -O- and -NR9-. The variables R6, R7, R8, R9 may be independently selected from the group consisting of -H, and a substituted or unsubstituted (C1-5C) hydrocarbyl and interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of - O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n2- and - (CH2-CH2-CH2-O) n2-, where n2 is about 1 to about 10,000. L1 can be selected from the group consisting of a bond and a (C1-C5o) hydrocarbylene substituted or uninterrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH - substituted or unsubstituted, - (CH2-CH2-0) n3-, and - (CH2-CH2-CH2-O) n3-, where n3 is about 1 to about 10,000. The AG variable may be the anionic group. Repetitive group A can be from about 0.001 mol% to about 99.999 mol% of the polymer stabilizer. Repetitive group B can be from about 0.001 mol% to about 99.999 mol% of the polymer stabilizer. In various embodiments, the repeating groups A and B together comprise about 100 mole percent of the polymer stabilizer.
In various embodiments, the polymer stabilizer may comprise repeating groups having the structure:
The group -S (O) (O) OH can be in the form of an acid or a salt thereof. Repetitive group A can be from about 0.001 mol% to about 99.999 mol% of the polymer stabilizer. Repetitive group B can be from about 0.001 mol% to about 99.999 mol% of the polymer stabilizer.
In various embodiments, the polymer stabilizer may also comprise repeating unit derived from a vinyl-substituted (C1-C20) heterocycle containing nitrogen. The vinyl-substituted, nitrogen-containing (C 1 -C 20) heterocycle repeating unit may comprise from about 0.001 mol% to about 99.999 mol% of the polymer stabilizer, from about 5 mol% to about 10 mol%. 50 mol%, or about 0.001 mol% or less, or less than, equal to, or greater than about 0.01 mol%, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 mol% or more of the polymer stabilizer. The vinyl substituted (C 1 -C 20) vinyl-substituted heterocycle vinyl moiety may be substituted on a nitrogen atom of the (C 1 -C 2) nitrogen-containing heterocycle. The (C1-C20) vinyl substituted heterocycle containing nitrogen may be N-vinylpyrrolidone.
The polymer stabilizer may also comprise a repeating unit of acrylic acid (eg, a repeating unit which may be prepared from a polymerized acrylic acid, or prepared from a polymerized material which is subsequently hydrolyzed to acrylic acid such as an acrylic acid ester or acrylamide). The repeating unit of acrylic acid may be from about 0.001 mol% to about 99.999 mol% of the polymer stabilizer, about 0.001 mol% to about 5 mol%, or about 0.001 mol% or less, or less than , equal to, or greater than about 0.01 mol%, 0.1, 1.2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35 , 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9 99.99, or about 99.999% by weight or more of the polymer stabilizer.
In certain embodiments, the repeating group which is a substituted ethylene is a repeating unit acrylamide, wherein the repeating group which contains an anionic group is a repeating unit of 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, wherein the polymer stabilizer also comprises a repeating unit of acrylic acid and a repeating unit of N-vinylpyrrolidone. In some embodiments, the acrylamide repeating unit, the AMPS repeating unit, the acrylic acid repeating unit, and the N-vinylpyrrolidone repeating unit may be about 100 mole percent of the polymer stabilizer. .
In some embodiments, the polymer stabilizer also comprises a repeating unit of acrylonitrile. The repeating unit of acrylonitrile may be from about 0.001 mol% to about 99.999 mol% of the polymer stabilizer, 0.001 mol% to about 10 mol%, or about 0.001 mol% or less, or less, of equal weight. at or greater than about 0.01 mole%, 0.1, 1, 2, 3.4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40 ,,,,,,,, 99, or about 99.999% by weight or more of the polymer stabilizer.
In some embodiments, the repeating group which is a substituted ethylene is a repeating unit acrylamide, wherein the repeating group which contains an anionic group is a repeating unit 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof. this, and the polymer stabilizer also comprises a repeating acrylonitrile unit.
In some embodiments, the acrylamide repeating unit, the AMPS repeating unit and the acrylonitrile repeating unit may be about 100 mole percent of the polymer stabilizer.
OTHER COMPONENTS
The cement activating composition, the cement composition, or a mixture comprising one or both of these elements may comprise any suitable additional component in any suitable proportion, so that the activating composition cement or the mixture of the cement activating composition and the cement composition can be used herein as described. All components listed in this section may be present or absent from the cement activating composition, the cement composition, or a mixture comprising one or both of these elements.
In some embodiments, the cement activating composition, the cement composition, or a mixture comprising one or both of these elements, comprises one or more viscosants. Viscosant may be any suitable viscosifier. The viscosifier may affect the viscosity of the cement activating composition, the cement composition, or a mixture comprising one or both of these at any time or location. In some embodiments, the viscosifier can increase the viscosity of at least one of: prior to injection into the subterranean formation; at the time of injection into the underground formation; during transfer through a tube placed in a borehole; once the cement activating composition, the cement composition, or a mixture comprising one or both of these elements, reaches a given subterranean location; some time after the composition or mixture reaches a given subterranean location. In some embodiments, the viscosifier may be from about 0.0001 wt% to about 10 wt% of the cement activating composition, the cement composition, or a mixture comprising one or both of these elements, about 0.004% by weight to about 0.01% by weight, or about 0.0001% by weight or more, 0.0005% by weight, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2 , 3, 4, 5, 6, 7, 8, 9, or about 10% by weight or more.
The viscosifier may comprise at least one of a substituted or unsubstituted polysaccharide, and a substituted or unsubstituted polyalkene (for example, a polyethylene, in which the ethylene unit is substituted or not, derived from ethylene corresponding substituted or unsubstituted), wherein the polysaccharide or polyalkene is crosslinked or not. The viscosifier may comprise a polymer comprising at least one repeating unit derived from a monomer selected from the group consisting of ethylene glycol, acrylamide, vinyl acetate, 2-acrylamidomethylpropanesulphonic acid or its salts , trimethylammoniumethyl acrylate halide and trimethylammoniumethyl methacrylate halide. The viscosifier may comprise a crosslinked gel or a crosslinkable gel. The viscosifier may comprise at least one of a linear polysaccharide and a poly ((C2-C10) alkene), wherein the (C2-C10) alkene is substituted or unsubstituted. The viscosifier may comprise at least one of a poly (acrylic acid) or (C 1 -C 5) alkyl esters thereof, a poly (methacrylic acid) or (C 1 -C 5) alkyl esters of those polyvinyl acetate, polyvinyl alcohol, poly (ethylene glycol), poly (vinyl pyrrolidone), polyacrylamide, poly (hydroxyethyl methacrylate), alginate, chitosan, curdlan, dextran , derivatized dextran, emulsan, galactoglucopolysaccharide, gellan gum, glucuronan, N-acetyl-glucosamine, N-acetyl-heparosan, hyaluronic acid, kefiran, lentinan, levan, mauran, pullulan , scleroglucan, schizophyllan, stewartan, succinoglycan, xanthan, diutane gum, welan gum, starch, derivatized starch, tamarind, gum tragacanth, guar gum, derivatized guar gum (eg, hydroxypropyl guar, carboxy methyl guar or carboxymethyl hydroxypropyl guar), gum ghatti, gum arabic, locust bean gum, karaya gum, cellulose, and derivatized cellulose (e.g., carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose or methyl hydroxyethyl cellulose).
In certain embodiments, the viscosifier may comprise at least one of a polyvinyl alcohol homopolymer, a polyvinyl alcohol copolymer, a crosslinked polyvinyl alcohol homopolymer and a copolymer. of crosslinked polyvinyl alcohol. The viscosifier may comprise a polyvinyl alcohol copolymer or a crosslinked polyvinyl alcohol copolymer comprising at least one of a linear, branched, block and random grafted vinyl alcohol copolymer and at least one (C2-C5o) ) substituted or unsubstituted hydrocarbyl having at least one unsaturated aliphatic CC bond thereon; and substituted or unsubstituted (C2-C5o) alkene. The viscosifier may comprise a polyvinyl alcohol copolymer or a crosslinked polyvinyl alcohol copolymer comprising at least one copolymer of a linear, branched, block and random grafted vinyl alcohol and at least one of a vinyl phosphonic acid , a diphosphonic acid vinylidene, a 2-acrylamido-2-methylpropanesulfonic acid, a (C 1 -C 20) alkenoic acid, propenoic acid, butenoic acid, pentenoic acid, hexenoic acid, acid octenoic acid, nonenoic acid, decenoic acid, acrylic acid, methacrylic acid, hydroxypropyl acrylic acid, acrylamide, fumaric acid, methacrylic acid, hydroxypropyl acrylic acid, vinyl phosphonic acid, diphosphonic acid vinylidene, itaconic acid, crotonic acid, mesoconic acid, citraconic acid, sulfonic acid styrene, allyl sulfonic acid, methallyl sulfonic acid, sulphonic acid vinyl and a summer r (C 1 -C 20) alkyl thereof. The viscosifier may comprise a polyvinyl alcohol copolymer or a crosslinked polyvinyl alcohol copolymer comprising at least one copolymer of a linear, branched, block and random grafted vinyl alcohol and at least one of a vinyl acetate , a vinyl propanoate, a vinyl butanoate, a vinyl pentanoate, a vinyl hexanoate, a vinyl 2-methyl butanoate, a vinyl 3-ethylpentanoate and a a vinyl 3-ethylhexanoate, a maleic anhydride, a substituted or unsubstituted (C1-C20) alkenoic acid or an unsubstituted (C1-C20) alkanoic anhydride, a substituted or unsubstituted (C1-C20) alkenoic acid, substituted or unsubstituted (C1-C20) alkenoic anhydride, propenoic acid anhydride, butenoic acid anhydride, pentenoic acid anhydride, hexenoic acid anhydride, acid anhydride octenoic acid, an anhydride of nonenoic acid, an anhydride of decenoic acid, an anhydride of acrylic anhydride, fumaric acid anhydride, methacrylic acid anhydride, hydroxypropyl acrylic acid anhydride, vinyl phosphonic acid anhydride, vinyl diphenyl vinylidene anhydride, itaconic acid, crotonic acid anhydride, mesoconic acid anhydride, citraconic acid anhydride, styrene sulfonic acid anhydride, allyl sulfonic acid anhydride, methallyl sulfonic acid, vinyl sulfonic acid anhydride and N- (C1-C10) alkenyl containing substituted nitrogen or unsubstituted (CrC10) heterocycle. The viscosifier may comprise a polyvinyl alcohol copolymer or a crosslinked polyvinyl alcohol copolymer comprising at least one graft copolymer, linear, branched, bulk and random which comprises a copolymer (polyvinyl alcohol / acrylamide), an alcohol copolymer (polyvinyl alcohol / 2-acrylamido-2-methylpropanesulfonic acid), a poly (acrylamide / 2-acylamido-2-methylpropanesulfonic acid) copolymer or an alcohol (polyvinyl / N-vinylpyrrolidone) copolymer. The viscosizer may comprise a crosslinked polyvinyl alcohol homopolymer or copolymer comprising a crosslinking agent containing at least one of chromium, aluminum, antimony, zirconium, titanium, calcium, boron, iron, silicon, copper, zinc, magnesium, and an ion thereof. The viscosifier may comprise a crosslinked polyvinyl alcohol homopolymer or copolymer comprising a crosslinking agent comprising at least one of an aldehyde, an aldehyde, a carboxylic acid or an ester forming compound thereof. thereof, a sulfonic acid or an ester thereof, a phosphonic acid or an ester thereof, an acid anhydride and epihalohydrin.
In various embodiments, the cement activating composition, the cement composition, or a mixture comprising one or both of these elements may comprise one or more crosslinking agents. The crosslinking agent may be any suitable crosslinking agent. In some instances, the crosslinking agent may be incorporated into a crosslinked viscosizer, and in other examples, the crosslinking agent may crosslink crosslinkable material (eg, bottom well). The crosslinking agent may comprise at least one of chromium, aluminum, antimony, zirconium, titanium, calcium, boron, iron, silicon, copper, zinc, magnesium, and an ion of these. The crosslinking agent may comprise at least one of boric acid, borax, a borate, a (C 1 -C 3 O) hydrocarbylboronic acid, a (C 1 -C 3) hydrocarbyl (C 1 -C 30) hydrocarbylboronic acid, (C 1 -C 30) hydrocarbylboronic acid modified polyacrylamide, ferric chloride, disodium octaborate tetrahydrate, sodium metaborate, sodium diborate, tetraborate, sodium, tetraborate disodium, pentaborate, ulexite, colemanite, magnesium oxide, zirconium lactate, zirconium triethanolamine, zirconium lactate triethanolamine, zirconium carbonate, zirconium acetylacetonate, zirconium malate, zirconium citrate, zirconium diisopropylamine lactate, zirconium glycolate, zirconium triethanol glycolate, zirconium lactate glycolate, titanium lactate, titanium malate, titanium citrate, lactate d ammonium titanium, titanium triethanol mine, titanium acetylacetonate, aluminum lactate and aluminum citrate. In some embodiments, the crosslinking agent may be a (C 1 -C 20) alkylenebiacrylamide (eg, methylenebisacrylamide), mono- or poly (C 1 -C 20) alkyl substituted with a poly (C 1 -C 4) 2o) alkenyl) (e.g., pentaerythritol allyl ether) and poly (C2-C20) alkenylbenzene (e.g., divinylbenzene). In some embodiments, the crosslinking agent may be at least one of an alkyl diacrylate, an ethylene glycol diacrylate, an ethylene glycol dimethacrylate, a diacrylate, and the like. of polyethylene glycol, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylol propane triacrylate, ethoxylated trimethylol propane trimethacrylate, an ethoxylated glyceryl triacrylate, an ethoxylated glyceryl trimethacrylate, an ethoxylated pentaerythritol tetraacrylate, an ethoxylated pentaerythritol tetramethacrylate, an ethoxylated dipentaerythritol hexaacrylate, a polyglyceryl monoethylene oxide polyacrylate, polyglyceryl polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, dimethacrylate neopentyl glycol, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylol propane triacrylate, trimethylolpropane trimethacrylate, tricyclodecanediacrylate, dimethanol tricyclodecane dimethacrylate, 1,6-hexanediol diacrylate, and dimethacrylate 1 , 6-hexanediol. The crosslinking agent may comprise from about 0.00001% by weight to about 5% by weight of the cement activating composition, the cement composition, or a mixture comprising one or both of these elements. about 0.001% by weight to about 0.01% by weight, or about 0.00001% by weight or less, or about 0.00005% by weight, 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, or about 5% by weight or more.
The cement activation composition, the cement composition, or a mixture comprising one or both of these elements may comprise any suitable fluid. For example, the fluid may be at least one of crude oil, methyl ether of dipropylene glycol, dimethyl ether of dipropylene glycol, methyl ether of dipropylene glycol, ether. of dipropylene glycol, dimethylformamide, diethylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, butylglycidyl ether, propylene carbonate, D-limonene, a C2-C40 fatty acid of the C1-C10 alkyl ester (e.g., a methyl ester of a fatty acid), tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 2-butoxy ethanol, butyl acetate, butyl lactate, furfuryl acetate, dimethyl sulfoxide, dimethylformamide, a fraction of the petroleum distillate (eg (eg, diesel, kerosene, naphtha, etc.) mineral oil, hydrocarbon oil, hydroc arbure containing a carbon-carbon aromatic linkage (eg, benzene, toluene), a hydrocarbon containing an alpha-olefin, xylenes, an ionic liquid, a methyl ethyl ketone, an oxalic acid, maleic or succinic acid ester methanol, ethanol, propanol (iso- or normal-), butyl alcohol (iso-, tert-, or normal-), an aliphatic hydrocarbon (e.g., cyclohexanone, hexane), water, brine, produced water, return water, brackish water, and seawater. The fluid can be from about 0.001% by weight to about 99.999% by weight of the cementitious activating composition, the cementitious composition or a mixture comprising one or both of these elements, or about 0.001% by weight or more, 0.01% by weight, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999% by weight or more.
The cement activating composition, the cement composition, or a mixture comprising one or both of these elements may comprise any suitable downhole fluid. The cementation activating composition may be admixed with any suitable downhole fluid prior to, during, or after the placement of the composition in the subterranean formation or contacting the composition with the subterranean material. In some examples, the cement activating composition is associated with a downhole fluid above the surface, and then the mixed composition is placed in an underground formation or contacted with an underground material. In another example, the cement activating composition is injected into the subterranean formation to mix with a downhole fluid, and the mixed composition is contacted with an underground material or is considered to be placed in the subterranean material. underground formation. Placement of the cement activating composition in the subterranean formation may include contacting the subterranean material with the mixture comprising the cement activating composition. Any appropriate weight percent of the cement activating composition, the cement composition, or a mixture comprising one or both of these elements, which is placed in the subterranean formation or is contacted with the subterranean material, may be downhole fluid, such as, for example, about 0.001% by weight to about 99.999% by weight, about 0.01% by weight to about 99.99% by weight, about 0 From 1 wt% to about 99.9 wt%, about 20 wt% to about 90 wt%, or about 0.001 wt% at least, or about 0.01 wt%, 0.1, 1, 2, 3.4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99, 9, 99.99% or about 99.999% by weight or more of the activating composition of the cement, the cement composition, or a mixture comprising one or both of these elements.
In some embodiments, the cement activating composition, the cement composition, or a mixture comprising one or both of these elements may comprise any amount of suitable material used in a bottom fluid. wells. For example, the cement activating composition, the cement composition, or a mixture comprising one or both of these elements may comprise a cement hardening activator, such as: a zeolite; an amine such as triethanolamine or diethanolamine; a silicate such as sodium silicate; zinc formate; calcium acetate; a Group IA or IIA hydroxide such as sodium hydroxide, magnesium hydroxide or calcium hydroxide; a monovalent salt such as sodium hydroxide; a divalent salt such as calcium chloride; a nanosilicon (e.g., silicon having a particle size of less than or equal to about 100 nanometers); a polyphosphate; and combinations thereof). The cement activating composition, the cement composition, or a mixture comprising one or both of these elements may comprise calcium chloride, triethanolamine, sodium silicate, zinc formate, calcium, sodium hydroxide, water, saline, an aqueous base, an acid, an oil, an organic solvent, an oily phase synthetic fluid, an aqueous solution, an alcohol or a polyol, an cellulose, starch, alkalinity control agents, acidity control agents, density control agents, density modifiers, emulsifiers, dispersants, polymeric stabilizers, a polyacrylamide, a polymer or a combination of polymers, antioxidants, heat stabilizers, foam control agents, solvents, diluents, plasticizer, a filler or an inorganic particle, a pigment, a n dye, a precipitating agent, oily wetting agents, curing retardation additives, surfactants, gases, weight reducing additives, high weight additives, materials of loss of circulation, filtration control additives, salts (e.g., any suitable salt, such as potassium salts such as potassium chloride, potassium bromide, potassium formate; calcium salts such as calcium chloride, calcium bromide, calcium formate; cesium salts such as cesium chloride, cesium bromide, cesium formate, or a combination thereof), fibers, thixotropic additives, grinders, crosslinking agents, rheology modifiers, hardening accelerators, hardening retarders, pH modifiers, chelating agents, scale inhibitors, enzymes, resins, water control materials, oxidants, markers, Portland cement, pozzolan cement, gypsum cement, high alumina cement, dairy cement, silicon cement, fly ash, metakaolin, shale, zeolite, a crystalline silica compound, amorphous silica, hydratable clays, microspheres, lime, or a combination thereof. Any suitable proportion of the activating composition of the cement, the cement composition, or a mixture comprising one or both of these elements, may comprise any optional component listed in this paragraph, such as, for example, about 0.001% by weight to about 99.999% by weight, about 0.01% by weight to about 99.99% by weight, about 0.1% by weight to about 99.9% by weight, about 20 to about 90% by weight, or about 0.001% by weight or more, or about 0.01% by weight, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60 , 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99% by weight, or about 99.999% by weight or more of the composition of activating the cement, the cement composition, or a mixture comprising one of these two elements.
System or apparatus.
In various embodiments, the present invention describes a system. The system may be any suitable system that can utilize or that can be generated by using an embodiment of the composition described herein in a subterranean formation, or that can be realized or generated by the execution of a method of using the composition described herein. The system may comprise a cement activating composition, such as, for example, any embodiment of the cement activating composition described herein. The system may also include an underground formation containing the cement activating composition therein. In some embodiments, the cement activation composition in the system may also include a downhole fluid, or the system may comprise a mixture of the cement activation composition and a downhole fluid. . In some embodiments, the system may include a tube, a pump configured to pump the composition into the subterranean formation through the tube. In various embodiments, the system comprises a mixture that contains the cement activating composition and a cement composition.
Various embodiments describe systems and apparatus configured to transport the composition described herein to an underground location and to use the composition therein, e.g., for a cementing operation. In various embodiments, the system or apparatus may include a pump fluidly coupled to a tube (eg, any suitable type of oilfield tube, such as a pipeline, a drill pipe, a production tube, etc.), the tube containing the cement activating composition or a mixture comprising this composition, as described herein.
The pump may be a high pressure pump in some embodiments. In the present context, the term "high pressure pump" describes a pump that is capable of conveying a fluid to an underground formation (eg, at the bottom of the well) at a pressure of about 1000 psi or more. In some embodiments, the high pressure pump may be able to fluidly transport particulate matter into the subterranean formation. Suitable high pressure pumps will be known to one skilled in the art and may include floating piston pumps and positive displacement pumps.
In other embodiments, the pump may be a low pressure pump. In the context of the present invention, the term "low pressure pump" corresponds to a pump that operates at a pressure close to 1000 psi or less. In some embodiments, a low pressure pump may be fluidly coupled to a high pressure pump that is fluidly coupled to the tubular portion. That is, in these embodiments, the low pressure pump may be configured to transport the cement activating composition to a high pressure pump. In these embodiments, the low pressure pump can "adjust" the pressure of the cement activating composition before it reaches the high pressure pump.
In some embodiments, the systems and apparatuses described herein may also include a mixing tank that is upstream of the pump and wherein the cement activating composition is prepared or mixed with other products. (eg, with a cement composition or with other additives). In various embodiments, the pump (e.g., a low pressure pump, a high pressure pump, or a combination thereof) can carry the cement activating composition or a mixture containing this composition of the mixing tank. or another source of the cement activating composition to the tube. In other embodiments, however, the cement-activating composition may be prepared off-site and transported to a site, in which case the cement-activating composition or the mixture containing the composition may be introduced into the site. tube by the pump directly from its shipping container (eg a truck, wagon, barge or the like) or from a transport pipe. In either case, the cement activating composition or the mixture containing the composition can be pumped into the pump, raised to the appropriate pressure and then introduced into the tube for transport to the subterranean formation.
[00101] Fig. 1 shows an illustrative diagram of systems and apparatuses that can carry embodiments of the activating composition of the cement or mixture containing this composition to an underground location, according to one or more embodiments. It should be noted that even though FIG. 1 illustrates, in general, a terrestrial system, it must be recognized that similar systems and apparatus can be operated in underwater sites as well. Embodiments of the present invention may have a different scale than that illustrated in FIG. 1. As illustrated in Figure 1, the system or apparatus 1 may comprise a mixing tank 10, wherein one embodiment of the cement activating composition or a mixture containing this composition may be prepared.
The activating composition of the cement or a mixture comprising this composition may be transported by line 12 to a head from 14, wherein the composition or the mixture containing the composition enters a tube 16, the tube 16 extending from the head from 14 to an underground formation 18. After ejection of the tube 16, the composition or mixture containing the composition may subsequently enter a subterranean formation 18. The pump 20 may be configured to increase the pressure of the composition or mixture containing the composition to a desired degree prior to its introduction into the tube 16. It should be recognized that the system or apparatus 1 is only an example in nature, and that various other components may be present which have not necessarily been described in Figure 1 for the sake of clarity. In some examples, additional components that may be present may include, but are not limited to, feed nozzles, valves, condensers, adapters, gaskets, gauges, sensors, compressors, pressure gauges , pressure sensors, flow meters, flow sensors, temperature probes, and the like. Although not illustrated in FIG. 1, at least a portion of the composition may, in some embodiments, return to the wellhead 14.
It must also be recognized that the activation composition of the disclosed cement or the mixture containing this composition may also directly or indirectly affect the various equipment and tools underground or downhole that may come into contact with the composition or the mixture containing this composition in operation. Such equipment and tools may include a wellbore casing, a wellbore liner, a completion train, insert trains, a drill pipe, a coiled tubing, a smooth cable, a cable line, drilling tube, drill blocks, sludge motors, downhole motors and / or pumps, motors and / or surface mounted pumps, centralizers, turbolizers, scrapers, floats (e.g. clogs, collars, valves, etc.), logging tools and associated telemetry equipment, actuators (eg electromechanical devices, hydromechanical devices, etc.), sliding sleeves, bushing sleeves production, plugs, screens, filters, flow control devices (eg, influx control devices, autonomous impulse control devices, outflow control devices, etc. .), coupling devices (by e x., an electrohydraulic wet connection, a dry connection, an inductive coupler, etc.), control lines (eg, electrical, fiber optic, hydraulic, etc.), monitoring lines, drill bits, and crimpers, sensors and distributed sensors, well-bottom heat exchangers, valves and corresponding actuators, tool seals, plugs, cement plugs, support plugs, and other devices or components of the wellbore insulation, etc. Any of these components may be part of the systems and apparatus generally described above and described in Figure 1.
Composition for the treatment of an underground formation
Various embodiments describe an activating liquid cement composition for the treatment of an underground formation. The cement activation composition may be any suitable composition that can be used to realize an embodiment of the underground formation treatment method described herein.
For example, the activating composition of the liquid cement may comprise water, an alkali sulfate salt, a polyphosphate salt and a polymer stabilizer. The polymer stabilizer may comprise a repeating group which is ethylene substituted with a group selected from the group consisting of -C (O) OH, a salt thereof, a substituted (C1-C20) hydrocarbyl ester or no of it; -C (O) NR'2, wherein in each case R1 is independently selected from the group consisting of (C1-C20) hydrocarbyl substituted or unsubstituted; and -CN. In each case, the ethylene is independently also substituted or not. The polymer stabilizer may also include a repeating group that includes an anionic moiety.
In various embodiments, the liquid cement activating composition comprises water, an alkali sulfate salt, a polyphosphate salt, and a polymer stabilizer. The water may be from about 30% by weight to about 95% by weight of the liquid cement activating composition. The alkali sulfate salt may be from about 0.001% by weight to about 40% by weight of the liquid cement activating composition. The polyphosphate salt can be from about 0.001% by weight to about 30% by weight of the liquid cement activating composition. The polymer stabilizer can be from about 0.001% by weight to about 30% by weight of the liquid cement activating composition. The polymer stabilizer may comprise repeating groups having the structure:
Each time, the repetitive units are found independently in the illustrated direction or in the opposite direction. The repeating units may have a block or random copolymer arrangement. The variables R2, R3, and R4 can be independently selected from the group consisting of -H, and (C1-C5o) hydrocarbyl substituted or uninterrupted by 0, 1,2 or 3 groups independently selected from the group consisting of -O -, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-O) n1-, and - (CH2-CH2-CH2-O) n-, where n1 is about 1 to about 10,000. variable R5 may be independently selected from the group consisting of C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted or unsubstituted therefrom; -C (O) NR'2, wherein in each case R1 is independently selected from the group consisting of (C1-C20) hydrocarbyl substituted or unsubstituted; and -CN. Variable A can be chosen from the group consisting of -O- and -NR9-. The variables R6, R7, R8, R9 may be independently selected from the group consisting of -H, and a (C1 -C50) hydrocarbyl substituted or unsubstituted and interrupted by 0, 1,2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n2- and - (CH2-CH2-CH2-O) n2-, where n2 is about 1 to about 10,000. The variable L1 may be selected from the group consisting of a bond and a (C1-C5o) hydrocarbylene substituted or uninterrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n3-, and - (CH2-CH2-CH2-O) n3-, where n3 is about 1 to about 10,000. The AG variable may be the anionic group . Repetitive group A can be from about 0.001 mol% to about 99.999 mol% of the polymer stabilizer. Repetitive group B can be from about 0.001 mol% to about 99.999 mol% of the polymer stabilizer.
In some embodiments, the present invention describes a blend that includes an embodiment of the cement activating composition and an embodiment of the cement composition described herein, such as, eg, a composition. cement containing pumice (eg a cement composition containing pozzolan cement). In various embodiments, the present invention describes a cured product of a blend comprising the activating composition of the cement and the cementitious composition.
Process for the preparation of a composition for the treatment of a subterranean formation
In various embodiments, the present invention describes a process for preparing a composition for the treatment of an underground formation. The process may be any suitable method that produces a composition described herein. For example, the method may include preparing a liquid cement activating composition for treating a subterranean formation, such as any embodiment of the cement activating composition described herein. The activating composition of the liquid cement may comprise water, an alkali sulfate salt, a polyphosphate salt and a polymer stabilizer. The polymer stabilizer may be any embodiment of a polymer stabilizer described herein. The polymer stabilizer may comprise a repeating group which is ethylene substituted with a group selected from the group consisting of -C (O) OH, a salt thereof, a substituted or unsubstituted (C1-C20) hydrocarbyl ester of it; -C (O) NR'2, wherein in each case R1 is independently selected from the group consisting of (C1-C20) hydrocarbyl substituted or unsubstituted; and -CN. In each case, the ethylene is independently also substituted or not. The polymer stabilizer may also include a repeating group that includes an anionic moiety.
Examples [00108] Various embodiments of the present invention may be better understood by reference to the following Examples which are presented for illustrative purposes. The present invention is not limited to the Examples given herein.
[00109] General Liquiment® 5581F is a polycarboxyl ether dispersant available from BASF Corporation. SA-1015 ™ suspending agent is an additive available from Halliburton Corporation. Halad®-344 is a copolymer derived from acrylamido-methyl-propane sulfonate (AMPS) and dimethylacrylamide (DMA), available from Halliburton Corporation. Halad®-200 is a copolymer derived from acrylamido-methyl-propane sulfonate (AMPS), dimethylacrylamide (DMA), N-vinyl pyrrolidone and acrylic acid, available from Halliburton Corporation. Halad®-413 is a copolymer derived from acrylamide, acrylonitrile and 2-acrylamido-2-methylpropanesulfonic acid (AMPS), with AMPS groups grafted onto lignite, available from Halliburton Corporation. LeLAP-1 is a polyvinyl alcohol, available from Halliburton Corporation. HZ-30 ™ is a polyacrylamide that can partially hydrolyze upon storage or upon contact with an aqueous medium, available from Halliburton Corporation. The% by weight bwP describes the weight percentage of pozzolan in a sample of 800 g of liquid paste of a pumice cement (434.82 g, 54.35% by weight). Pozzolan was the only pumice found in the liquid clay sample of pumice cement.
Example 1. Sample A. Activation System Not Containing AMPS / DMA Copolymer (Comparative).
The activation system was mixed in the order and concentrations given in Table 1. The activator was mixed in a blender of the "American Petroleum Institute (API)" in about 240 g of H 2 O, about 1300-1500 rpm.
[00111] Table 1.
[00112] Immediate separation occurred after mixing. The top layer appeared after allowing the solution to stand for about 24 hours. The appearance of the yellow, milky upper layer seems to be dependent on the length of time during which the solution was left at rest, without intervention. It was very difficult to homogenize again the second layer of solution during stirring. Figure 2 illustrates a photo of an activation system after 7 days
Example 2. Sample B. Activation System with AMPS / DMA Copolymer.
[00113] The activation system was mixed in the order and concentrations given in Table 2. The activator was mixed in a 1ΆΡΙ mixer in about 240 g of H 2 O at about 1300-1500 rpm.
[00114] Table 2.
The sample remained homogeneous from the moment the mixture was stopped until the mark of 7 days, after which this photo was taken. Brookfield viscosity measurements indicate a stable paste at around 400 cP. Figure 3 illustrates a photo of the activation system after 7 days.
Example 3 Sample C. Activation System with AMPS / Acrylamide / Acrylonitrile Copolymer and Viscosant
The activation system was mixed in the order and concentrations given in Table 3. The activator was mixed in a mélang mixer in about 240 g H 2 O at about 1300-1500 rpm.
[00117] Table 3.
The sample showed signs of separation after 15 to 20 minutes after mixing as indicated by the darker layer at the bottom of the photo. A clear separation between the upper and lower layers was visible after 3 days. Figure 4 illustrates a photo of the activation system after 3 days. The darkest dark layer indicates the beginning of a darker layer forming from a clearer and larger top layer.
Example 4. Sample D. Activation System with AMPS / DMA Copolymer and Viscosant.
The activation system was mixed in the order and concentrations given in Table 4. The activator was mixed in a mélang mixer in about 240 g H 2 O at about 1300-1500 rpm.
[00120] Table 4.
The SA-1015 ™ suspending agent was initially added and mixed for 2 to 3 minutes until complete yield and production of a thick gel. The addition of Liquiment® 5581F significantly thickened the solution during mixing. An additional shear force (2000 rpm) was used to reintroduce a vortex during mixing. The mixture begins to separate slowly after mixing. After 3 days, the milky upper layer appeared, and the intermediate layer was distinguished from the clear lower layer. It has been very difficult to homogenize the second layer of solution again during stirring.
Figure 5 illustrates a photo of the activation system after 3 days.
Example 5. Sample E. Activation System with AMPS / DMA Copolymer and Viscosant.
[00122] The activation system was mixed in the order and concentrations given in Table 5. The activator was mixed in a mélang mixer in about 240 g of H 2 O at about 1300-1500 rpm.
Table 5.
[00124] The system begins to separate slowly after mixing. The sample demonstrates a third top layer after about 24 hours after initial mixing. When compared to the previous activator (Sample D), with exactly the same preparation and the order of addition, a much more distinct and visible separation is created as a function of time.
It was very difficult to homogenize again the second layer of solution during stirring. Figure 6 illustrates a photo of the activation system after 4 days.
Example 6. Sample F. Activation System with AMPS / DMA Copolymer and Viscosant.
[00125] The activation system was mixed in the order and concentrations given in Table 6. The activator was mixed in a mélang mixer in about 240 g of H 2 O at about 1300-1500 rpm.
Table 6.
[00127] The sample separated immediately after mixing. The sample demonstrated a top layer of foam 1 to 3 hours after mixing. A lesser amount of SA-1015 ™ suspending agent appears to accelerate the separation process, as well as creating another layer above the solution. It was very difficult to homogenize again the second layer of solution during stirring. Figure 7 illustrates a photo of the activation system after 3 days. The fourth layer above the solution was not present in the other samples.
Example 7. Sample G. Activation system not containing AMPS / DMA copolymer (comparative).
The activation system was mixed in the order and concentrations given in Table 7. The activator was mixed in a mélang mixer in about 240 g H 2 O at about 1300-1500 rpm.
Table 7.
The sample immediately separated after completion of mixing. A third small layer of foam appeared above the solution. It was very difficult to homogenize again the second layer of solution during stirring. Figure 8 illustrates a photo of the activation system after 3 days.
Example 8. Sample H. Activation System Not Containing AMPS / DMA Copolymer (Comparative).
The activation system was mixed in the order and concentrations given in Table 8. The activator was mixed in a mélang mixer in about 240 g H 2 O at about 1300-1500 rpm.
Table 8.
The sample was extremely thick after mixing. The sample slowly separated with much of the solution occupied by Liquiment® 5581F. Small amounts of Liquiment® 5581F remained in the lower layer. This was not observed in any of the previous samples. It was very difficult to homogenize again the second layer of solution during stirring. Figure 9 illustrates a photo of the activation system after 3 days. Small amounts of Liquiment® 5581F were visible in the lower layer.
EXAMPLE 9 Sample activation system with AMPS / Acrylamide / N-vinylpyrrolidone / acrylic acid copolymer
[00134] The activation system was mixed in the order and concentrations given in Table 9. The activator was mixed in a mélang mixer in about 24Cg H2O at about 1300-1500 rpm.
[00135] Table 9
The sample remained homogeneous from the moment of stopping the mixture until at least 48 hours later. Figure 10 illustrates a photo of the activation system after 24 h.
Example 10. Sample J. Activation System with Polyvinyl Alcohol Polymer (Comparative).
[00137] The activation system was mixed in the order and concentrations given in Table 10. The activator was mixed in a ΓΑΡ1 mixer in about 240 g of H 2 O at about 1300-1500 rpm.
Table 10.
[00139] The sample separated immediately. The sample separated into 4 distinct layers after 24 h. Figure 11 illustrates a photo of the activation system after 24 hours.
Example 11. Sample K. Activation System with Acrylamide / Acrylic Acid Copolymer (Comparative).
The activation system was mixed according to the standard procedure, in the order and concentrations given in Table 11. The activator was mixed in an API blender with 200 g of water to account for 40 g of water present in the HZ-30 solution (the HZ-30 activity was 20%, thus 50 g of the HZ-30 solution is needed to place 10 g of the HZ-30 polymer in the activator). HZ-30 solution was added to the water before the start of mixing. The speed of the mixer was about 1300-1500 rpm.
[00141] Table 11
[00142] The sample separated immediately. The sample separated into 4 distinct layers after 24 h. Figure 12 illustrates a photo of the activation system after 24 h.
Example 12. Analysis of Examples 1 to 11.
Example A is a conventional system of sodium sulphate and sodium hexametaphosphate with the dispersant Liquiment® 5581F (BASF) with polycarboxylate ether. As can be seen in the image of FIG. 2, this system separates immediately into two distinct phases or layers and does not retain its homogeneity. In addition, it is difficult to homogenize by stirring after separation. In order to determine if the order of addition of ingredients influenced the homogeneity of the system, Examples G and H were prepared. Although Examples G and H were prepared by adding the ingredients in different sequences, the separation was still observed. The separation in Example H was slower, but still within 1 to 2 hours of preparation.
Example B has the same formula of sodium sulfate, sodium hexametaphosphate and Liquiment® 5581F as described for Example A, but contains 0.5% by weight of pumice (bwP). Halad®-344 (copolymer of AMPS and dimethyl acrylamide) added thereto. As shown in FIG. 3, the suspension thus obtained remained homogeneous without demonstrating phase separation for 7 days. Both Example A and Example B were prepared in the same way. The rheology measurements were performed on Examples A and B with a Brookfield LV series viscometer with a # 2 axis at 60 rpm. The average viscosity after several measurements for each was 114 cP for Example A and 399 cP for Example B. This result provoked reflection that an increase in viscosity, achieved by adding the copolymer, may be responsible for improving the suspension, homogeneity and overall stability of the activation system.
In order to study the influence of the viscosity on the stability of the activation system, Examples D, E and F were prepared. These examples were composed of SA-1015 ™ suspending agent and a viscosizer. If the stabilization effect resulted from an increase in the viscosity of the system that allowed greater uniformity and homogeneity, the addition of the suspension aid must also provide stabilization. It was found that regardless of (1) the concentration of the suspension aid or (2) the sequence of adding the suspension aid, separation could not be suppressed. The separation rate for each example ranged from days (3 days, D) to hours (within 24 hours, E) to minutes (immediate separation, F). None of the Examples D, E or F remained homogeneous with the addition of the aid to the suspension. Figures 5, 6 and 7 show images of separate activation systems for Examples D, E and F, respectively.
The interest of the study was then focused on the interaction of the activation system with the polymer fluid loss additive. Examples C, I, J and K were prepared and mixed in the same proportions as Example B. Example C contained FIalad®-413 (acrylonitrile, acrylamide, AMPS grafted onto lignite), Example I contained Halad®-200 (heteropolymer of AMPS, acrylamide, N-vinylpyrrolidone and acrylic acid), Example J contained LAP-1 (polyvinyl alcohol) and Example K contained HZ ™ -30 (polyacrylamide). Example C demonstrated signs of separation immediately after preparation, a small bottom layer becoming visible. After 3 days, the separation into two distinct layers was clearly visible. Example I behaves identically to Example B, remaining stable after preparation and for at least 2 days. Examples J and K separated immediately after preparation into two separate layers. Through these observations, it is obvious that the addition of Halad®-200, which, in comparison with other polymers tested in this series, is more like Halad®-344 in terms of chemical composition, stabilizes the system. activation to allow a long storage life.
[00147] Although not definitive so far, the experiments suggest that an acrylic copolymer with a charged functionality, when added to an activation system of sodium sulfate and sodium hexametaphosphate , creates the most stable combination. Halad®-413, which contains AMPS, separated the least in comparison to the other polymer additives tested; however, the lignite component may very well prevent the desired level of stability.
[00148] The addition of a copolymer additive such as Halad®-344 also gave the advantage of providing fluid loss control to the activated cement paste in the absence of the disadvantages of the waste additive. premix fluid with the dry cement mixture. The following data presented in Tables 12 and 13 allow comparison of the activation system of Example A with the more stable activation system of Example B.
[00149] Table 12. Example A vs. Example B.
[00150] Table 13. Examples A and B. 6D and 3D refer to rheometric decomposition values at 3 and 6 rpm, respectively. The "up" and "down" indications refer to the fact that the measurement was taken when the rpm was increasing ("up") or decreasing ("down"). The data presented in the table shows viscometer gradient readings of a Fann 35 viscometer with a Fann stress stress adapter and a No. 1 spring.
[00151] The data indicate that the activation system of the invention (Example B) gives equally good or better results in pumping time, fluid loss, and 24 h compressive force measurements in comparison to the classical activation system (Example A). Fann® stress stress adapter (FYSA) rheology measurements taken on activated cement pastes at temperatures of 80 ° F, 130 ° F and 180 ° F were comparable for Example A and B. the incorporation of a polymeric additive into the activation system provides desirable properties to the cement paste and the cured cement matrix, and does not affect the rheology of the activated paste either. This is in addition to the stabilizing advantage that the polymer provides and which allows for a longer storage life and improved handling. Data collection was performed according to 1ΆΡ1 10B-2 / ISO 10426-2 Recommended Practice for Testing Well Cements.
[00152] The terms and expressions that have been used are used as terms of description and not limitation, and there is no intention in the use of such terms and expressions to exclude a any equivalent of the illustrated and described features or parts thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the present invention. Thus, it should be understood that even though the present invention has not been specifically disclosed by specific embodiments and possible features, the modification and variation of the concepts disclosed herein may be sought by one skilled in the art, and such modifications and variations are considered to be within the scope of the embodiments of the present disclosure.
Additional embodiments.
The following exemplary embodiments are given, the numbering thereof should not be construed as an indication of significance levels: [00154] Embodiment 1 describes a method for treating an underground formation the method comprising: placing in the subterranean formation a liquid cement activating composition comprising water; an alkali sulfate salt; a polyphosphate salt; and a polymer stabilizer comprising a repeating group which is an ethylene substituted with a group selected from the group consisting of -C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted or unsubstituted it, -C (O) NR'2, wherein in each case R1 is independently selected from the group consisting of a (C1-C20) unsubstituted or substituted hydrocarbyl, -CN, and combinations thereof; wherein, in each case, the ethylene is independently also substituted or unsubstituted, and a repeating group which comprises an anionic group.
[00155] Embodiment 2 describes the method of Embodiment 1, wherein the method also comprises obtaining or using the composition, wherein the obtaining or use of the composition is further accomplished. above the surface.
Embodiment 3 describes the method of any one of Embodiments 1 to 2, wherein the method also comprises obtaining or using the composition, wherein obtaining or using of the composition is done in the underground formation.
Embodiment 4 describes the process of any one of Embodiments 1 to 3, further comprising mixing the cement activating composition with a cementitious composition.
[00158] Embodiment 5 describes the method of Embodiment 4, wherein the mixing of the cement activating composition and the cement composition is above the surface, wherein the placement of the Activating composition of the liquid cement in the subterranean formation comprises placing a mixture of the liquid cement activating composition and the cement composition in the subterranean formation.
[00159] Embodiment 6 describes the method of any of Embodiments 4 to 5, wherein the mixture of the cement activating composition and the cement composition is in the subterranean formation.
Embodiment 7 describes the method of any of embodiments 4 to 6, wherein about 0.001 wt% to about 99.999 wt% of the mixture of the cement activating composition and the Cement composition is the activating composition of cement.
Embodiment 8 describes the process of any one of embodiments 4 to 7, wherein about 10 wt.% To about 50 wt.% Of the mixture of the cement activator composition and the Cement composition is the activating composition of cement.
[00162] Embodiment 9 describes the method of any of embodiments 4 to 8, wherein the cement composition may contain Portland cement, pozzolan cement, gypsum cement, removed alumina content, dairy cement, silica cement, or a combination thereof.
Embodiment 10 describes the method of any of embodiments 4 to 9, wherein the cement composition comprises a pozzolan cement, wherein the activating composition is from about 60% to about 95%. % of the weight of pozzolan in the cement composition.
Embodiment 11 describes the method of any one of Embodiments 4 to 10, wherein the cement composition comprises a lime-pozzolan cement.
Embodiment 12 describes the method of any of embodiments 4 to 11, wherein the cement composition is a retarded cure cement composition.
Embodiment 13 describes the method of any of embodiments 4 to 12, further comprising curing the cement activating composition and the cement composition.
Embodiment 14 describes the process of any one of Embodiments 1 to 13 wherein the water is from about 30% by weight to about 95% by weight of the cement activating composition.
Embodiment 15 describes the process of any one of Embodiments 1 to 14, wherein the water is about 60% by weight to about 80% by weight of the cement activating composition.
Embodiment 16 describes the process of any one of Embodiments 1 to 15, wherein the alkali sulfate salt is from about 0.001 wt.% To about 40 wt.% Of the cement activating composition. .
Embodiment 17 describes the process of any one of Embodiments 1 to 16, wherein the alkali sulfate salt is from about 1% by weight to about 15% by weight of the activating composition of the present invention. cement.
Embodiment 18 describes the process of any one of Embodiments 1 to 17, wherein the alkali sulfate salt comprises potassium sulfate, calcium sulfate, lithium sulfate, sodium sulfate, and the like. sodium, or a combination thereof.
Embodiment 19 describes a method of any one of embodiments 1 to 18, wherein the alkali sulfate salt is sodium sulfate.
Embodiment 20 describes the process of any one of Embodiments 1 to 19, wherein the polyphosphate salt is from about 0.001% by weight to about 30% by weight of the cement activating composition. .
Embodiment 21 describes the process of any one of Embodiments 1 to 20, wherein the polyphosphate salt is from about 1% by weight to about 15% by weight of the cement activating composition. .
Embodiment 22 describes the process of any one of embodiments 1 to 21, wherein a polyphosphate salt comprises a polymeric metaphosphate salt, a phosphate salt, or a combination thereof.
Embodiment 23 describes the process of any one of Embodiments 1 to 22, wherein the polyphosphate salt comprises sodium hexametaphosphate, sodium trimetaphosphate, sodium tetrametaphosphate, pentametaphosphate, and the like. sodium, sodium heptametaphosphate, sodium octametaphosphate, and combinations thereof.
Embodiment 24 describes the process of any one of Embodiments 1 to 23, wherein the polyphosphate salt is hexametaphosphate.
Embodiment 25 describes the method of any one of embodiments 1 to 24, wherein the cement activating composition also comprises a dispersing agent.
Embodiment 26 describes the process of Embodiment 25, wherein the dispersing agent is from about 0.001 wt.% To about 40 wt.% Of the cement activating composition.
Embodiment 27 describes the method of any of embodiments 25 to 26, wherein the dispersing agent is from about 1% by weight to about 25% by weight of the activating composition of the present invention. cement.
Embodiment 28 describes the method of any of embodiments 25 to 27, wherein the dispersing agent comprises a superplasticizer dispersing agent, a sulfonated formaldehyde dispersing agent, an agent polycarboxyl ether dispersion, or a combination thereof.
Embodiment 29 describes the process of any of embodiments 25 to 28, wherein the dispersing agent is a polycarboxyl ether.
Embodiment 30 describes the process of any one of Embodiments 1 to 29, wherein the polymer stabilizer is from about 0.001 wt% to about 30 wt% of the cement activating composition. .
Embodiment 31 describes the method of any one of embodiments 1 to 30, wherein the polymer stabilizer is from about 0.1 wt.% To about 10 wt.% Of the activating composition. cement.
[00185] Embodiment 32 describes the process of any one of embodiments 1 to 31, wherein the repeating group which is a substituted ethylene is from about 0.001 mol% to about 99.999 mol% of the polymer stabilizer. .
Embodiment 33 describes the process of any one of embodiments 1 to 32, wherein the repeating group which is a substituted ethylene is from about 0.001 mol% to about 25 mol% of the polymer stabilizer. .
Embodiment 34 describes the method of any one of Embodiments 1 to 33, wherein the repeating group which is a substituted ethylene has the structure:
wherein R2, R3, and R4 are independently selected from the group consisting of -H, and non-substituted or unsubstituted (substituted) C10-dihydrocarbyl, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, - S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) ni-, and - (CH2-CH2-CH2-O) n- where n1 is about 1 to about 10,000. R5 is independently selected from the group consisting of -C (O) OH, a salt thereof, a (C 1 -C 20) hydrocarbyl ester substituted or unsubstituted thereof, -C (O) NR '2, in which each time R1 is independently selected from the group consisting of (C1-C20) hydrocarbyl substituted or unsubstituted, and -CN.
Embodiment 35 describes the method of embodiment 34 wherein R2, R3, and R4 are independently (C1-C20) unsubstituted hydrocarbyl.
Embodiment 36 describes the method of any of embodiments 34 to 35, wherein R2, R3, and R4 are independently (C1-C10) alkyl.
[00190] Embodiment 37 describes the method of any one of Embodiments 34-36, wherein R2, R3, and R4 are -H.
Embodiment 38 describes the method of any one of Embodiments 34 to 37, wherein R5 is -C (O) NR'2, wherein in each case R! is independently the (C1-C20) unsubstituted hydrocarbyl.
Embodiment 39 describes the method of any one of embodiments 34 to 38, wherein R 5 is -C (O) NR '2, wherein in each case R 1 is (C 1 -C 5) alkyl.
Embodiment 40 describes the method of any one of embodiments 34 to 39, wherein R 5 is -C 1 NR 4, wherein R 1 is methyl.
Embodiment 41 describes the method of any one of embodiments 34 to 40, wherein the repeating group which is a substituted ethylene has the structure:
Embodiment 42 describes the method of any one of embodiments 1 to 41, wherein the repeating group that comprises an ionic group represents about 0.001 mol% to about 99.999 mol% of the polymer stabilizer. .
Embodiment 43 describes the process of any one of Embodiments 1 to 42, wherein the repeating group which comprises an anionic group represents from about 25 mole% to about 99.999 mole% of the polymer stabilizer. .
Embodiment 44 describes the method of any one of Embodiments 1 to 43, wherein the anionic group in the repeating group that contains the anionic group is in the form of an acid or a salt of it.
Embodiment 45 describes the method of any one of Embodiments 1 to 44, wherein the repetitive group which comprises an anionic moiety has the structure:
wherein A is selected from the group consisting of -O- and -NR9-, R6, R7, R8, R9 are independently selected from the group consisting of -H, and (C1-C5o) substituted or unsubstituted hydrocarbyl, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n2-, and - (CH2-CH2-CH2- 0) n2-, where n2 is about 1 to about 10,000. L1 is selected from the group consisting of a bond and substituted or unsubstituted (C1-C50) hydrocarbylene interrupted by 0, 1, 2 or 3 independently selected groups in the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n3-, and - (CH2-CH2-CH2-O) n3-, where n3 is about 1 at about 10,000. AG is an anionic group.
Embodiment 46 describes the method of Embodiment 45, wherein A is -NR9-.
Embodiment 47 describes the method of Embodiment 46 wherein R9 is selected from the group consisting of -H and (C1-C10) alkyl.
Embodiment 48 describes the method of any one of Embodiments 46 to 47, wherein A is -NH-.
Embodiment 49 describes the method of any of embodiments 45 to 48, wherein R6, R7, R8 are independently selected from the group consisting of -H and (C] -C20 hydrocarbyl unsubstituted.
Embodiment 50 describes the method of any of embodiments 45 to 49, wherein R6, R7, R8 are independently selected from the group consisting of -H and (C1-C10) non-alkyl. substituted.
Embodiment 51 describes the method of any one of Embodiments 45 to 50, wherein R6, R7, R8 are -H.
Embodiment 52 describes the process of any one of embodiments 45 to 51, wherein L 1 is (C 1 -C 20) hydrocarbylene which is unsubstituted or substituted with a (C 1 -C 10) alkyl or otherwise unsubstituted.
Embodiment 53 describes the method of any of embodiments 45 to 52, wherein L1 is (C1-C20) alkylene which is unsubstituted or substituted with (C1-C5) alkyl or otherwise unsubstituted.
Embodiment 54 describes the method of any of embodiments 45 to 53, wherein L 1 is (C 1 -C 10) alkylene which is unsubstituted or substituted with methyl or otherwise unsubstituted.
Embodiment 55 describes the method of any one of embodiments 45 to 54, wherein L1 is 2-methyl substituted prop-1,2-ylene.
Embodiment 56 describes the method of any one of Embodiments 45 to 55, wherein L1 has the structure:
Embodiment 57 describes the method of any one of Embodiments 45 to 56, wherein the AG is -S (O) (O) -OH a salt thereof.
Embodiment 58 describes the method of any one of Embodiments 1 to 57, wherein the repetitive group which comprises an anionic moiety has the structure:
wherein the -S (O) (O) OH group is in the form of an acid or a salt thereof.
Embodiment 59 describes the method of any one of embodiments 1 to 58, wherein the polymer stabilizer comprises repeating groups having the structure: wherein
each time, the repeating units are independently found in the illustrated direction or in the opposite direction, the repeating units have a block or random copolymer arrangement, R2, R3, and R4 are independently selected from the group consisting of -H, and substituted or unsubstituted (C1-C5o) hydrocarbyl, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2- 0) ni-, and - (CH2-CH2-CH2-O) n-, where n1 is about 1 to about 10,000, R5 is independently selected from the group consisting of -C (O) OH, a salt thereof; ci, a (C1-C20) hydrocarbyl ester substituted or unsubstituted thereof, -C (O) NR'2, wherein in each case R1 is independently selected from the group consisting of a (C1-C20) hydrocarbyl substituted or unsubstituted, and -CN, A is selected from the group consisting of -O- and -NR9-, R6, R7, R8, R9 are independently selected from the group consisting of -H, and (C1 -C50) substituted hydrocarbyl or not, interrupted by 0, 1,2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or not, - (CH2-CH2-0) n2-, and - (CH2 -CH2-CH2-0) n2-, where n2 is from about 1 to about 10,000. L1 is selected from the group consisting of a bond and substituted or unsubstituted (C1-C5o) hydrocarbylene interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n3-, and - (CH2-CH2-CH2-0) n3-, where n 3 is about 1 to about 10,000, AG is the anionic group, repetitive group A is about 0.001 mol% to about 99.999 mol% of the polymer stabilizer, and repetitive group B is about 0.001 mol% to about 99.999 mol% of the polymer stabilizer.
Embodiment 60 describes the method of any one of Embodiments 1 to 59, wherein the polymer stabilizer comprises repeating groups having the structure: wherein
the group -S (O) (O) OH is in the form of an acid or a salt thereof, the repeating group A is about 0.001 mol% to about 99.999 mol% of the polymer stabilizer and the repeating group B is from about 0.001 mol% to about 99.999 mol% of the polymer stabilizer.
Embodiment 61 describes the method of any one of Embodiments 1 to 60, wherein the polymer stabilizer also comprises a repeating unit formed from a (C1-C20) heterocycle substituted by the vinyl and containing nitrogen.
Embodiment 62 describes the method of Embodiment 61, wherein the repeating unit formed from a vinyl-substituted (C1-C20) heterocycle containing nitrogen is about 0.001% by weight. mole at about 99.999 mol% of the polymer stabilizer.
Embodiment 63 describes the method of any of embodiments 61 to 62, wherein the repeating unit formed from a (C 1 -C 2) heterocycle substituted by vinyl and containing nitrogen represents about 5 mol% to about 50 mol% of the polymer stabilizer.
Embodiment 64 relates to the method of any one of embodiments 61 to 63, wherein the vinyl substituted (C 1 -C 20) heterocycle substituted by vinyl and containing nitrogen is substituted on a nitrogen atom of the (C1-C20) heterocycle containing nitrogen.
Embodiment 65 describes the method of any of embodiments 61 to 64, wherein the (C 1 -C 20) vinyl-substituted heterocycle containing nitrogen is N-vinylpyrrolidone.
Embodiment 66 describes the method of any one of Embodiments 1 to 65, wherein the polymer stabilizer also comprises a repeating unit of acrylic acid.
Embodiment 67 describes the method of Embodiment 66, wherein the repeating unit of acrylic acid is about 0.001 mol% to about 5 mol% of the polymer stabilizer.
Embodiment 68 describes the process of any one of Embodiments 1 to 67, wherein the repeating group which is a substituted ethylene is a repeating acrylamide imitate, wherein the repeating group which contains an anionic moiety is a repeating unit of 2-acrylamido-2-methylpropanesulphonic acid or a salt thereof, wherein the polymer stabilizer also comprises a repeating unit of acrylic acid and a repeating unit of N-vinylpyrrolidone.
Embodiment 69 describes the method of any one of embodiments 1 to 68, wherein the polymer stabilizer also comprises a repeating unit of acrylonitrile.
[00223] Embodiment 70 describes the method of Embodiment 69, wherein the repeating unit of acrylic acid is about 0.001 mol% to about 10 mol% of the polymer stabilizer.
Embodiment 71 describes the method of any one of embodiments 69 to 70, wherein the repeating group which is a substituted ethylene is a repeating unit acrylamide, wherein the repeating group which contains an anionic group is a repeating unit of 2-acryiamido-2-methylpropanesulphonic acid or a salt thereof.
Embodiment 72 describes the method of any one of Embodiments 1 to 71, wherein the cement activating composition also comprises calcium chloride, triethanolamine, sodium silicate, formate and the like. zinc, calcium acetate, sodium hydroxide, water, saline solution, an aqueous base, an oil, an organic solvent, an oily phase synthetic fluid, an aqueous solution, alcohol or polyol, cellulose, starch, an alkalinity control agent, an acidity controlling agent, a density control agent, a density modifier, an emulsifier, a dispersing agent, a polymeric stabilizer, polyacrylamide, polymer or combination of polymers, antioxidant, heat stabilizer, foam control agent, solvent, diluent, plasticizer, filler or inorganic particle, pigment, a dye, an agent precipitation, an oily wetting agent, a curing retardant additive, a surfactant, a corrosion inhibitor, a gas, a weight reducing additive, a heavy duty additive, a material of loss of circulation, an additive filtration control system, a salt, a fiber, a thixotropic additive, a mill, a crosslinking agent, a gas, a rheology modifier, a hardening accelerator, a hardening retarder, a looting modifier, an agent for chelation, pie inhibitor, enzyme, resin, water control material, polymer, oxidizer, marker, Portland cement, pozzolan cement, gypsum cement, content cement high in aluminum, a dairy cement, a silica cement, fly ash, metakaolin, shale, zeolite, a crystalline silica compound, amorphous silica, fibers, hydratable clay, microspheres, pozzolan lime , or a c combination of these.
Embodiment 73 describes the method of any one of Embodiments 1 to 72, wherein placing the cement activating composition in the subterranean formation comprises pumping the activating composition of the cement through a tube placed in a wellbore and in an underground formation.
Embodiment 74 describes a system for performing the method of any one of Embodiments 1 to 73, the system comprising: a tube placed in an underground formation; and a pump configured to pump the activation composition of the liquid cement into the subterranean formation through the tube.
Embodiment 75 discloses a method for treating a subterranean formation, the method comprising: placing in the subterranean formation a liquid cement activating composition comprising water which is about 30% by weight to about 95% by weight of the liquid cement activating composition; an alkali sulfate salt which is from about 0.001% by weight to about 40% by weight of the liquid cement activating composition; a polyphosphate salt which represents from about 0.001% by weight to about 30% by weight of the liquid cement activating composition; and a polymer stabilizer which represents about 0.001 wt.% to about 30 wt.% of the liquid cement activating composition, the polymer stabilizer comprising repeating groups having the structure:
wherein each time the repeating units are independently found in the illustrated direction or in the opposite direction, the repeating units have a block or random copolymer arrangement, R2, R3, and R4 are independently selected from the group consisting of - H, and (C 1 -C 5 O) hydrocarbyl substituted or unsubstituted, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or not, - (CH 2 -CH 2 -O) n-, and - (CH 2 -CH 2 -CH 2 -O) n-, where n is about 1 to about 10,000, R 5 is independently selected from the group consisting of -C (O) OH, a salt thereof, a substituted or unsubstituted (C1-C20) hydrocarbyl thereof, -C (O) NR1 2, wherein in each case R1 is independently selected from the group consisting of C2o) substituted or unsubstituted hydrocarbyl, and -CN, A is selected from the group consisting of -O- and -NR9-, R6, R7, R8, R9 are independently selected from the group consisting of -H, and C1- C5o) hydrocarby substituted or uninterrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n2-, and - ( CH2-CH2-CH2-0) n2-, where n2 is from about 1 to about 10,000. L1 is selected from the group consisting of a bond and substituted or unsubstituted (C1-C5o) hydrocarbylene interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of - O-, -S-, -ΝΗ- substituted or unsubstituted, - (CH2-CH2-O) n3-, and - (CH2-CH2-CH2-O) n3- where n3 is about 1 to about 10,000, AG is an anionic group, repeating group A is about 0.001 mole% to about 25 mole% polymer stabilizer, and repetitive group B is about 25 mole% to about 10 mole percent. about 99.999 mol% of the polymer stabilizer.
Embodiment 76 describes a method for treating a subterranean formation, the method comprising: placing in the subterranean formation a liquid cement activating composition comprising water which is about 30% by weight to about 95% by weight of the liquid cement activating composition; an alkali sulfate salt which is from about 0.001% by weight to about 40% by weight of the liquid cement activating composition; a polyphosphate salt which represents from about 0.001% by weight to about 30% by weight of the liquid cement activating composition; and a polymer stabilizer which represents about 0.001 wt.% to about 30 wt.% of the liquid cement activating composition, the polymer stabilizer comprising repeating groups having the structure:
wherein in each case the repeating units are independently found in the illustrated direction or in the opposite direction, the repeating units have a block or random copolymer arrangement, the group -S (O) (O) OH is under the In the form of an acid or a salt thereof, the repeating group A represents about 0.001 mol% to about 25 mol% of the polymer stabilizer, and the repeating group B is about 25 mol% to about 99.999 mol%. mol% of the polymer stabilizer.
Embodiment 77 describes a system comprising: a tube placed in an underground formation; and a pump configured to pump an activating composition of the liquid cement into the subterranean formation through the tube, wherein the cement activating composition comprises water; an alkali sulfate salt; a polyphosphate salt; and a polymer stabilizer comprising a repeating group which is an ethylene substituted with a group selected from the group consisting of -C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted or unsubstituted it, -C (O) NR'2, wherein in each case R1 is independently selected from the group consisting of a (C] -C20) substituted or unsubstituted hydrocarbyl, -CN, and combinations thereof wherein, in each case, the ethylene is independently also substituted or unsubstituted, and a repeating group which comprises an anionic group.
Embodiment 78 describes a liquid cement activation composition for the treatment of an underground formation, the cement activating composition comprising: water; an alkali sulfate salt; a polyphosphate salt; and a polymer stabilizer comprising a repeating group which is an ethylene substituted with a group selected from the group consisting of -C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted or unsubstituted it, -C (O) NR12, wherein in each case R1 is independently selected from the group consisting of (C1-C20) unsubstituted or substituted hydrocarbyl, -CN, and combinations thereof, wherein in each case, the ethylene is independently also substituted or unsubstituted, and a repeating group which comprises an anionic group.
Embodiment 79 describes a liquid cement activating composition for the treatment of an underground formation, the cement activating composition comprising: water which is about 30% by weight to about 95% by weight weight of the activating liquid cement composition; an alkali sulfate salt which is from about 0.001% by weight to about 40% by weight of the liquid cement activating composition; a polyphosphate salt which represents from about 0.001% by weight to about 30% by weight of the liquid cement activating composition; and a polymer stabilizer which represents about 0.001 wt.% to about 30 wt.% of the liquid cement activating composition, the polymer stabilizer comprising repeating groups having the structure:
wherein each time the repeating units are independently found in the illustrated direction or in the opposite direction, the repeating units have a block or random copolymer arrangement, R2, R3, and R4 are independently selected from the group consisting of - H, and (C1-C5o) substituted or unsubstituted hydrocarbyl, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or not, - (CH2- CH2-0) ni-, and - (CH2-CH2-CH2-O) n-, where n1 is about 1 to about 10,000, R5 is independently selected from the group consisting of -C (O) OH, a salt of the latter, a (C 1 -C 20) hydrocarbyl ester substituted or unsubstituted thereof, -C (O) NR '2, wherein in each case R 1 is independently selected from the group consisting of a (C 1 -C 20) ) substituted or unsubstituted hydrocarbyl, and -CN, A is selected from the group consisting of -O- and -NR9-, R6, R7, R8, R9 are independently selected from the group consisting of -H, and (Cf-C5o) ) hydrocarby substituted or unsubstituted, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or not, - (CH2-CH2-0) n2-, and - (CH 2 -CH 2 -CH 2 -O) n 2 - where n 2 is from about 1 to about 10,000. L 1 is selected from the group consisting of a bond and substituted or unsubstituted (C 1 -C 6) hydrocarbyl interrupted by 0, 1 , 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n3-, and - (CH2-CH2-CH2-0) n3 where n3 is about 1 to about 10,000, AG is an anionic group, repeating group A is about 0.001 mole% to about 25 mole% polymer stabilizer, and repeating group B is about 25 mole% about 99.999 mol% of the polymer stabilizer.
Embodiment 80 describes a process for the preparation of a composition for the treatment of an underground formation, the process comprising: preparing a liquid cement activating composition for treating a formation underground, the cement activation composition comprising: water; an alkali sulfate salt; a polyphosphate salt; and a polymer stabilizer comprising a repeating group which is an ethylene substituted with a group selected from the group consisting of -C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted thereof. ci, -C (O) NR'2, wherein in each case R1 is independently selected from the group consisting of a (C1-C20) unsubstituted or substituted hydrocarbyl, -CN, and combinations thereof, wherein in each case, the ethylene is independently also substituted or unsubstituted, and a repeating group which comprises an anionic group.
Embodiment 81 describes the method, system or composition of any or any combination of Embodiments 1 to 80 optionally configured so that all of the elements or options described are available for use or for selection.

权利要求:
Claims (80)
[1" id="c-fr-0001]
CLAIMS What is claimed:
A method for treating a subterranean formation, the method comprising: placing in the subterranean formation a liquid cement activating composition comprising water; an alkali sulfate salt; a polyphosphate salt; and a polymer stabilizer comprising a repeating group which is an ethylene substituted with a group selected from the group consisting of -C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted therewith ci, -C (O) NR12, wherein in each case R1 is independently selected from the group consisting of a (C1-C20) unsubstituted or substituted hydrocarbyl, -CN, and combinations thereof; wherein, in each case, the ethylene is independently also substituted or unsubstituted, and a repeating group which comprises an anionic group.
[2" id="c-fr-0002]
The method of claim 1, wherein the method further comprises obtaining or using the composition, wherein obtaining or using the composition is above the surface.
[3" id="c-fr-0003]
The method of claim 1, wherein the method also comprises obtaining or using the composition, wherein obtaining or using the composition is in the subterranean formation.
[4" id="c-fr-0004]
The method of claim 1, further comprising mixing the cement activating composition with a cementitious composition.
[5" id="c-fr-0005]
The method of claim 4, wherein the mixing of the cement activating composition and the cement composition is above the surface, wherein placing the liquid cement activating composition in the Underground formation includes placing a mixture of the liquid cement activating composition and the cement composition into the subterranean formation.
[6" id="c-fr-0006]
The method of claim 4, wherein the mixture of the cement activating composition and the cement composition is in the subterranean formation.
[7" id="c-fr-0007]
The process of claim 4, wherein about 0.001 wt.% To about 99.999 wt.% Of the mixture of the cement activating composition and the cement composition is the cement activating composition.
[8" id="c-fr-0008]
The process of claim 4, wherein about 10 wt.% To about 50 wt.% Of the mixture of the cement activating composition and the cement composition is the cement activating composition.
[9" id="c-fr-0009]
The method of claim 4, wherein the cement composition may contain Portland cement, pozzolan cement, gypsum cement, alumina-removed cement, dairy cement, silica cement, or combination of these.
[10" id="c-fr-0010]
The method of claim 4, wherein the cement composition comprises a pozzolan cement, wherein the activating composition comprises from about 60% to about 95% of the weight of the pozzolan in the cement composition.
[11" id="c-fr-0011]
The method of claim 4, wherein the cement composition comprises a lime-pozzolan cement.
[12" id="c-fr-0012]
The method of claim 4, wherein the cement composition is a retarded cure cement composition.
[13" id="c-fr-0013]
The method of claim 4, further comprising curing the cement activating composition and the cement composition.
[14" id="c-fr-0014]
The process of Claim 1 wherein the water is from about 30% by weight to about 95% by weight of the cement activating composition.
[15" id="c-fr-0015]
The process of claim 1 wherein the water is from about 60 wt% to about 80 wt% of the cement activating composition.
[16" id="c-fr-0016]
The process of Claim 1 wherein the alkali sulfate salt is from about 0.001 wt.% To about 40 wt.% Of the cement activating composition.
[17" id="c-fr-0017]
17. The process of claim 1 wherein the alkali sulfate salt is from about 1% by weight to about 15% by weight of the cement activating composition.
[18" id="c-fr-0018]
The method of claim 1, wherein the alkali sulfate salt comprises potassium sulfate, calcium sulfate, lithium sulfate, sodium sulfate, or a combination thereof.
[19" id="c-fr-0019]
19. The process of Claim 1 wherein the alkali sulfate salt is sodium sulfate.
[20" id="c-fr-0020]
The process of Claim 1 wherein the polyphosphate salt is from about 0.001 wt.% To about 30 wt.% Of the cement activating composition.
[21" id="c-fr-0021]
21. The process of Claim 1 wherein the polyphosphate salt is from about 1% by weight to about 15% by weight of the cement activating composition.
[22" id="c-fr-0022]
The process of claim 1, wherein a polyphosphate salt comprises a polymeric metaphosphate salt, a phosphate salt, or a combination thereof.
[23" id="c-fr-0023]
The method of claim 1, wherein the polyphosphate salt comprises sodium hexametaphosphate, sodium trimetaphosphate, sodium tetrametaphosphate, sodium pentametaphosphate, sodium heptametaphosphate, sodium octametaphosphate, and combinations thereof. of these.
[24" id="c-fr-0024]
24. The process of claim 1 wherein the polyphosphate salt is sodium hexametaphosphate.
[25" id="c-fr-0025]
25. The process of claim 1, wherein the cement activating composition also comprises a dispersing agent.
[26" id="c-fr-0026]
The method of claim 25, wherein the dispersing agent is from about 0.001 wt.% To about 40 wt.% Of the cement activating composition.
[27" id="c-fr-0027]
The method of claim 25, wherein the dispersing agent is from about 1% by weight to about 25% by weight of the cement activating composition.
[28" id="c-fr-0028]
28. The method of claim 25, wherein the dispersing agent comprises a superplasticizer dispersing agent, a sulfonated formaldehyde dispersing agent, a polycarboxyl ether dispersing agent, or a combination thereof.
[29" id="c-fr-0029]
The method of claim 25, wherein the dispersing agent is a polycarboxyl ether.
[30" id="c-fr-0030]
The method of claim 1, wherein the polymer stabilizer is from about 0.001 wt.% To about 30 wt.% Of the cement activating composition.
[31" id="c-fr-0031]
31. The process of claim 1 wherein the polymer stabilizer is from about 0.1 wt.% To about 10 wt.% Of the cement activating composition.
[32" id="c-fr-0032]
32. The process of claim 1, wherein the repeating group which is a substituted ethylene is from about 0.001 mol% to about 99.999 mol% of the polymer stabilizer.
[33" id="c-fr-0033]
33. The process of claim 1, wherein the repeating group which is a substituted ethylene is from about 0.001 mol% to about 25 mol% of the polymer stabilizer.
[34" id="c-fr-0034]
The process of claim 1, wherein the repeating group which is a substituted ethylene has the structure:

wherein R2, R3, and R4 are independently selected from the group consisting of -H, and (C1-C5o) hydrocarbyl substituted or unsubstituted, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O -, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-O) n-, and - (CH2-CH2-CH2-O) n-, where n1 is about 1 to about 10 000. R5 is independently selected from the group consisting of -C (O) OH, a salt thereof, a substituted or unsubstituted (C1-C20) hydrocarbyl ester thereof, -C (O) NR12, wherein in each case R1 is independently selected from the group consisting of (C1-C20) hydrocarbyl substituted or unsubstituted, and -CN.
[35" id="c-fr-0035]
35. The process of claim 34 wherein R2, R3, and R4 are independently unsubstituted (C1-C20) hydrocarbyl.
[36" id="c-fr-0036]
36. The process of claim 34, wherein R2, R3, and R4 are independently (C1-C10) alkyl.
[37" id="c-fr-0037]
37. The method of claim 34, wherein R2, R3, and R4 are -H.
[38" id="c-fr-0038]
38. The process of claim 34, wherein R5 is -C (O) NR12, wherein in each case R1 is independently (C1-C20) unsubstituted hydrocarbyl.
[39" id="c-fr-0039]
39. The process of claim 34, wherein R5 is -C (O) NRI2, wherein in each case R1 is (C1-C8) alkyl.
[40" id="c-fr-0040]
40. The process of claim 34, wherein R5 is -C101NR1, wherein R1 is methyl.
[41" id="c-fr-0041]
41. The process of claim 34, wherein the repeating group which is a substituted ethylene has the structure:


[42" id="c-fr-0042]
42. The process of claim 1, wherein the repeating group which comprises an anionic group represents about 0.001 mol% to about 99.999 mol% of the polymer stabilizer.
[43" id="c-fr-0043]
The process of claim 1, wherein the repeating group which comprises an anionic group is from about 25 mole% to about 99.999 mole percent of the polymer stabilizer.
[44" id="c-fr-0044]
44. The process of claim 1, wherein the anionic group in the repeating group that contains the anionic group is in the form of an acid or a salt thereof.
[45" id="c-fr-0045]
The method of claim 1, wherein the repeating group which comprises an anionic group has the structure:

wherein A is selected from the group consisting of -O- and -NR9-, R6, R7, R8, R9 are independently selected from the group consisting of -H, and (C1-C50) substituted or unsubstituted hydrocarbyl, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n2-, and - (CH2-CH2-CH2- 0) n2-, where n2 is from about 1 to about 10,000. L1 is selected from the group consisting of a bond and substituted or unsubstituted (C1-C5o) hydrocarbylene interrupted by 0, 1, 2 or 3 independently selected groups in the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) "3-, and - (CH2-CH2-CH2-O) n3-, where n3 is about 1 to about 10,000. AG is an anionic group.
[46" id="c-fr-0046]
46. The process of claim 45, wherein A is -NR9-.
[47" id="c-fr-0047]
47. The process of claim 46 wherein R9 is selected from the group consisting of -H and (C1-C10) alkyl.
[48" id="c-fr-0048]
48. The method of claim 46, wherein A is -NH-.
[49" id="c-fr-0049]
49. The process of claim 45, wherein R6, R7, R8 are independently selected from the group consisting of -H and unsubstituted (C1-C20) hydrocarbyl.
[50" id="c-fr-0050]
The method of claim 45, wherein R6, R7, R8 are independently selected from the group consisting of -H and unsubstituted (C1-C10) alkyl.
[51" id="c-fr-0051]
The method of claim 45, wherein R6, R7, R8 are -H.
[52" id="c-fr-0052]
52. The process of claim 45, wherein L1 is (C1-C20) hydrocarbylene which is unsubstituted or substituted with (C1-C10) alkyl and otherwise unsubstituted.
[53" id="c-fr-0053]
53. The process of claim 45, wherein L1 is (C1-C20) alkylene which is unsubstituted or substituted with (C1-C5) alkyl and otherwise unsubstituted.
[54" id="c-fr-0054]
54. The process of claim 45, wherein L1 is (C1-C10) alkylene which is unsubstituted or substituted with methyl and otherwise unsubstituted.
[55" id="c-fr-0055]
55. The process of claim 45, wherein L1 is prop-l, 2-ylene substituted with 2-methyl.
[56" id="c-fr-0056]
The method of claim 45, wherein L1 has the structure:


[57" id="c-fr-0057]
57. The process of claim 45, wherein AG is -S (O) (O) -OH or a salt thereof.
[58" id="c-fr-0058]
The method of claim 1, wherein the repeating group which comprises an anionic group has the structure:

wherein the -S (O) (O) OH group is in the form of an acid or a salt thereof.
[59" id="c-fr-0059]
The method of claim 1, wherein the polymer stabilizer comprises repeating groups having the structure:

wherein each time the repeating units are independently found in the illustrated direction or in the opposite direction, the repeating units have a block or random copolymer arrangement, R2, R3, and R4 are independently selected from the group consisting of - H, and (C1-C5o) substituted or unsubstituted hydrocarbyl, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or not, - (CH2- CH2-0) ni-, and - (CH2-CH2-CH2-O) n-, where n1 is about 1 to about 10,000, R5 is independently selected from the group consisting of -C (O) OH, a salt of thereof, a substituted or unsubstituted (C1-C20) hydrocarbyl thereof, -C (O) NR12, wherein in each case R1 is independently selected from the group consisting of a (C1-C20) hydrocarbyl substituted or unsubstituted, and -CN, A is selected from the group consisting of -O- and -NR9-, R6, R7, R8, R9 are independently selected from the group consisting of -H, and C1-Csoihydrocarby Substituted or unsubstituted, interrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or not, - (CH2-CH2-0) n2-, and - (CH2-CH2-CH2-Q) n2-, where n2 is about 1 to about 10,000. L1 is selected from the group consisting of a bond and substituted or unsubstituted (C1-C5o) hydrocarbylene interrupted by 0, 1 , 2 or 3 groups independently selected from the group consisting of - O-, -S-, -ΝΗ- substituted or unsubstituted, - (CH2-CH2-O) n3-, and - (CH2-CH2-CH2-O) n3 where n3 is about 1 to about 10,000, AG is an anionic group, repeating group A is about 0.001 mol% to about 99.999 mol% of the polymer stabilizer, and repetitive group B is about 0.001% male. about 99.999 mol% of the polymer stabilizer.
[60" id="c-fr-0060]
The method of claim 1, wherein the polymer stabilizer comprises repeating groups having the structure:

wherein the -S (O) (O) OH group is in the form of an acid or a salt thereof, the repeating group A represents about 0.001 mol% to about 99.999 mol% of the stabilizer for polymer, and repetitive group B is about 0.001 mol% to about 99.999 mol% of the polymer stabilizer.
[61" id="c-fr-0061]
The method of claim 1, wherein the polymer stabilizer also comprises a repeating unit formed from a vinyl-substituted (C1-C20) heterocycle containing nitrogen.
[62" id="c-fr-0062]
The process of claim 61, wherein the repeating unit formed from a nitrogen-substituted (C1-C20) heterocycle containing vinyl represents from about 0.001 mol% to about 99.999 mol% of the stabilizer. for polymer.
[63" id="c-fr-0063]
The process of claim 61, wherein the repeating unit formed from a nitrogen-substituted (C1-C20) heterocycle containing vinyl represents from about 5 mole% to about 50 mole% of the stabilizer. for polymer.
[64" id="c-fr-0064]
The method of claim 61, wherein the vinyl-substituted (C 1 -C 20) vinyl-substituted heterocycle vinyl moiety is substituted on a nitrogen atom of the (C 1 -C 2) nitrogen-containing heterocycle. .
[65" id="c-fr-0065]
65. The process of claim 61, wherein the vinyl-substituted (C1-C20) heterocycle containing nitrogen is N-vinylpyrrolidone.
[66" id="c-fr-0066]
The method of claim 1, wherein the polymer stabilizer also comprises a repeating unit of acrylic acid.
[67" id="c-fr-0067]
The process of claim 66, wherein the repeating unit of acrylic acid is from about 0.001 mol% to about 5 mol% of the polymer stabilizer.
[68" id="c-fr-0068]
The process of claim 1, wherein the repeating group which is a substituted ethylene is a repeating unit acrylamide, wherein the repeating group which contains an anionic group is a repeating unit of 2-acrylamido-2-methylpropane sulfonic acid or a salt thereof, wherein the stabilizing polymer also comprises a repeating unit of acrylic acid and a repeating unit of N-vinylpyrrolidone.
[69" id="c-fr-0069]
The method of claim 1, wherein the polymer stabilizer also comprises a repeating unit of acrylonitrile.
[70" id="c-fr-0070]
The process of claim 69, wherein the acrylonitrile repeating unit is from about 0.001 mol% to about 10 mol% of the polymer stabilizer.
[71" id="c-fr-0071]
The method of claim 69, wherein the repeating group which is a substituted ethylene is a repeating unit of acrylamide, wherein the repeating group which comprises an anionic group is the repeating group of 2-acrylamido-2-methylpropane acid. sulfonic acid or a salt thereof.
[72" id="c-fr-0072]
72. The process of claim 1, wherein the cement activating composition also comprises calcium chloride, triethanolamine, sodium silicate, zinc formate, calcium acetate, sodium hydroxide, sodium hydroxide and the like. water, a saline solution, an aqueous base, an oil, an organic solvent, a synthetic fluid in the oily phase, an aqueous solution, the alcohol or the polyol, the cellulose, the starch, a control agent of the alkalinity, an acid control agent, a density control agent, a density modifier, an emulsifier, a dispersing agent, a polymer stabilizer, a polyacrylamide, a polymer or a combination of polymers, a antioxidant, heat stabilizer, foam control agent, solvent, diluent, plasticizer, filler or inorganic particle, pigment, dye, precipitating agent, oily wetting agent, a delay additive of d urea, a surfactant, a corrosion inhibitor, a gas, a weight reducing additive, a heavy duty additive, a material of loss of circulation, a filtration control additive, a salt, a fiber, a thixotropic additive, a grinder, a crosslinking agent, a gas, a rheology modifier, a hardening accelerator, a hardening retarder, a pH modifier, a chelating agent, a pie inhibitor, an enzyme, a resin , a water control material, a polymer, an oxidant, a marker, a Portland cement, a pozzolan cement, a gypsum cement, a high aluminum content cement, a dairy cement, a silica cement , fly ash, metakaolin, shale, zeolite, a crystalline silica compound, amorphous silica, fibers, hydratable clay, microspheres, pozzolan lime, or a combination thereof
[73" id="c-fr-0073]
The method of claim 1, wherein placing the cement activating composition in the subterranean formation comprises pumping the cement activating composition through a tube in a wellbore and an underground formation. .
[74" id="c-fr-0074]
74. A system for performing the method of claim 1, the system comprising: a tube placed in a subterranean formation; and a pump configured to pump the activation composition of the liquid cement into the subterranean formation through the tube.
[75" id="c-fr-0075]
A method of treating a subterranean formation, the method comprising: placing in the subterranean formation a liquid cement activating composition comprising water which is about 30% by weight to about 95% by weight of the composition activation of the liquid cement; an alkali sulfate salt which is from about 0.001% by weight to about 40% by weight of the liquid cement activating composition; a polyphosphate salt which represents from about 0.001% by weight to about 30% by weight of the liquid cement activating composition; and a polymer stabilizer which represents about 0.001 wt.% to about 30 wt.% of the liquid cement activating composition, the polymer stabilizer comprising repeating groups having the structure:

wherein each time the repeating units are independently found in the illustrated direction or in the opposite direction, the repeating units have a block or random copolymer arrangement, R2, R3, and R4 are independently selected from the group consisting of - H, and (C1-C5o) substituted or unsubstituted hydrocarbyl, interrupted by 0, 1,2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or not, - (CH2- CH2-0) ni-, and - (CH2-CH2-CH2-O) n-, where n1 is about 1 to about 10,000, R5 is independently selected from the group consisting of -C (O) OH, a salt of the latter, a (C 1 -C 20) hydrocarbyl ester substituted or unsubstituted thereof, -CXOJNR 4, wherein in each case R 1 is independently selected from the group consisting of a (C 1 -C 20) hydrocarbyl substituted or unsubstituted and -CN, A is selected from the group consisting of -O- and -NR9-, R6, R7, R8, R9 are independently selected from the group consisting of -H, and (Cj-C5o) hydrocarbyl substituted or unsubstituted, interrupted by 0,1,2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n2-, and - ( CH2-CH2-CH2-0) n2-, where n2 is from about 1 to about 10,000. L1 is selected from the group consisting of a linkage and (C1-C5o) hydrocarbylene substituted or uninterrupted by 0, 1, 2 or 3 groups independently selected from the group consisting of - O-, -S-, -ΝΗ- substituted or unsubstituted, - (CH2-CH2-O) "3-, and - (CH2-CH2-CH2-O) n3- where n3 is about 1 to about 10,000, AG is an anionic group, repeating group A is about 0.001 mole% to about 25 mole% polymer stabilizer, and repetitive group B is about 25 mole% to about 10 mole percent. about 99.999 mol% of the polymer stabilizer.
[76" id="c-fr-0076]
A process for treating a subterranean formation, the process comprising: placing in the subterranean formation a liquid cement activating composition comprising water which is about 30% by weight to about 95% by weight of the composition activation of the liquid cement; an alkali sulfate salt which is from about 0.001% by weight to about 40% by weight of the liquid cement activating composition; a polyphosphate salt which represents from about 0.001% by weight to about 30% by weight of the liquid cement activating composition; and a polymer stabilizer which is from about 0.001 wt% to about 30 wt% of the liquid cement activating composition, the polymer stabilizer comprising repeating groups having the structure: wherein

each time, the repeating units are independently found in the illustrated direction or in the opposite direction, the repeating units have a block or random copolymer arrangement, the group -S (O) (O) 0H is in the form of an acid or a salt thereof, the repeating group A is about 0.001 mol% to about 25 mol% of the polymer stabilizer, and the repeating group B is about 25 mol% to about 99.999 mol%. mole of the stabilizer for polymer.
[77" id="c-fr-0077]
77. System comprising: a tube placed in an underground formation; and a pump configured to pump an activating composition of the liquid cement into the subterranean formation through the tube, wherein the cement activating composition comprises water; an alkali sulfate salt; a polyphosphate salt; and a polymer stabilizer comprising a repeating group which is an ethylene substituted with a group selected from the group consisting of -C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted or unsubstituted it, -C (O) NR * 2, wherein in each case R1 is independently selected from the group consisting of a (C1-C20) unsubstituted or substituted hydrocarbyl, -CN, and combinations thereof, wherein, in each case, the ethylene is independently also substituted or unsubstituted, and a repeating group which comprises an anionic group.
[78" id="c-fr-0078]
78. Activating liquid cement composition for treating a subterranean formation, the cement activating composition comprising: water; an alkali sulfate salt; a polyphosphate salt; and a polymer stabilizer comprising a repeating group which is an ethylene substituted with a group selected from the group consisting of -C (O) OH, a salt thereof, a (C1-C20) hydrocarbyl ester substituted or unsubstituted it, -C (O) NR12, wherein in each case R1 is independently selected from the group consisting of (C1-C20) unsubstituted or substituted hydrocarbyl, -CN, and combinations thereof, wherein in each case, the ethylene is independently also substituted or unsubstituted, and a repeating group which comprises an anionic group.
[79" id="c-fr-0079]
79. Activating liquid cement composition for the treatment of a subterranean formation, the cement activating composition comprising: water which is from about 30% by weight to about 95% by weight of the dii activation composition liquid cement; An alkali sulfate salt which comprises from about 0.001% by weight to about 40% by weight of the liquid cement activating composition; a polyphosphate salt which represents from about 0.001% by weight to about 30% by weight of the liquid cement activating composition; and a polymer stabilizer which represents about 0.001 wt.% to about 30 wt.% of the liquid cement activating composition, the polymer stabilizer comprising repeating groups having the structure:

wherein each time the repeating units are independently found in the illustrated direction or in the opposite direction, the repeating units have a block or random copolymer arrangement, R2, R3, and R4 are independently selected from the group consisting of - H, and (C1-C5o) substituted or unsubstituted hydrocarbyl, interrupted by 0,1,2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or not, - (CH2- CH2-0) ni-, and - (CH2-CH2-CH2-O) n-, where n1 is about 1 to about 10,000, R5 is independently selected from the group consisting of -C (O) OH, a salt of this, a substituted or unsubstituted (C1-C20) hydrocarbyl thereof, -C (O) NR * 2, wherein in each case R1 is independently selected from the group consisting of a (C1-C20) ) substituted or unsubstituted hydrocarbyl, and -CN, A is selected from the group consisting of -O- and -NR9-, R6, R7, R8, R9 are independently selected from the group consisting of -H, and (C1-C5o) ) hydrocarbyl substituted or unsubstituted, interrupted by 0, 1,2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or not, - (CH2-CH2-0) n2-, and - ( CH2-CH2-CH2-0) n2-, where n2 is from about 1 to about 10,000. L1 is selected from the group consisting of a bond and substituted or unsubstituted (C1-C50) hydrocarbyl interrupted by 0. 1 , 2 or 3 groups independently selected from the group consisting of -O-, -S-, -NH- substituted or unsubstituted, - (CH2-CH2-0) n3-, and - (CH2-CH2-CH2-0) n3 where n3 is about 1 to about 10,000, AG is an anionic group, repeating group A is about 0.001 mole% to about 25 mole% polymer stabilizer, and repeating group B is about 25 mole% about 99.999 mol% of the polymer stabilizer.
[80" id="c-fr-0080]
80. Process for the preparation of a composition for the treatment of a subterranean formation, the process comprising: preparing a liquid cement activating composition for the treatment of a subterranean formation, the activating composition of the cement comprising: water; an alkali sulfate salt; a polyphosphate salt; and a polymer stabilizer comprising a repeating group which is an ethylene substituted with a group selected from the group consisting of -C (Q) OH, a salt thereof, a (C 1 -C 20) hydrocarbyl ester substituted or unsubstituted thereof, -C (O) NR'2, wherein in each case R1 is independently selected from the group consisting of a (C1-C20) unsubstituted or substituted hydrocarbyl, -CN, and combinations thereof wherein, in each case, the ethylene is independently also substituted or unsubstituted, and a repeating group which comprises an anionic group.

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同族专利:

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公开号 | 公开日

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US20210139763A1|2021-05-13|

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NO20180114A1|2018-01-25|

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WO2017034547A1|2017-03-02|

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US20180230357A1|2018-08-16|

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US10927288B2|2021-02-23|

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GB2557053A8|2018-06-27|

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GB2557053A|2018-06-13|

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AU2015406713B2|2020-09-10|

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法律状态:
2017-07-26| PLFP| Fee payment|Year of fee payment: 2 |

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2018-07-18| PLFP| Fee payment|Year of fee payment: 3 |

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2018-08-31| PLSC| Publication of the preliminary search report|Effective date: 20180831 |

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2020-04-10| ST| Notification of lapse|Effective date: 20200306 |

优先权:

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申请号 | 申请日 | 专利标题

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PCT/US2015/046702|WO2017034547A1|2015-08-25|2015-08-25|Cement activator composition for treatment of subterranean formations|

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