Patent Grant
12077504
This disclosure relates to the analysis of petroleum reservoirs using tracers, and methods of making tracers.
A petroleum reservoir is an underground pool of hydrocarbon compounds contained in porous or fractured rock formations. The petroleum in the reservoir is accessed through one or more borings in the earth that penetrate the material above the reservoir and enable transport of the petroleum to the surface. Water flooding is used, for example, to increase the pressure within the reservoir, thereby increasing oil production rates; and to displace hydrocarbons with the reservoir. Water is ideal for flooding reservoirs due to its ready availability and immiscibility with hydrocarbons. Determining the presence of fluid flow paths between oil wells, and the flow capacity between them, allows for a more detailed description of reservoir heterogeneity and facilitates water flood rate management.
Cross-well tracers, also referred to as inter-well tracers, can be used to obtain information about reservoir fluid flow patterns by injecting the tracer at an injection location, and subsequently retrieving and analyzing a quantity of the injected tracer at a producing location downstream from the injection location. The ease-of-use and overall utility of a cross-well tracer depends on a number of attributes, including (1) lesser retention in rock and earth that the tracer is exposed to when traversing a fluid flow path in a reservoir, (2) thermal stability and inertness to the various compounds and materials the tracer encounters in the reservoir, (3) minimal purification, workup, and derivatization after extraction from the reservoir, (4) detectability at lesser concentrations after extraction from the reservoir, (5) a measurable and sensitive response independent of minor variations in the structure of the tracer, and (6) detectability of the response over competing measurement signals attributable to natural constituents in fluid extracted from a reservoir, such as polyaromatic hydrocarbons and salts (that is, background noise).
This disclosure features complexing agents for use as cross-well tracers. The complexing agents exhibit weak retention in rock, are thermally and chemically stable, and are typically used without purification after extraction. Instead of undergoing chemical derivatization after extraction, the complexing agents can conveniently be exposed to compositions including one or more lanthanide ions to form complexes.
The complexes formed, when exposed to excitation light, emit a fluorescence signal that is temporally delayed relative to fluorescence signals from other components of the extracted reservoir fluid. As a result, time-gated detection methods can be used to eliminate the fluorescence signals from the other components, allowing essentially background-free measurement of the complexes. Detection of tracer concentrations of parts-per-quadrillion (ppq) or even less, on a mass/mass (m/m) basis, can be achieved. For example, tracer concentrations of 100 ppq m/m or less (such as 50 ppq m/m or less, 25 ppq m/m or less, 20 ppq m/m or less, 15 ppq m/m or less, 10 ppq m/m, 5 ppq m/m, 2 ppq m/m, 1 ppq m/m) can be achieved. Within extracted fluid, tracer concentrations of 10 picomolar (pM) or less (such as 1 pM or less, 500 femtomolar (fM) or less, 200 fM or less, 100 fM or less, 50 fM or less, 25 fM or less, 15 fM or less, 10 fM or less, 5 fM or less, 1 fM or less, 500 attomolar (aM) or less, 200 aM or less, 100 aM or less, 50 aM or less) can be quantitatively detected.
Complexing agents can also be derivatized to generate libraries of structurally unique identifiers which can be independently injected at multiple injection locations and extracted at a producing location, thus allowing the evaluation and comparison of fluid flow paths that span from each of the injection location to the producing location. Thus, the disclosed complexing agents can be used to reduce the time and costs associated with mapping the connectivity and heterogeneity of petroleum reservoirs and the management of water flooding-based petroleum extraction.
In a first aspect, this disclosure features methods for analyzing a fluid extracted from a reservoir. The methods can include the steps of introducing a first composition that includes a first complexing agent into a reservoir at a first location, extracting a fluid from the reservoir at a second location different from the first location, where the extracted fluid includes a concentration of the first complexing agent, combining the fluid with a second composition that includes a concentration of a lanthanide ion to form a third composition having a concentration of a complex formed by the first complexing agent and the lanthanide ion, exposing a quantity of the complex to electromagnetic radiation for a first time period ending at a time to, detecting fluorescence emission from the quantity of the complex for a second time period starting at a time t1>t0, where t1-t0 is greater than 2 microseconds, and determining information about a fluid flow path between the first location and the second location within the reservoir based on the detected fluorescence emission.
Examples of the methods can include any one or more of the following features.
The complex can include water. The complex can have a 1:1:2 molar ratio of lanthanide ion to first complexing agent to water. Alternatively, the complex can have a 1:2:0 molar ratio of lanthanide ion to first complexing agent to water. As another alternative, the complex can have a 1:2:1 molar ratio of lanthanide ion to first complexing agent to water. As a further alternative, the complex can have a 1:3:0 molar ratio of lanthanide ion to first complexing agent to water.
The lanthanide ion can be a member of the group that includes samarium, europium, terbium, and dysprosium.
The methods can include, prior to extracting the fluid from the reservoir, introducing a fourth composition with a second complexing agent into the reservoir at a third location, where the third location is different from the first location and the second location, and where the extracted fluid includes a concentration of the second complexing agent. The amount of the first complexing agent introduced into the reservoir can be the same as the amount of the second complexing agent introduced into the reservoir.
The methods can include, prior to extracting the fluid from the reservoir, introducing a fourth composition with a second complexing agent into the reservoir at a third location, where the third location is different from the first location and the second location, and introducing a fifth composition with a third complexing agent into the reservoir at a fourth location, where the fourth location is different from the first location, the second location, and the third location, and where the extracted fluid includes a concentration of the second complexing agent and a concentration of the third complexing agent. The amounts of the first, second, and third complexing agents introduced into the reservoir can be the same.
The methods can include, prior to combining the fluid with the second composition, separating the first complexing agent from the second complexing agent in the fluid, and separating the third complexing agent from the first and second complexing agents if the fluid includes the third complexing agent. The steps of separating the first and third complexing agents can include performing a chromatographic separation.
A wavelength of the electromagnetic radiation can be in an ultraviolet spectral region. The time interval t1−t0 can be greater than 5 microseconds (for example, greater than 25 microseconds).
The information about the fluid flow path can include any one or more of a concentration of the first complexing agent, a concentration of the second complexing agent, and a concentration of the third complexing agent.
The first complexing agent can be a tridentate ligand. The first complexing agent can be a compound having a general structure given by Formula (I), or an anion or salt of the structure given by Formula (I):
In Formula (I), X can be present or absent, and when present, can be a member of the group that includes: C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each of C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene can be optionally interrupted by one O, S, or NH.
In Formula (I), R can be a member of the group that includes (i) hydrogen, (ii) —ORa, (iii) C1-4 alkoxy, optionally substituted with 1-3 independent units of Rb, (iv) C1-4 haloalkoxy, (v) —COH, (vi) —CO2Ra, (vii) —CONRaRa, (viii) cyano, (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, (xii) —NRaC(O)Ra, (xiii) -aryl that is optionally substituted with 1-3 independent units of Rb, (xiv) -heteroaryl including from 5-10 ring atoms, where 1-4 ring atoms are each independent members of the group that includes N, NH, O, and S, and where the heteroaryl can be optionally substituted with 1-3 independent units of Rb, (xv) —C3-10 cycloalkyl that is optionally substituted with 1-4 independent units of Rb, (xvi) -heterocyclyl, including from 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes N, NH and O, and where the heterocyclyl can be optionally substituted with 1-4 independent units of Rb, (xvii) C1-4 thioalkoxy, (xviii) —N3, (xix) —CO2H, (xx) —C(O)Ra, (xxi) —SO1-2(Ra), and (xxii) —OnP(O)nY2, where each occurrence of n can independently be 0 or 1, and where each occurrence Y can independently be one of —ORa, NRaRa, and C1-6 alkyl.
Each occurrence of Ra in Formula (I) can independently be one of (i) H, (ii) C1-8 alkyl optionally substituted with from 1-3 independent units of Rb, (iii) —(C0-6 alkylene)—C3-10 cycloalkyl, where the cycloalkyl is optionally substituted with from 1-4 independent units of Rb, (iv) —(C0-6 alkylene)-heterocyclyl including from 3-10 ring atoms, where 1-3 of the ring atoms can each be independently members of the group that includes NH, O, and S, and where the heterocyclyl can optionally be substituted with from 1-4 independent units of Rb, (v) —(C0-6 alkylene)-(C6-10 aryl), where the aryl can be optionally substituted with from 1-5 independent units of Rb, or (vi) —(C0-6 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms can each be independent members of the group that includes N, NH, O, and S, and where the heteroaryl can optionally be substituted with from 1-3 independent units of Rb.
Each occurrence of Rb in Formula (I) can be an independent member of the group that includes (i) halo, (ii) cyano, (iii) C1-6 alkyl, (iv) C2-6 alkenyl, (v) C2-6 alkynyl, (vi) C1-4 haloalkyl, (vii) C1-4 alkoxy, (viii) C1-4 haloalkoxy, (ix) —(C0-3 alkylene)—C3-6 cycloalkyl optionally substituted with 1-4 independent units of C1-4 alkyl, (x) —(C0-3 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms are each independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of C1-4 alkyl, (xi) —(C0-3 alkylene)-phenyl, (xii) —(C0-3 alkylene)-heteroaryl including from 5-10 ring atoms, where 1-4 of the ring atoms can each be independent members of the group that includes N, NH, O, and S, (xiii) —S(O)1-2(C1-4 alkyl), (xiv) —NR′R″, (xv) —OH, (xvi) —S(O)1-2(NR′R″), (xvii) —C1-4 thioalkoxy, (xviii) —NO2, (xix) —N(R′)(C(═O)C1-3 alkyl), (xx) —C(═O)(C1-4 alkyl), (xxi) —C(═O)O(C1-4 alkyl), (xxii) —C(═O)OH, and (xxiii) —C(═O)N(R′)(R″).
Each occurrence of R′ and R″ can be an independent member of the group that includes H and C1-4 alkyl, or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached can form a ring that includes from 3-8 ring atoms, and the ring can include: (a) from 1-7 ring carbon atoms; and (b) 0-3 ring heteroatoms, in addition to the atom attached to R′ and R″, which are each independent members of the group that includes N, NH, O, and S.
In Formula (I), X can be C1-10 alkylene. R can be selected from the group that includes (ii) —ORa, where the Ra of —ORa is not (i) H or (ii) C1-8 alkyl substituted with —(C0-3 alkylene)—C3-6 cycloalkyl, (vi) —CO2Ra, where the Ra of —CO2Ra is not H, (viii) cyano, (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, (xii) —NRaC(O)Ra, (xiii) -aryl that is optionally substituted with from 1-3 independent units of Rb, (xiv) -heteroaryl including from 5-10 ring atoms, where 1-4 ring atoms are independent members of the group that includes N, NH, O, and S, where the heteroaryl is optionally substituted with from 1-3 independent units of Rb, (xv) —C3-10 cycloalkyl that is optionally substituted with from 1-4 independent units of Rb, (xvi) -heterocyclyl including from 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes N, NH and O, and where the heterocyclyl is optionally substituted with from 1-4 independent units of Rb, (xx) —C(O)Ra, and (xxi) —SO1-2(Ra). Each occurrence of Ra can be an independent members of the group that includes (i) H, (ii) C1-8 alkyl optionally substituted with from 1-3 independent units of Rb, (iii) —(C0-6 alkylene)—C3-10 cycloalkyl, where the cycloalkyl is optionally substituted with from 1-4 independent units of Rb, (iv) —(C0-6 alkylene)-heterocyclyl including from 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (v) —(C0-6 alkylene)-(C6-10 aryl), where the aryl is optionally substituted with 1-5 independent units of Rb, or (vi) —(C0-6 alkylene)-heteroaryl including from 5-10 ring atoms, where 1-4 of the ring atoms can be independent members of the group that includes N, NH, O, and S, and where the heteroaryl can be optionally substituted with 1-3 independent units of Rb. Each occurrence of Rb can be an independent member of the group that includes (i) halo, (ii) cyano, (iii) C1-6 alkyl, (iv) C2-6 alkenyl, (v) C2-6 alkynyl, (vi) C1-4 haloalkyl, (vii) C1-4 alkoxy, (viii) C1-4 haloalkoxy, (ix) —(C0-3 alkylene)-C3-6 cycloalkyl optionally substituted with 1-4 independent units of C1-4 alkyl, (x) —(C0-3 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms can be independent members of the group that includes NH, O, and S, and where the heterocyclyl can be optionally substituted with 1-4 independent units of C1-4 alkyl; (xi) —(C0-3 alkylene)-phenyl; (xii) —(C0-3 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms can be independent members of the group that includes N, NH, O, and S, (xiii) —S(O)1-2(C1-4 alkyl), (xiv) —NR′R″, (xv) —OH, (xvi) —S(O)1-2(NR′R″), (xvii) —C1-4 thioalkoxy, (xviii) —NO2, (xix) —N(R′)(C(═O)C1-3 alkyl), (xx) —C(═O)(C1-4 alkyl), (xxi) —C(═O)O(C1-4 alkyl), (xxii) —C(═O)OH, and (xxiii) —C(═O)N(R′)(R″). Each occurrence of R′ and R″ can be an independent member of the group that includes H and C1-4 alkyl, or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached can form a ring that includes 3-8 ring atoms, where the ring includes (a) 1-7 ring carbon atoms, and (b) 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″), which are each independent members of the group that includes N, NH, O, and S.
In Formula (I), X can be —CH2—. In Formula (I), R can be (ii) —ORa, where the Ra of —ORa is not (i) H or (ii) C1-8 alkyl substituted with —C0-3 alkylene)—C3-6 cycloalkyl.
In Formula (I), R can be a member of the group that includes (ix) —NRaRa, where one Ra is H, (x) —NRaC(O)NRaRa, where at least one Ra is H, (xi) —NRaC(O)ORa, where the Ra bonded to N is H, and (xii) —NRaC(O)Ra.
In Formula (I), R can be a member of the group that includes (vi) —CO2Ra, where the Ra of —CO2Ra is not H, and (xx) —C(O)Ra.
The first complexing agent can be tetradentate.
The first complexing agent can be a compound having a general structure given by Formula (II), or an anion or salt of a compound having the general structure of Formula (II):
In Formula (II), each of X1 and X2 can be independently present or absent, and when one or both are present, each can be an independent member of the group that includes C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH.
In Formula (II), each R1 and R2 is an independent member of the group that includes (i) hydrogen, (ii) —ORa, (iii) C1-4 alkoxy optionally substituted with 1-3 independent units of Rb, (iv) C1-4 haloalkoxy, (v) —COH, (vi) —CO2Ra, (vii) —CONRaRa, (viii) cyano, (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, (xii) —NRaC(O)Ra, (xiii) -aryl that is optionally substituted with 1-3 independent units of Rb, (xiv) -heteroaryl including 5-10 ring atoms, where 1-4 ring atoms are each independent members of the group that includes N, NH, O, and S, and where the heteroaryl is optionally substituted with 1-3 independent units of Rb, (xv) —C3-10 cycloalkyl that is optionally substituted with 1-4 independent units of Rb, (xvi) -heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms can each be independent members of the group that includes N, NH and O, where the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (xvii) C1-4 thioalkoxy, (xviii) —N3, (xix) —CO2H, (xx) —C(O)Ra, (xxi) —SO1-2(Ra), and (xxii) —OnP(O)nY2, where each n is independently 0 or 1, and each Y is an independent member of the group that includes —ORa, NRaRa, and C1-6 alkyl.
Each occurrence of Ra can be an independent member of the group that includes (i) H, (ii) C1-8 alkyl optionally substituted with 1-3 independent units of Rb, (iii) —(C0-6 alkylene)—C3-10 cycloalkyl, where the cycloalkyl is optionally substituted with 1-4 independent units of Rb, (iv) —(C0-6 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (v) —(C0-6 alkylene)-(C6-10 aryl), where the aryl is optionally substituted with 1-5 independent units of Rb, or (vi) —(C0-6 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes N, NH, O, and S, and the heteroaryl is optionally substituted with 1-3 independent units of Rb.
Each occurrence of Rb can be an independent member of the group that includes (i) halo, (ii) cyano, (iii) C1-6 alkyl, (iv) C2-6 alkenyl, (v) C2-6 alkynyl, (vi) C1-4 haloalkyl, (vii) C1-4 alkoxy, (viii) C1-4 haloalkoxy, (ix) —(C0-3 alkylene)—C3-6 cycloalkyl optionally substituted with 1-4 independent units of C1-4 alkyl, (x) —(C0-3 alkylene)-heterocyclyl including from 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of C1-4 alkyl, (xi) —(C0-3 alkylene)-phenyl, (xii) —(C0-3 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes of N, NH, O, and S, (xiii) —S(O)1-2(C1-4 alkyl), (xiv) —NR′R″, (xv) —OH, (xvi) —S(O)1-2(NR′R″), (xvii) —C1-4 thioalkoxy, (xviii) —NO2, (xix) —N(R′)(C(═O)C1-3 alkyl), (xx) —C(═O)(C1-4 alkyl), (xxi) —C(═O)O(C1-4 alkyl), (xxii) —C(═O)OH, and (xxiii) —C(═O)N(R′)(R″).
Each occurrence of R′ and R″ can be an independent member of the group that includes H and C1-4 alkyl, or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached can form a ring including 3-8 ring atoms, where the ring includes (a) 1-7 ring carbon atoms, and (b) 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″) which are each independent members of the group that includes N, NH, O, and S.
In Formula (II), each of X1 and X2 can be independently present or absent, and when one or both are present, each can be an independent member of the group that includes C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH. Each of R1 and R2 can be an independent member of the group that includes (ii) —OR′, (iii) C1-4 alkoxy optionally substituted with 1-3 independent units of Rb, (iv) C1-4 haloalkoxy, (vi) —CO2Ra, (vii) —CONRaRa, (viii) cyano, (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, (xii) —NRaC(O)Ra, (xiii) -aryl that is optionally substituted with 1-3 independent units of Rb, (xiv) -heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes N, NH, O, and S, and where the heteroaryl is optionally substituted with 1-3 independent units of Rb, (xv) —C3-10 cycloalkyl that is optionally substituted with 1-4 independent units of Rb, (xvi) —heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes N, NH and O, and where the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (xix) —CO2H, (xx) —C(O)Ra, and (xxi) —SO1-2(Ra). Each occurrence of Ra can be an independent member of the group that includes (i) H, (ii) C1-8 alkyl optionally substituted with 1-3 independent units of Rb, (iii) —(C0-6 alkylene)-C3-10 cycloalkyl, where the cycloalkyl is optionally substituted with 1-4 independent units of Rb, (iv) —(C0-6 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 ring atoms are independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (v) —(C0-6 alkylene)-(C6-10 aryl), where the aryl is optionally substituted with 1-5 independent units of Rb, or (vi) —(C0-6 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms can be independent members of the group that includes N, NH, O, and S, and where the heteroaryl is optionally substituted with 1-3 independent units of Rb. Each occurrence of Rb can be an independent member of the group that includes (i) halo, (ii) cyano, (iii) C1-6 alkyl, (iv) C2-6 alkenyl, (v) C2-6 alkynyl, (vi) C1-4 haloalkyl, (vii) C1-4 alkoxy, (viii) C1-4 haloalkoxy, (ix) —(C0-3 alkylene)—C3-6 cycloalkyl optionally substituted with 1-4 independent units of C1-4 alkyl, (x) —(C0-3 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 ring atoms are independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of C1-4 alkyl, (xi) —(C0-3 alkylene)-phenyl, (xii) —(C0-3 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 ring atoms are independent members of the group that includes N, NH, O, and S, (xiii) —S(O)1-2(C1-4 alkyl), (xiv) —NR′R″, (xv) —OH, (xvi) —S(O)1-2(NR′R″), (xvii) —C1-4 thioalkoxy, (xviii) —NO2, (xix) —N(R′)(C(═O)C1-3 alkyl), (xx) —C(═O)(C1-4 alkyl), (xxi) —C(═O)O(C1-4 alkyl), (xxii) —C(═O)OH, and (xxiii) —C(═O)N(R′)(R″). Each occurrence of R′ and R″ can be an independent member of the group that includes H and C1-4 alkyl, or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached can form a ring including 3-8 ring atoms, where the ring includes (a) 1-7 ring carbon atoms, and (b) 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″), which are each independent members of the group that includes N, NH, O, and S.
In Formula (II), X1 and X2 can both be absent.
In Formula (II), R1 and R2 can each be independent members of the group that includes (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, and (xii) —NRaC(O)Ra. Alternatively, in Formula (II), R1 and R2 can each be independent members of the group that includes (ix) —NHRa, (x) —NHC(O)NHRa, (xi) —NHC(O)ORa, and (xii) —NHC(O)Ra. As another alternative, in Formula (II), R1 and R2 can each be (ix) —NHRa.
In Formula (II), Ra can be (ii) C1-8 alkyl substituted with 1-3 independent units of Rb, where at least one of the Rb is (xv) —OH. Alternatively, in Formula (II), R1 and R2 can each be (x) —NHC(O)NHRa. As another alternative, in Formula (II), R1 and R2 can each be (xi) —NHC(O)ORa. As a further alternative, in Formula (II), R1 and R2 can each be (xii) —NHC(O)Ra.
In Formula (II), each of R1 and R2 can be the same, or alternatively, each of R1 and R2 can be different.
The first complexing agent can be a compound having a general structure given by Formula (III), or an anion or salt of a compound having the general structure of Formula (III):
In Formula (III), each of X1 and X2 can be independently present or absent, and when one or both are present, each can be an independent member of the group that includes C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH.
In Formula (II), each R1 and R2 is an independent member of the group that includes (i) hydrogen, (ii) —ORa, (iii) C1-4 alkoxy optionally substituted with 1-3 independent units of Rb, (iv) C1-4 haloalkoxy, (v) —COH, (vi) —CO2Ra, (vii) —CONRaRa, (viii) cyano, (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, (xii) —NRaC(O)Ra, (xiii) -aryl that is optionally substituted with 1-3 independent units of Rb, (xiv) -heteroaryl including 5-10 ring atoms, where 1-4 ring atoms are each independent members of the group that includes N, NH, O, and S, and where the heteroaryl is optionally substituted with 1-3 independent units of Rb, (xv) —C3-10 cycloalkyl that is optionally substituted with 1-4 independent units of Rb, (xvi) -heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms can each be independent members of the group that includes N, NH and O, where the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (xvii) C1-4 thioalkoxy, (xviii) —N3, (xix) —CO2H, (xx) —C(O)Ra, (xxi) —SO1-2(Ra), (xxii) —OnP(O)nY2, where each n is independently 0 or 1, and (xxiii) halo (e.g., —F, —Cl, —Br, or —I), and each Y is an independent member of the group that includes —ORa, NRaRa, and C1-6 alkyl.
Each occurrence of Ra can be an independent member of the group that includes (i) H, (ii) C1-8 alkyl optionally substituted with 1-3 independent units of Rb, (iii) —(C0-6 alkylene)—C3-10 cycloalkyl, where the cycloalkyl is optionally substituted with 1-4 independent units of Rb, (iv) —(C0-6 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (v) —(C0-6 alkylene)-(C6-10 aryl), where the aryl is optionally substituted with 1-5 independent units of Rb, or (vi) —(C0-6 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes N, NH, O, and S, and the heteroaryl is optionally substituted with 1-3 independent units of Rb.
Each occurrence of Rb can be an independent member of the group that includes (i) halo, (ii) cyano, (iii) C1-6 alkyl, (iv) C2-6 alkenyl, (v) C2-6 alkynyl, (vi) C1-4 haloalkyl, (vii) C1-4 alkoxy, (viii) C1-4 haloalkoxy, (ix) —(C0-3 alkylene)—C3-6 cycloalkyl optionally substituted with 1-4 independent units of C1-4 alkyl, (x) —(C0-3 alkylene)-heterocyclyl including from 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of C1-4 alkyl, (xi) —(C0-3 alkylene)-phenyl, (xii) —(C0-3 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes of N, NH, O, and S, (xiii) —S(O)1-2(C1-4 alkyl), (xiv) —NR′R″, (xv) —OH, (xvi) —S(O)1-2(NR′R″), (xvii) —C1-4 thioalkoxy, (xviii) —NO2, (xix) —N(R′)(C(═O)C1-3 alkyl), (xx) —C(═O)(C1-4 alkyl), (xxi)—C(═O)O(C1-4 alkyl), (xxii) —C(═O)OH, and (xxiii) —C(═O)N(R′)(R″).
Each occurrence of R′ and R″ can be an independent member of the group that includes H and C1-4 alkyl, or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached can form a ring including 3-8 ring atoms, where the ring includes (a) 1-7 ring carbon atoms, and (b) 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″) which are each independent members of the group that includes N, NH, O, and S.
In Formula (III), each of X1 and X2 can be independently present or absent, and when one or both are present, each can be an independent member of the group that includes C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH. Each of R1 and R2 can be an independent member of the group that includes (ii) —ORa, (iii) C1-4 alkoxy optionally substituted with 1-3 independent units of Rb, (iv) C1-4 haloalkoxy, (vi) —CO2Ra, (vii) —CONRaRa, (viii) cyano, (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, (xii) —NRaC(O)Ra, (xiii) -aryl that is optionally substituted with 1-3 independent units of Rb, (xiv) -heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes N, NH, O, and S, and where the heteroaryl is optionally substituted with 1-3 independent units of Rb, (xv) —C3-10 cycloalkyl that is optionally substituted with 1-4 independent units of Rb, (xvi) -heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes N, NH and O, and where the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (xix) —CO2H, (xx) —C(O)Ra, and (xxi) —SO1-2(Ra). Each occurrence of Ra can be an independent member of the group that includes (i) H, (ii) C1-8 alkyl optionally substituted with 1-3 independent units of Rb, (iii) —(C0-6 alkylene)—C3-10 cycloalkyl, where the cycloalkyl is optionally substituted with 1-4 independent units of Rb, (iv) —(C0-6 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 ring atoms are independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (v) —(C0-6 alkylene)-(C6-10 aryl), where the aryl is optionally substituted with 1-5 independent units of Rb, or (vi) —(C0-6 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms can be independent members of the group that includes N, NH, O, and S, and where the heteroaryl is optionally substituted with 1-3 independent units of Rb. Each occurrence of Rb can be an independent member of the group that includes (i) halo, (ii) cyano, (iii) C1-6 alkyl, (iv) C2-6 alkenyl, (v) C2-6 alkynyl, (vi) C1-4 haloalkyl, (vii) C1-4 alkoxy, (viii) C1-4 haloalkoxy, (ix) —(C0-3 alkylene)—C3-6 cycloalkyl optionally substituted with 1-4 independent units of C1-4 alkyl, (x) —(C0-3 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 ring atoms are independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of C1-4 alkyl, (xi) —(C0-3 alkylene)-phenyl, (xii) —(C0-3 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 ring atoms are independent members of the group that includes N, NH, O, and S, (xiii) —S(O)1-2(C1-4 alkyl), (xiv) —NR′R″, (xv) —OH, (xvi) —S(O)1-2(NR′R″), (xvii) —C1-4 thioalkoxy, (xviii) —NO2, (xix) —N(R′)(C(═O)C1-3 alkyl), (xx) —C(═O)(C1-4 alkyl), (xxi) —C(═O)O(C1-4 alkyl), (xxii) —C(═O)OH, and (xxiii) —C(═O)N(R′)(R″). Each occurrence of R′ and R″ can be an independent member of the group that includes H and C1-4 alkyl, or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached can form a ring including 3-8 ring atoms, where the ring includes (a) 1-7 ring carbon atoms, and (b) 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″), which are each independent members of the group that includes N, NH, O, and S.
In Formula (III), X1 and X2 can both be absent. In Formula (III), R1 and R2 can each be independent members of the group that includes (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, and (xii) —NRaC(O)Ra. Alternatively, in Formula (III), R1 and R2 can each be independent members of the group that includes (ix) —NHRa, (x) —NHC(O)NHRa, (xi) —NHC(O)ORa, and (xii) —NHC(O)Ra. As another alternative, in Formula (III), R1 and R2 can each be (ix) —NHRa.
In Formula (III), Ra can be (ii) C1-8 alkyl substituted with 1-3 independent units of Rb, where at least one of the Rb is (xv) —OH. Alternatively, in Formula (III), R1 and R2 can each be (x) —NHC(O)NHRa. As another alternative, in Formula (III), R1 and R2 can each be (xi) —NHC(O)ORa. As a further alternative, in Formula (III), R1 and R2 can each be (xii) —NHC(O)Ra.
In Formula (III), each of R1 and R2 can be the same, or alternatively, each of R1 and R2 can be different.
Embodiments of the methods can also include any of the other features discussed, including features associated with different embodiments, in any combination unless expressly stated otherwise.
In another aspect, this disclosure features methods of forming a complex that includes a complexing agent and a lanthanide ion, the methods including introducing the complexing agent into a subterranean reservoir at a first location, allowing the complexing agent to propagate through at least a portion of the reservoir to a second location different from the first location, extracting the complexing agent from the reservoir at the second location, and combining the extracted complexing agent with a solution that includes the lanthanide ion to form the complex, where the complexing agent has a general structure given by Formula (I), or an anion or salt of the structure given by Formula (I):
In Formula (I), X can be present or absent, and when present, can be a member of the group that includes: C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each of C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene can be optionally interrupted by one O, S, or NH. R can be a member of the group that includes (i) hydrogen, (ii) —ORa, (iii) C1-4 alkoxy, optionally substituted with 1-3 independent units of Rb, (iv) C1-4 haloalkoxy, (v) —COH, (vi) —CO2Ra, (vii) —CONRaRa, (viii) cyano, (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, (xii) —NRaC(O)Ra, (xiii) -aryl that is optionally substituted with 1-3 independent units of Rb, (xiv) -heteroaryl including from 5-10 ring atoms, where 1-4 ring atoms are each independent members of the group that includes N, NH, O, and S, and where the heteroaryl can be optionally substituted with 1-3 independent units of Rb, (xv) —C3-10 cycloalkyl that is optionally substituted with 1-4 independent units of Rb, (xvi) -heterocyclyl, including from 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes N, NH and O, and where the heterocyclyl can be optionally substituted with 1-4 independent units of Rb, (xvii) C1-4 thioalkoxy, (xviii) —N3, (xix) —CO2H, (xx) —C(O)Ra, (xxi) —SO1-2(Ra), and (xxii) —OnP(O)nY2, where each occurrence of n can independently be 0 or 1, and where each occurrence Y can independently be one of —ORa, NRaRa, and C1-6 alkyl. Each occurrence of Ra in Formula (I) can independently be one of (i) H, (ii) C1-8 alkyl optionally substituted with from 1-3 independent units of Rb, (iii) —(C0-6 alkylene)—C3-10 cycloalkyl, where the cycloalkyl is optionally substituted with from 1-4 independent units of Rb, (iv) —(C0-6 alkylene)-heterocyclyl including from 3-10 ring atoms, where 1-3 of the ring atoms can each be independently members of the group that includes NH, O, and S, and where the heterocyclyl can optionally be substituted with from 1-4 independent units of Rb, (v) —(C0-6 alkylene)-(C6-10 aryl), where the aryl can be optionally substituted with from 1-5 independent units of Rb, or (vi) —(C0-6 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms can each be independent members of the group that includes N, NH, O, and S, and where the heteroaryl can optionally be substituted with from 1-3 independent units of Rb. Each occurrence of Rb in Formula (I) can be an independent member of the group that includes (i) halo, (ii) cyano, (iii) C1-6 alkyl, (iv) C2-6 alkenyl, (v) C2-6 alkynyl, (vi) C1-4 haloalkyl, (vii) C1-4 alkoxy, (viii) C1-4 haloalkoxy, (ix) —(C0-3 alkylene)—C3-6 cycloalkyl optionally substituted with 1-4 independent units of C1-4 alkyl, (x) —(C0-3 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms are each independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of C1-4 alkyl, (xi) —(C0-3 alkylene)-phenyl, (xii) —(C0-3 alkylene)-heteroaryl including from 5-10 ring atoms, where 1-4 of the ring atoms can each be independent members of the group that includes N, NH, O, and S, (xiii) —S(O)1-2(C1-4 alkyl), (xiv) —NR′R″, (xv) —OH, (xvi) —S(O)1-2(NR′R″), (xvii) —C1-4 thioalkoxy, (xviii) —NO2, (xix) —N(R′)(C(═O)C1-3 alkyl), (xx) —C(═O)(C1-4 alkyl), (xxi) —C(═O)O(C1-4 alkyl), (xxii) —C(═O)OH, and (xxiii) —C(═O)N(R′)(R″). Each occurrence of R′ and R″ can be an independent member of the group that includes H and C1-4 alkyl, or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached can form a ring that includes from 3-8 ring atoms, and the ring can include: (a) from 1-7 ring carbon atoms; and (b) 0-3 ring heteroatoms, in addition to the atom attached to R′ and R″, which are each independent members of the group that includes N, NH, O, and S.
Embodiments of the methods can include any one or more of the following features.
X, R, each occurrence of Ra, each occurrence of Rb, each occurrence of R′ and R″, and combinations of these structural units, can have any of the features discussed in connection with Formula (I) for these structural units.
The complex can include water. The complex can include a molar ratio of lanthanide ion to complexing agent to water of 1:1:2, or 1:2:1, or 1:3:0. The lanthanide ion can be selected from the group that includes samarium, europium, terbium, and dysprosium.
Embodiments of the methods can also include any of the other features discussed, including features associated with different embodiments, in any combination unless expressly stated otherwise.
In a further aspect, this disclosure features methods of forming a complex that includes a complexing agent and a lanthanide ion, the methods including introducing the complexing agent into a subterranean reservoir at a first location, allowing the complexing agent to propagate through at least a portion of the reservoir to a second location different from the first location, extracting the complexing agent at a second location, and combining the extracted complexing agent with a solution that includes the lanthanide ion to form the complex, where the complexing agent has a general structure given by Formula (II), or an anion or salt of the structure given by Formula (II):
In Formula (II), each of X1 and X2 can be independently present or absent, and when one or both are present, each can be an independent member of the group that includes C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH. Each R1 and R2 is an independent member of the group that includes (1) hydrogen, (ii) —ORa, (iii) C1-4 alkoxy optionally substituted with 1-3 independent units of Rb, (iv) C1-4 haloalkoxy, (v) —COH, (vi) —CO2Ra, (vii) —CONRaRa, (viii) cyano, (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, (xii) —NRaC(O)Ra, (xiii) -aryl that is optionally substituted with 1-3 independent units of Rb, (xiv) -heteroaryl including 5-10 ring atoms, where 1-4 ring atoms are each independent members of the group that includes N, NH, O, and S, and where the heteroaryl is optionally substituted with 1-3 independent units of Rb, (xv) —C3-10 cycloalkyl that is optionally substituted with 1-4 independent units of Rb, (xvi) -heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms can each be independent members of the group that includes N, NH and O, where the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (xvii) C1-4 thioalkoxy, (xviii) —N3, (xix) —CO2H, (xx) —C(O)Ra, (xxi) —SO1-2(Ra), and (xxii) —OnP(O)nY2, where each n is independently 0 or 1, and each Y is an independent member of the group that includes —ORa, NRaRa, and C1-6 alkyl. Each occurrence of Ra can be an independent member of the group that includes (i) H, (ii) C1-8 alkyl optionally substituted with 1-3 independent units of Rb, (iii) —(C0-6 alkylene)—C3-10 cycloalkyl, where the cycloalkyl is optionally substituted with 1-4 independent units of Rb, (iv) —(C0-6 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (v) —(C0-6 alkylene)-(C6-10 aryl), where the aryl is optionally substituted with 1-5 independent units of Rb, or (vi) —(C0-6 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes N, NH, O, and S, and the heteroaryl is optionally substituted with 1-3 independent units of Rb. Each occurrence of Rb can be an independent member of the group that includes (i) halo, (ii) cyano, (iii) C1-6 alkyl, (iv) C2-6 alkenyl, (v) C2-6 alkynyl, (vi) C1-4 haloalkyl, (vii) C1-4 alkoxy, (viii) C1-4 haloalkoxy, (ix) —(C0-3 alkylene)—C3-6 cycloalkyl optionally substituted with 1-4 independent units of C1-4 alkyl, (x) —(C0-3 alkylene)-heterocyclyl including from 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of C1-4 alkyl, (xi) —(C0-3 alkylene)-phenyl, (xii) —(C0-3 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes of N, NH, O, and S, (xiii) —S(O)1-2(C1-4 alkyl), (xiv) —NR′R″, (xv) —OH, (xvi) —S(O)1-2(NR′R″), (xvii) —C1-4 thioalkoxy, (xviii) —NO2, (xix) —N(R′)(C(═O)C1-3 alkyl), (xx) —C(═O)(C1-4 alkyl), (xxi) —C(═O)O(C1-4 alkyl), (xxii) —C(═O)OH, and (xxiii) —C(═O)N(R′)(R″). Each occurrence of R′ and R″ can be an independent member of the group that includes H and C1-4 alkyl, or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached can form a ring including 3-8 ring atoms, where the ring includes (a) 1-7 ring carbon atoms, and (b) 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″) which are each independent members of the group that includes N, NH, O, and S.
Embodiments of the methods can include any one or more of the following features.
X1, X2, R2, each occurrence of Ra, each occurrence of Rb, each occurrence of R′ and R″, and combinations of these structural units, can have any of the features discussed in connection with Formula (II) for these structural units.
The complex can include water. A molar ratio of lanthanide ion to complexing agent to water can be 1:1:2 or 1:2:0. The lanthanide ion can be selected from the group that includes samarium, europium, terbium, and dysprosium.
Embodiments of the methods can also include any of the other features discussed, including features associated with different embodiments, in any combination unless expressly stated otherwise.
In another aspect, this disclosure features methods of forming a complex that includes a complexing agent and a lanthanide ion, the methods including introducing the complexing agent into a subterranean reservoir at a first location, allowing the complexing agent to propagate through at least a portion of the reservoir to a second location different from the first location, extracting the complexing agent at a second location, and combining the extracted complexing agent with a solution that includes the lanthanide ion to form the complex, where the complexing agent has a general structure given by Formula (III), or an anion or salt of the structure given by Formula (III):
In Formula (III), each of X1 and X2 can be independently present or absent, and when one or both are present, each can be an independent member of the group that includes C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH. Each R1 and R2 is an independent member of the group that includes (i) hydrogen, (ii) —ORa, (iii) C1-4 alkoxy optionally substituted with 1-3 independent units of Rb, (iv) C1-4 haloalkoxy, (v) —COH, (vi) —CO2Ra, (vii) —CONRaRa, (viii) cyano, (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, (xii) —NRaC(O)Ra, (xiii) -aryl that is optionally substituted with 1-3 independent units of Rb, (xiv) -heteroaryl including 5-10 ring atoms, where 1-4 ring atoms are each independent members of the group that includes N, NH, O, and S, and where the heteroaryl is optionally substituted with 1-3 independent units of Rb, (xv) —C3-10 cycloalkyl that is optionally substituted with 1-4 independent units of Rb, (xvi) -heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms can each be independent members of the group that includes N, NH and O, where the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (xvii) C1-4 thioalkoxy, (xviii) —N3, (xix) —CO2H, (xx) —C(O)Ra, (xxi) —SO1-2(Ra), (xxii) —OnP(O)nY2, where each n is independently 0 or 1, and (xxiii) halo (e.g., —F, —Cl, —Br, or —I), and each Y is an independent member of the group that includes —ORa, NRaRa, and C1-6 alkyl. Each occurrence of Ra can be an independent member of the group that includes (i) H, (ii) C1-8 alkyl optionally substituted with 1-3 independent units of Rb, (iii) —(C0-6 alkylene)—C3-10 cycloalkyl, where the cycloalkyl is optionally substituted with 1-4 independent units of Rb, (iv) —(C0-6 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (v) —(C0-6 alkylene)-(C6-10 aryl), where the aryl is optionally substituted with 1-5 independent units of Rb, or (vi) —(C0-6 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes N, NH, O, and S, and the heteroaryl is optionally substituted with 1-3 independent units of Rb. Each occurrence of Rb can be an independent member of the group that includes (i) halo, (ii) cyano, (iii) C1-6 alkyl, (iv) C2-6 alkenyl, (v) C2-6 alkynyl, (vi) C1-4 haloalkyl, (vii) C1-4 alkoxy, (viii) C1-4 haloalkoxy, (ix) —(C0-3 alkylene)—C3-6 cycloalkyl optionally substituted with 1-4 independent units of C1-4 alkyl, (x) —(C0-3 alkylene)-heterocyclyl including from 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of C1-4 alkyl, (xi) —(C0-3 alkylene)-phenyl, (xii) —(C0-3 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes of N, NH, O, and S, (xiii) —S(O)1-2(C1-4 alkyl), (xiv) —NR′R″, (xv) —OH, (xvi) —S(O)1-2(NR′R″), (xvii) —C1-4 thioalkoxy, (xviii) —NO2, (xix) —N(R′)(C(═O)C1-3 alkyl), (xx) —C(═O)(C1-4 alkyl), (xxi) —C(═O)O(C1-4 alkyl), (xxii) —C(═O)OH, and (xxiii) —C(═O)N(R′)(R″). Each occurrence of R′ and R″ can be an independent member of the group that includes H and C1-4 alkyl, or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached can form a ring including 3-8 ring atoms, where the ring includes (a) 1-7 ring carbon atoms, and (b) 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″) which are each independent members of the group that includes N, NH, O, and S.
Embodiments of the methods can include any one or more of the following features.
X1, X2, R1, R2, each occurrence of Ra, each occurrence of Rb, each occurrence of R′ and R″, and combinations of these structural units, can have any of the features discussed in connection with Formula (III) for these structural units.
The complex can include water. A molar ratio of lanthanide ion to complexing agent to water can be 1:1:2 or 1:2:0. The lanthanide ion can be selected from the group that includes samarium, europium, terbium, and dysprosium.
Embodiments of the methods can also include any of the other features discussed, including features associated with different embodiments, in any combination unless expressly stated otherwise.
In a further aspect, this disclosure features complexing agents having a general structure given by Formula (I), and anions and salts of the general structure of Formula (I):
In Formula (I), X can be present or absent, and when present, can be a member of the group that includes: C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each of C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene can be optionally interrupted by one O, S, or NH. R can be a member of the group that includes (i) hydrogen, (ii) —ORa, (iii) C1-4 alkoxy, optionally substituted with 1-3 independent units of Rb, (iv) C1-4 haloalkoxy, (v) —COH, (vi) —CO2Ra, (vii) —CONRaRa, (viii) cyano, (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, (xii) —NRaC(O)Ra, (xiii) -aryl that is optionally substituted with 1-3 independent units of Rb, (xiv) -heteroaryl including from 5-10 ring atoms, where 1-4 ring atoms are each independent members of the group that includes N, NH, O, and S, and where the heteroaryl can be optionally substituted with 1-3 independent units of Rb, (xv) —C3-10 cycloalkyl that is optionally substituted with 1-4 independent units of Rb, (xvi) -heterocyclyl, including from 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes N, NH and O, and where the heterocyclyl can be optionally substituted with 1-4 independent units of Rb, (xvii) C1-4 thioalkoxy, (xviii) —N3, (xix) —CO2H, (xx) —C(O)Ra, (xxi) —SO1-2(Ra), and (xxii) —OnP(O)nY2, where each occurrence of n can independently be 0 or 1, and where each occurrence Y can independently be one of —ORa, NRaRa, and C1-6 alkyl. Each occurrence of Ra in Formula (I) can independently be one of (i) H, (ii) C1-8 alkyl optionally substituted with from 1-3 independent units of Rb, (iii) —(C0-6 alkylene)-C3-10 cycloalkyl, where the cycloalkyl is optionally substituted with from 1-4 independent units of Rb, (iv) —(C0-6 alkylene)-heterocyclyl including from 3-10 ring atoms, where 1-3 of the ring atoms can each be independently members of the group that includes NH, O, and S, and where the heterocyclyl can optionally be substituted with from 1-4 independent units of Rb, (v) —(C0-6 alkylene)-(C6-10 aryl), where the aryl can be optionally substituted with from 1-5 independent units of Rb, or (vi) —(C0-6 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms can each be independent members of the group that includes N, NH, O, and S, and where the heteroaryl can optionally be substituted with from 1-3 independent units of Rb. Each occurrence of Rb in Formula (I) can be an independent member of the group that includes (i) halo, (ii) cyano, (iii) C1-6 alkyl, (iv) C2-6 alkenyl, (v) C2-6 alkynyl, (vi) C1-4 haloalkyl, (vii) C1-4 alkoxy, (viii) C1-4 haloalkoxy, (ix) —(C0-3 alkylene)—C3-6 cycloalkyl optionally substituted with 1-4 independent units of C1-4 alkyl, (x) —(C0-3 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms are each independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of C1-4 alkyl, (xi) —(C0-3 alkylene)-phenyl, (xii) —(C0-3 alkylene)-heteroaryl including from 5-10 ring atoms, where 1-4 of the ring atoms can each be independent members of the group that includes N, NH, O, and S, (xiii) —S(O)1-2(C1-4 alkyl), (xiv) —NR′R″, (xv) —OH, (xvi) —S(O)1-2(NR′R″), (xvii) —C1-4 thioalkoxy, (xviii) —NO2, (xix) —N(R′)(C(═O)C1-3 alkyl), (xx) —C(═O)(C1-4 alkyl), (xxi) —C(═O)O(C1-4 alkyl), (xxii) —C(═O)OH, and (xxiii) —C(═O)N(R′)(R″). Each occurrence of R′ and R″ can be an independent member of the group that includes H and C1-4 alkyl, or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached can form a ring that includes from 3-8 ring atoms, and the ring can include: (a) from 1-7 ring carbon atoms; and (b) 0-3 ring heteroatoms, in addition to the atom attached to R′ and R″, which are each independent members of the group that includes N, NH, O, and S.
Embodiments of the complexing agents can include any one or more of the following features.
X, R, each occurrence of Ra, each occurrence of Rb, each occurrence of R′ and R″, and combinations of these structural units, can have any of the features discussed in connection with Formula (I) for these structural units.
Embodiments of the complexing agents can also include any of the other features discussed, including features associated with different embodiments, in any combination unless expressly stated otherwise.
In another aspect, this disclosure features complexing agents having a general structure given by Formula (II), and anions and salts of the general structure of Formula (II):
In Formula (II), each of X1 and X2 can be independently present or absent, and when one or both are present, each can be an independent member of the group that includes C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH. Each R1 and R2 is an independent member of the group that includes (i) hydrogen, (ii) —ORa, (iii) C1-4 alkoxy optionally substituted with 1-3 independent units of Rb, (iv) C1-4 haloalkoxy, (v) —COH, (vi) —CO2Ra, (vii) —CONRaRa, (viii) cyano, (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, (xii) —NRaC(O)Ra, (xiii) -aryl that is optionally substituted with 1-3 independent units of Rb, (xiv) -heteroaryl including 5-10 ring atoms, where 1-4 ring atoms are each independent members of the group that includes N, NH, O, and S, and where the heteroaryl is optionally substituted with 1-3 independent units of Rb, (xv) —C3-10 cycloalkyl that is optionally substituted with 1-4 independent units of Rb, (xvi) -heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms can each be independent members of the group that includes N, NH and O, where the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (xvii) C1-4 thioalkoxy, (xviii) —N3, (xix) —CO2H, (xx) —C(O)Ra, (xxi) —SO1-2(Ra), and (xxii) —OnP(O)nY2, where each n is independently 0 or 1, and each Y is an independent member of the group that includes —ORa, NRaRa, and C1-6 alkyl. Each occurrence of Ra can be an independent member of the group that includes (i) H, (ii) C1-8 alkyl optionally substituted with 1-3 independent units of Rb, (iii) —(C0-6 alkylene)—C3-10 cycloalkyl, where the cycloalkyl is optionally substituted with 1-4 independent units of Rb, (iv) —C0-6 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (v) —(C0-6 alkylene)-(C6-10 aryl), where the aryl is optionally substituted with 1-5 independent units of Rb, or (vi) —(C0-6 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes N, NH, O, and S, and the heteroaryl is optionally substituted with 1-3 independent units of Rb. Each occurrence of Rb can be an independent member of the group that includes (i) halo, (ii) cyano, (iii) C1-6 alkyl, (iv) C2-6 alkenyl, (v) C2-6 alkynyl, (vi) C1-4 haloalkyl, (vii) C1-4 alkoxy, (viii) C1-4 haloalkoxy, (ix) —(C0-3 alkylene)—C3-6 cycloalkyl optionally substituted with 1-4 independent units of C1-4 alkyl, (x) —(C0-3 alkylene)-heterocyclyl including from 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of C1-4 alkyl, (xi) —(C0-3 alkylene)-phenyl, (xii) —(C0-3 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes of N, NH, O, and S, —S(O)1-2(C1-4 alkyl), (xiv) —NR′R″, (xv) —OH, (xvi) —S(O)1-2(NR′R″), (xvii) —C1-4 thioalkoxy, (xviii) —NO2, (xix) —N(R′)(C(═O)C1-3 alkyl), (xx) —C(═O)(C1-4 alkyl), (xxi) —C(═O)O(C1-4 alkyl), (xxii) —C(═O)OH, and (xxiii) —C(═O)N(R′)(R″). Each occurrence of R′ and R″ can be an independent member of the group that includes H and C1-4 alkyl, or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached can form a ring including 3-8 ring atoms, where the ring includes (a) 1-7 ring carbon atoms, and (b) 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″) which are each independent members of the group that includes N, NH, O, and S.
Embodiments of the complexing agents can include any one or more of the following features.
X1, X2, R1, R2, each occurrence of Ra, each occurrence of Rb, each occurrence of R′ and R″, and combinations of these structural units, can have any of the features discussed in connection with Formula (II) for these structural units.
Embodiments of the complexing agents can also include any of the other features discussed, including features associated with different embodiments, in any combination unless expressly stated otherwise.
In a further aspect, this disclosure features complexing agents having a general structure given by Formula (III), and anions and salts of the general structure of Formula (III):
In Formula (III), each of X1 and X2 can be independently present or absent, and when one or both are present, each can be an independent member of the group that includes C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH. Each R1 and R2 is an independent member of the group that includes (i) hydrogen, (ii) —ORa, (iii) C1-4 alkoxy optionally substituted with 1-3 independent units of Rb, (iv) C1-4 haloalkoxy, (v) —COH, (vi) —CO2Ra, (vii) —CONRaRa, (viii) cyano, (ix) —NRaRa, (x) —NRaC(O)NRaRa, (xi) —NRaC(O)ORa, (xii) —NRaC(O)Ra, (xiii) -aryl that is optionally substituted with 1-3 independent units of Rb, (xiv) -heteroaryl including 5-10 ring atoms, where 1-4 ring atoms are each independent members of the group that includes N, NH, O, and S, and where the heteroaryl is optionally substituted with 1-3 independent units of Rb, (xv) —C3-10 cycloalkyl that is optionally substituted with 1-4 independent units of Rb, (xvi) -heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms can each be independent members of the group that includes N, NH and O, where the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (xvii) C1-4 thioalkoxy, (xviii) —N3, (xix) —CO2H, (xx) —C(O)Ra, (xxi) —SO1-2(Ra), (xxii) —OnP(O)nY2, where each n is independently 0 or 1, and (xxiii) halo (e.g., —F, —Cl, —Br, or —I), and each Y is an independent member of the group that includes —ORa, NRaRa, and C1-6 alkyl. Each occurrence of Ra can be an independent member of the group that includes (i) H, (ii) C1-8 alkyl optionally substituted with 1-3 independent units of Rb, (iii) —(C0-6 alkylene)—C3-10 cycloalkyl, where the cycloalkyl is optionally substituted with 1-4 independent units of Rb, (iv) —(C0-6 alkylene)-heterocyclyl including 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and the heterocyclyl is optionally substituted with 1-4 independent units of Rb, (v) —(C0-6 alkylene)-(C6-10 aryl), where the aryl is optionally substituted with 1-5 independent units of Rb, or (vi) —(C0-6 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes N, NH, O, and S, and the heteroaryl is optionally substituted with 1-3 independent units of Rb. Each occurrence of Rb can be an independent member of the group that includes (i) halo, (ii) cyano, (iii) C1-6 alkyl, (iv) C2-6 alkenyl, (v) C2-6 alkynyl, (vi) C1-4 haloalkyl, (vii) C1-4 alkoxy, (viii) C1-4 haloalkoxy, (ix) —(C0-3 alkylene)—C3-6 cycloalkyl optionally substituted with 1-4 independent units of C1-4 alkyl, (x) —(C0-3 alkylene)-heterocyclyl including from 3-10 ring atoms, where 1-3 of the ring atoms are independent members of the group that includes NH, O, and S, and where the heterocyclyl is optionally substituted with 1-4 independent units of C1-4 alkyl, (xi) —(C0-3 alkylene)-phenyl, (xii) —(C0-3 alkylene)-heteroaryl including 5-10 ring atoms, where 1-4 of the ring atoms are independent members of the group that includes of N, NH, O, and S, (xiii) —S(O)1-2(C1-4 alkyl), (xiv) —NR′R″, (xv) —OH, (xvi) —S(O)1-2(NR′R″), (xvii) —C1-4 thioalkoxy, (xviii) —NO2, (xix) —N(R′)(C(═O)C1-3 alkyl), (xx) —C(═O)(C1-4 alkyl), (xxi) —C(═O)O(C1-4 alkyl), (xxii) —C(═O)OH, and (xxiii) —C(═O)N(R′)(R″). Each occurrence of R′ and R″ can be an independent member of the group that includes H and C1-4 alkyl, or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached can form a ring including 3-8 ring atoms, where the ring includes (a) 1-7 ring carbon atoms, and (b) 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″) which are each independent members of the group that includes N, NH, O, and S.
Embodiments of the complexing agents can include any one or more of the following features.
X1, X2, R1, R2, each occurrence of Ra, each occurrence of Rb, each occurrence of R′ and R″, and combinations of these structural units, can have any of the features discussed in connection with Formula (III) for these structural units.
Embodiments of the complexing agents can also include any of the other features discussed, including features associated with different embodiments, in any combination unless expressly stated otherwise.
As used throughout, the terms “about” and “approximately” are used interchangeably, and when used to refer to modify a numerical value, encompass a range of uncertainty of the numerical value of from ½ of the numerical value to twice the numerical value.
As used throughout, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise.
As used throughout, the term “distinguishing moiety” refers to a moiety bonded to the fluorescent (for example, aromatic) portion of a complexing agent that distinguishes the complexing agent on the basis of chemical structure from other complexing agents with different moieties bound to their respective fluorescent portions.
As used throughout, the terms “tracer”, “cross-well tracer”, and “inter-well tracer” each refer to a compound or agent (for example, a complexing agent) that is typically injected into one location of a reservoir, and then extracted from another location (that is, as part of a sample of fluid extracted from the reservoir). The presence or absence of the tracer, for example, can provide information about the connectivity between the injection and extraction locations, and the concentration of the tracer can provide information about flow capacity between the two locations.
As used throughout, the term “hydrocarbon” refers to a fluid that includes 1% or more by volume of one or more organic compounds from natural sources. For example, the one or more organic compounds can include naturally occurring compounds extracted or otherwise liberated from a subterranean reservoir. The fluid can also include other compounds such as, but not limited to, water.
The details of one or more embodiments are set forth in the accompanying drawings and the description. Other features will also be apparent from the description, drawings, and claims.
Like reference symbols in the various drawings indicate like elements.
Using cross-well tracers to map the connectivity and heterogeneity of hydrocarbon reservoirs enables the identification of wells that are contributing to hydrocarbon production and fluid tracing, allowing informed adjustment of well rates to achieve a more balanced water flood. Further, for mature fields under peripheral water flooding programs that could benefit from infill drilling, implementation of a full-field cross-well tracer program that elucidates the existence of faults and greater permeability zones can greatly reduce the uncertainties for waterflood management and justify the expensive drilling/workover programs for the field.
A commonly used category of tracer is fluorinated benzoic acids (FBA's). FBA's have exhibited weak interactions with reservoir matrices and can be detected using ultra-sensitive gas chromatography mass spectrometry (GC/MS). When using GC/MS to detect FBA tracers under favorable conditions (that is, under correct ionization mode), the FBA's can be detected between 10-100 parts per trillion (ppt), depending on the fluorinated benzoic acid used and the unique response of the other components that naturally occur in produced fluids. In general, separate calibrations are used for each different analyte that undergoes mass spectral analysis.
Recent simulations have suggested that data obtained from long-term deployment of inter-well tracers may improve both history matching and production optimization in realistic reservoir models. To facilitate the collection and quantification of injected tracers in large fields, the present disclosure features families of inter-well tracers that can be detected rapidly (e.g., in real time or near-real time), that can be sampled automatically with reduced work-up relative to conventional tracers, that can be transported comparatively long distances between injection and production sites, and that exhibit reduced retention in the reservoir matrix relative to conventional tracers.
After injection at a particular location in a reservoir, the molecular tracers (also referred to as complexing agents) described are able to traverse a pathway from the injection location to a designated producing well for extraction. The tracers are designed to have relatively high solubility in fluids that naturally occur and circulate in reservoirs (for example, water or hydrocarbon compounds), and a relatively weak affinity for the various bedrock and earth formations that the tracers are exposed to while moving through the reservoir.
These features contribute to the tracers disclosed herein having a relatively high reservoir mobility. For certain tracers, having a relatively high mobility manifests as having a relatively low retention in reservoir rocks. For example, in some embodiments, the tracers disclosed herein have a retention in reservoir rocks of less than 50 micrograms per gram (μg/g) of reservoir rocks (such as less than 40 μg/g, less than 30 μg/g, less than 20 μg/g, less than 15 μg/g, less than 10 μg/g, less than 5 μg/g, less than 2 μg/g, less than 1 μg/g).
Without wishing to be bound by theory, it is believed that the various structural features of the tracers may be responsible for the relatively high reservoir fluid solubility and relatively low earth retention characteristics of the tracers. This may be due, for example, to the combination of polar functional groups and lipophilic aromatic groups present in some embodiments of the tracers. The relatively high mobility of the tracers will later be demonstrated and discussed in the context of mobility experiments that simulate the conditions that the tracers encounter in reservoirs.
The tracers, after recovery from a producing well, are optically detectable in the produced fluid at parts per quadrillion concentrations or less after a facile and selective complex formation step with trivalent lanthanide elements, and with minimal background signal due to other contaminants. Not wishing to be bound by theory, it is believed that when used as inter-well tracers, the disclosed complexing agents encounter reservoir fluids with excess naturally-occurring divalent and trivalent ions. Such divalent and trivalent ions may bind with lanthanide ions competitively, generating complexes that may also fluoresce, thus contributing to the fluorescence background. The fluorescence background may also contain, for example, contributions due to polyaromatic hydrocarbons (PAH's).
Without wishing to be bound by theory, the long excited state lifetime occurs due to parity-forbidden transitions between lanthanide ion excited and ground states, which occur significantly more slowly than parity-allowed state-to-state transitions during excitation and further, significantly more slowly than background fluorescence arising from parity allowed excited-to-ground state transitions among other components of the reservoir fluid. When a lanthanide ion is in close proximity to a sensitizing chromophore that either has a strong dipole moment or is anionic such that is can associate ionically with the lanthanide ion, significant enhancement of the lanthanide ion luminescence occurs because the sensitization process circumvents the LaPorte selection rules that normally forbid f-f transitions.
This difference in time scales separates the luminescence signal of the lanthanide complex from the background fluorescent signals 102, which are emitted from the other components (which, in some embodiments, are contaminants) found in the extracted fluid, and become undetectable at a time ti. In turn, the difference in excited state lifetimes and concomitant difference in the temporal evolution of emission from the lanthanide complexes and background components allows gating of the optical detector such that the detector can be used to measure luminescence from the complex alone, after fluorescence from background components in the extracted fluid has decayed.
In addition to reducing or eliminating confounding effects of background fluorescence, the relatively greater sensitivity that can be achieved when measuring the disclosed tracers is in part due to the relatively strong luminescence emission of the complexes.
As a result, luminescence can be enhanced by, for example, three orders of magnitude relative to a bare lanthanide ion. The luminescence intensities of lanthanide ions can be enhanced to this degree by exposing the ions to a molar excess of tracer (also referred to as complexing agent) relative to the ion. It is believed that this results in the exclusion of water molecules from the formed complex, thus maximizing the number of complexing ligands included in the complex.
Another feature of the disclosed tracers is the ability to derivatize the tracers with functional groups (also referred to as “distinguishing moieties”) to generate analogs. Each of several of these analogs can be injected at a different injection location in a reservoir. After extracting a fluid from a producing well, the various analogs can be separated by virtue of their different chemical identities. The resulting purified tracers form complexes with lanthanide ions and are detected via luminescence emission. Since the light-capturing portion of each tracer is the same, each complex will luminesce with similar intensity, and over a similar temporal window. This allows for information to be gathered on multiple flow paths extending between different injection sites and a common recovery site.
Analyzing a Fluid Extracted from a Reservoir
In step 1004, a fluid is extracted from the reservoir at a second location different from the first location, the fluid including a concentration of the first complexing agent that is present in the fluid following injection at the first location in step 1002. The fluid may also include materials and compounds typically found in the earth's crust, for example: water, heavy metals (for example, iron, manganese, chromium, vanadium, or zirconium), salts (for example, potassium salts, calcium salts, magnesium salts, or sodium salts (for example, sodium chloride)), naturally occurring radioactive material (for example, uranium, thorium, radium, or radon), zinc, lead, sulfur, barium, or any combination of the previously listed components. In some embodiments, the fluid includes hydrocarbons (for example, hydrocarbons derived from various forms of petroleum including, but not limited to, paraffinic petroleum, paraffinic-naphthenic petroleum, naphthenic petroleum, paraffinic-naphthenic-aromatic petroleum, and aromatic petroleum) and polyaromatic hydrocarbons. In some embodiments, a separation of the complexing agent from one or more of the other components in the fluid is performed, for example to reduce or eliminate spectral contributions from the other components (that is, “background noise”) during measurement, a discussion of which is forthcoming.
In step 1006, the extracted fluid (or a separated/purified portion of the fluid) is combined with a second composition including a concentration of a lanthanide ion to form a third composition that includes a concentration of a complex formed by the first complexing agent and the lanthanide ion. As previously discussed, a separation of the complex that is formed from one or more of the other components in the third composition can optionally be performed at this stage to purify the complex prior to subsequent detection.
In step 1008, a quantity of the third composition (or a purified solution derived from the third composition) is exposed to electromagnetic radiation to detect (and, in some embodiments, quantitatively measure) the complex. In some embodiments, the wavelength of the exciting electromagnetic radiation is in the ultraviolet region of the spectrum.
In general, exposure to the illumination radiation occurs for a first time period ending at a time t0. As explained previously, background components in the third composition undergo fluorescence from time t0 (which is defined as the time point at which the excitation process has ended) until a later time t1 (which is defined as the time point at which fluorescence from the background components has decayed to an intensity level that is no longer detectable).
In step 1010, luminescence emission is detected from the irradiated complex, beginning at time t1>t0. In general, the interval t1−t0 is selected to ensure that the measured luminescence emission from the irradiated complex is not contaminated with significant contributions from background components (that is, other components present in the third composition). In some embodiments, for example, the interval t1−t0 is greater than 2 microseconds (for example, greater than 5 microseconds, greater than 8 μs, greater than 10 μs, greater than 15 μs, greater than 20 μs, greater than 25 μs, greater than 30 μs, greater than 35 μs, greater than 40 μs, greater than 50 μs, or greater than 100 μs).
In step 1012, information is determined about fluid flow between the first location (the injection site) and the second location (the extraction site) within the reservoir based on the detected luminescence emission. The information can indicate, for example, whether a particular injection bore and extraction bore are interconnected through the reservoir, and, if connected, can also indicate how fluid flows through the reservoir.
For example, if a tracer is introduced into a reservoir and subsequent sample extraction from a producing bore shows the presence of the tracer, a connection exists between the point of injection and the point of extraction.
Correlations between the presence of the tracer in the extracted fluid and the elapsed time between injection and detection of the tracer can also provide information about fluid flow through the reservoir. As an example, the elapsed time between injection and the appearance of the tracer in the extracted fluid (for example, in a measurement process where fluid is extracted periodically and analyzed) can provide information about the fluid flow capacity of the reservoir, the interconnected-ness of flow pathways, and residual oil saturation, which is difficult to acquire directly by other means.
In some embodiments, the information includes the concentration of the first complexing agent. Due to the enhancement of luminescence of the complexes and reduction or elimination of background fluorescence, as discussed previously, a minimum concentration of the first complexing agent in the third composition (formed in step 1006) that can be detected is between about 1 part per million and about 1 part per sextillion (for example, about 1 part per million and about 299 parts per billion, about 300 parts per billion (ppb) and about 1.1 parts per billion (ppb), about 1 part per billion (ppb) and about 499 parts per quadrillion (ppq), about 500 parts per quadrillion and about 1.1 parts per quadrillion, about 1 part per quadrillion (ppb) and about 499 parts per quintillion (ppq), about 500 parts per quintillion and about 1.1 parts per quintillion, about 1 part per quintillion and about 499 parts per sextillion, about 500 parts per sextillion and about 1 part per sextillion).
In general, it is possible to use more than one (for example, 2, 3, 4, 5, from 6 to 10, from 11 to 20, from 21 to 50, or from 51 to 100) complexing agents in the disclosed methods, for example to determine information about flow paths between multiple injection locations and an extraction location of a reservoir.
In
Although not shown in
Typically, at each location, the complexing agent introduced differs from the complexing agents introduced at the other locations so that information specific to the flow path between that location and the extraction location can be determined. Each of the complexing agents that are introduced can correspond to one of the complexing agents discussed in a subsequent section.
Further, in some embodiments, step 1106 is omitted and the resulting method includes the introduction of only the first and second complexing agents, with subsequent steps excluding the processing and presence of the third complexing agent.
In step 1108, a fluid is extracted from the reservoir at a second location that differs from each of the locations where the various compositions were introduced into the reservoir. The extracted fluid generally includes a quantity (that is, a concentration) of each of the first, second, and third complexing agents. Optionally, a separation procedure can be performed on the extracted fluid to isolate portions of the first, second, and third complexing agents from one another to facilitate analysis of the complexing agents.
Suitable separation procedures for isolating the different complexing agents include, but are not limited to, chromatographic separation techniques such as liquid chromatography and gas chromatography. In general, these techniques can isolate a relative large number of different complexing agents from an initial mixture. For example,
In step 1110, the extracted fluid (or the complexing agents isolated from the extracted fluid) is (are) combined with a second composition that includes a concentration of one or more types of lanthanide ions to form a third composition. In general, complexes are formed between each of the complexing agents present in the extracted fluid and the one or more types of lanthanide ions. Following formation of the different types of complexes (for example, complexes involving lanthanide ions and each of the first, second, and third complexing agents), a separation procedure is typically performed to isolate quantities of the various types of complexes. Each type of complex formed acts, in effect, as a “reporter” for fluid flow information within the reservoir between the injection site of the corresponding complexing agent and the extraction site. A variety of different separation procedures can be used in step 1110, including (but not limited to) chromatographic methods (for example, liquid chromatography), extraction, and fractionation.
In step 1112, each of the isolated quantities of the various complexes are exposed to electromagnetic radiation for a time period ending at time t0 to induce luminescence emission from each of the complexes. The luminescence emission is detected in step 1114 starting at time t1>t0, following the end of the illumination. As discussed previously, the interval t1−t0 is selected so that at time t1, fluorescence emission from background components has decayed to a nearly (or completely) undetectable level, such that measurement of luminescence emission from each of the complexes occurs without confounding spectral contributions from background components. As in the methods of
In step 1116, information is determined about fluid flow paths between the various injection sites of the complexing agents (the first, third, and fourth locations) and the extraction site (the second location) from the measured luminescence of each of the complexes formed from complexing agents recovered at the extraction site. As discussed previously in connection with
To purify the extracted reservoir fluid from location 1208, the example process shown in
Each complexing agent, now substantially isolated from the other complexing agents, is then combined with a composition that includes lanthanide ions to form complexes, and fluorescence/luminescence spectroscopy methods are used to detect and, in some embodiments, determine quantitative information about the complexes.
Complexing Agents
A variety of different complexing agents can be used as molecular tracers to determine information associated with petroleum reservoirs according to the methods that have been discussed. In this section of the disclosure, various example complexing agents are described. It should be understood that any of the complexing agents discussed in this section can be used alone or in combination with any of the methods discussed in the previous sections of this disclosure to determine information about subsurface reservoirs and fluid flow through the reservoirs. In particular, any of the first, second, and third complexing agents referenced previously can be selected from among the various compounds corresponding to Formula (I), Formula (II), Formula (III), or any combination of these, as will be explained in detail.
In some embodiments, the complexing agent is a compound of Formula (I), or an anion or salt thereof:
where:
X is present or absent, and when present, is selected from the group consisting of: C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH;
R is selected from the group consisting of:
(xv) —C3-10 cycloalkyl that is optionally substituted with from 1-4 Rb,
each occurrence of Ra is independently selected from the group consisting of:
each occurrence of Rb is independently selected from the group consisting of:
each occurrence of R′ and R″ is independently selected from the group consisting of: H and C1-4 alkyl; or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached forms a ring including from 3-8 ring atoms, where the ring includes: (a) from 1-7 ring carbon atoms; and (b) from 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″), which are each independently selected from the group consisting of N, NH, O, and S.
In some embodiments,
X is C1-10 alkylene;
R is selected from the group consisting of:
each occurrence of Ra is independently selected from the group consisting of:
each occurrence of Rb is independently selected from the group consisting of:
each occurrence of R′ and R″ is independently selected from the group consisting of: H and C1-4 alkyl; or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached forms a ring including from 3-8 ring atoms, where the ring includes: (a) from 1-7 ring carbon atoms; and (b) from 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″), which are each independently selected from the group consisting of N, NH, O, and S.
In some embodiments, X is —CH2—. In some embodiments, X1 and X2 are both absent.
In some embodiments, R is (ii) —ORa, and where the Ra of —ORa is not (i) H or (ii) C1-8 alkyl substituted with —(C0-3 alkylene)-C3-6 cycloalkyl.
In some embodiments, R is selected from the group consisting of:
In some embodiments, R is selected from the group consisting of:
In any of the previous embodiments, each occurrence of Ra is independently selected from the group consisting of:
In any of the previous embodiments, each occurrence of Rb is independently selected from the group consisting of:
In any of the previous embodiments, each occurrence of Rb is independently selected from the group consisting of:
In any of the previous embodiments, each occurrence of R′ and R″ is independently selected from the group consisting of: H and C1-4 alkyl.
In some embodiments, the complexing agent is a compound of Formula (II), or an anion or salt thereof:
where:
each of X1 and X2 is independently present or absent, and when one or both are present, each is independently selected from the group consisting of: C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH;
each of R1 and R2 is independently selected from the group consisting of:
each occurrence of Ra is independently selected from the group consisting of:
each occurrence of Rb is independently selected from the group consisting of:
each occurrence of R′ and R″ is independently selected from the group consisting of: H and C1-4 alkyl; or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached forms a ring including from 3-8 ring atoms, where the ring includes: (a) from 1-7 ring carbon atoms; and (b) from 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″), which are each independently selected from the group consisting of N, NH, O, and S.
In some embodiments, each of X1 and X2 is independently present or absent, and when one or both are present, each is independently selected from the group consisting of: C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH;
each of R1 and R2 is independently selected from the group consisting of:
each occurrence of Ra is independently selected from the group consisting of:
each occurrence of Rb is independently selected from the group consisting of:
each occurrence of R′ and R″ is independently selected from the group consisting of: H and C1-4 alkyl; or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached forms a ring including from 3-8 ring atoms, where the ring includes: (a) from 1-7 ring carbon atoms; and (b) from 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″), which are each independently selected from the group consisting of N, NH, O, and S.
In some embodiments, X1 and X2 are both —CH2—. In some embodiments, X1 and X2 are both absent.
In some embodiments, R1 and R2 are independently selected from:
In some embodiments, R1 and R2 are independently selected from:
In some embodiments, R1 and R2 are each (ix) —NHRa (for example, —NH2). In certain of these embodiments, Ra is selected from (ii) C1-8 alkyl substituted with from 1-3 independently selected Rb, where at least one of the Rb is (xv) —OH.
In some embodiments, R1 and R2 are each (x) —NHC(O)NHRa. In some embodiments, R1 and R2 are each (xi) —NHC(O)ORa. In some embodiments, R1 and R2 are each (xii) —NHC(O)Ra.
In some embodiments, each of R1 and R2 is the same. In some embodiments, each of R1 and R2 is different.
In any of the previous embodiments, each occurrence of Ra is independently selected from the group consisting of:
In any of the previous embodiments, each occurrence of Rb is independently selected from the group consisting of:
In any of the previous embodiments, each occurrence of Rb is independently selected from the group consisting of:
In any of the previous embodiments, each occurrence of R′ and R″ is independently selected from the group consisting of: H and C1-4 alkyl.
In some embodiments, the complexing agent is a compound of Formula (III), or an anion or salt thereof:
where:
each of X1 and X2 is independently present or absent, and when one or both are present, each is independently selected from the group consisting of: C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH;
each of R1 and R2 is independently selected from the group consisting of:
each occurrence of Ra is independently selected from the group consisting of:
each occurrence of Rb is independently selected from the group consisting of:
each occurrence of R′ and R″ is independently selected from the group consisting of: H and C1-4 alkyl; or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached forms a ring including from 3-8 ring atoms, where the ring includes: (a) from 1-7 ring carbon atoms; and (b) from 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″), which are each independently selected from the group consisting of N, NH, O, and S.
In some embodiments, each of X1 and X2 is independently present or absent, and when one or both are present, each is independently selected from the group consisting of: C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene, where each C1-10 alkylene, C2-10 alkenylene, and C2-10 alkynylene is optionally interrupted by one O, S, or NH;
each of R1 and R2 is independently selected from the group consisting of:
each occurrence of Ra is independently selected from the group consisting of:
each occurrence of Rb is independently selected from the group consisting of:
each occurrence of R′ and R″ is independently selected from the group consisting of: H and C1-4 alkyl; or, if R′ and R″ are bonded to the same atom, R′ and R″ together with the atom to which each is attached forms a ring including from 3-8 ring atoms, where the ring includes: (a) from 1-7 ring carbon atoms; and (b) from 0-3 ring heteroatoms (in addition to the atom attached to R′ and R″), which are each independently selected from the group consisting of N, NH, O, and S.
In some embodiments, X1 and X2 are both —CH2—. In some embodiments, X1 and X2 are both absent.
In some embodiments, R1 and R2 are independently selected from:
In some embodiments, R1 and R2 are independently selected from:
In some embodiments, R1 and R2 are each (ix) —NHRa (for example, —NH2). In certain of these embodiments, Ra is selected from (ii) C1-8 alkyl substituted with from 1-3 independently selected Rb, where at least one of the Rb is (xv) —OH.
In some embodiments, R1 and R2 are each (x) —NHC(O)NHRa. In some embodiments, R1 and R2 are each (xi) —NHC(O)ORa. In some embodiments, R1 and R2 are each (xii) —NHC(O)Ra. In some embodiments, R1 and R2 are each —Cl.
In some embodiments, each of R1 and R2 is the same. In some embodiments, each of R1 and R2 is different.
In any of the previous embodiments, each occurrence of Ra is independently selected from the group consisting of:
In any of the previous embodiments, each occurrence of Rb is independently selected from the group consisting of:
In any of the previous embodiments, each occurrence of Rb is independently selected from the group consisting of:
In any of the previous embodiments, each occurrence of R′ and R″ is independently selected from the group consisting of: H and C1-4 alkyl.
In some embodiments, the complex includes water. In some embodiments, the complex includes two or more different complexing agents. Combinations of different complexing agents can be selected from among any of the agents disclosed previously.
In general, depending upon the one or more complexing agents used to form the complex and the lanthanide ion complexed, the resulting complex can have a variety of different geometries about the lanthanide ion. Examples of such geometries include, but are not limited to: trigonal bipyramidal; square pyramidal; octahedral; trigonal prismatic; pentagonal bipyramidal; face capped octahedral; trigonal prismatic, square face monocapped; cubic; square antiprismatic; dodecahedral; trigonal hexagonal bypyramidal; octahedral, trans-bicapped; trigonal prismatic, triangular face bicapped; trigonal prismatic, square face bicapped; and tricapped trigonal prismatic.
In general, any of the lanthanide elements can be used to form luminescent complexes for tracer detection. In some embodiments, the lanthanide ion in each complex can be selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. For example, the lanthanide ion is selected from the group consisting of samarium, europium, terbium, and dysprosium.
In some embodiments, the complex of Formula (I) includes a 1:1:2 molar ratio of lanthanide ion to complexing agent to water. In some embodiments, the complex of Formula (I) includes a 1:2:0 molar ratio of lanthanide ion to complexing agent to water.
In some embodiments, the complex of Formula (II) includes a 1:1:2 molar ratio of lanthanide ion to complexing agent to water. In some embodiments, the complex of Formula (II) includes a 1:2:1 molar ratio of lanthanide ion to complexing agent to water. In some embodiments, the complex of Formula (II) includes a 1:3:0 molar ratio of lanthanide ion to complexing agent to water.
Analysis and Enhancement of Reservoir Production
The information obtained using the methods described above can be used to analyze and improve reservoir production. Specifically, information obtained from cross-well tracers that incorporate the foregoing complexing agents can be used to adjust a variety of control parameters such as water injection rates and fluid extraction rates, to manage reservoir production. The use of tracer information can increase constraints on history matching processes that are used for reservoir analysis, and can provide a more cost-effective and non-instrusive method for monitoring and managing reservoirs than conventional methods such as pressure interference studies, loggings, additional well drillings, and tomography.
For example, inter-well tracer information can be integrated into algorithms such as an ensemble smoother with multiple data assimilation (ES-MDA-Tracer), which can improve history matching using using integrated production and tracer information, thereby generating accurate reservoir geological models with improved prediction accuracy. Such models can then be used to improve or optimize reservoir production.
Examples of methods of using tracer-derived information for analysis and improvement of reservoir production are described, for example, in U.S. patent application Ser. No. 15/786,372 entitled “Enhancing Reservoir Production Optimization Through Integrating Inter-Well Tracers”, filed on Oct. 17, 2017, the entire contents of which are incorporated herein by reference.
This section provides a number of specific examples to further illustrate the previous disclosure. These examples are not intended to limit the scope of the disclosure in any manner.
Compounds of Formula (I)
A variety of complexing agents of Formula (I), each having distinguishing moieties, were prepared through the derivatization of dimethyl 4-(hydroxymethyl)pyridine-2,6-dicarboxylate and dimethyl 4-chloropyridine-2,6-dicarboxylate as depicted in forthcoming Scheme 2. First, a versatile hydroxymethylated scaffold was prepared through hydroxymethylation of dimethyl pyridine-2,6-dicarboxylate (part “a”). Next, various transformations (for example, tosylation, iodination, part “b”) were carried out to generate a variety of complexing agents. Part “c” depicts the functionalization of a separate DPA derivative, dimethyl 4-chloropyridine-2,6-dicarboxylate, with imidazole-based moieties. Part “d” illustrates the functionalization of dimethyl 4-carboxypyridine-2,6-dicarboxylate, a synthetic precursor achieved from the oxidation of dimethyl 4-(hydroxymethyl)pyridine-2,6-dicarboxylate (shown in part “b”). Zwitterionic derivatives of DPA may also be synthesized from its imidazole-conjugated variants, as shown in part “e”.
A solution of dipicolinic acid (4.00 grams (g), 24 millimoles (mmol)) in methanol (50 milliliters (ml)) and concentrated sulfuric acid (10 ml) was heated for 18 hours (h). Water (30 ml) was added and the aqueous solution was neutralized with sodium carbonate. The solution was acidified with concentrated HCl and extracted with chloroform (4×25 ml). The combined extracts were dried, filtered and concentrated to leave a white solid. Crystallization from chloroform gave dimethyl dipicolinate as a white powder (2.87 g, 96%). Proton nuclear magnetic resonance spectral peaks (1H NMR) (500 Megahertz (MHz), CDCl3) δ=8.33 (doublet (d), 2H), 8.03 (triplet (t), 1H), 4.03 (singlet (s), 6H).
Solutions of Fe(ClO4)2·6H2O (4.64 g, 12.8 mmol) in H2O (4.7 mL) and H2O2 (30% weight/weight (w/w) aqueous solution, 8 mL, 77.6 mmol) were added dropwise at 0° C. over 30 minutes (min) to a mixture of DPA dimethyl ester (2.5 g, 12.8 mmol) 7, MeOH (7.5 mL) and HClO4 (70% w/w aqueous solution, 5.6 mL, 9.32 g, 64.9 mmol). The reaction mixture was allowed to warm up slowly to room temperature and it was stirred at this temperature for 3 h. The volatile components were evaporated under reduced pressure, and the pH of the residue was adjusted to 9 with saturated Na2CO3 solution. The aqueous solution was extracted with EtOAc (3×30 mL) and the combined organic phase was dried over MgSO4, filtered and the solvent was removed. The residue was recrystallized from toluene to give the titled compound (1.87 g, 65%) as white crystals. Melting point (mp): 158-159° C. (toluene) (literature mp (lit. mp): 154-158° C.), Rf=0.11 (SiO2 thin-layer chromatography (TLC); EtOAc-toluene 1:1). 1H NMR (500 MHz, CDCl3) δ=8.32 (s, 2H), 4.91 (d, 2H), 4.03 (s, 6H), 2.06 (t, 1H).
To a solution of dimethyl 4-(hydroxymethyl)pyridine-2,6-dicarboxylate (2 g, 8.8 mmol) in 50 ml acetone was added solid KMnO4 (4.21 g, 26.6 mmol), with stirring. The reaction mixture was allowed to stir for 3 hours at room temperature, then quenched with aqueous NaHSO3 within an ice bath. The resulting solution was then filtered over celite and the collected precipitate was washed with water. Concentration of the collected filtrate (to remove acetone) was followed by acidification of the remaining aqueous phase to pH 2 using 1 molar (M) HCl, which was then subjected to extraction with ethyl acetate. The combined organic phase was dried with MgSO4, filtered, and concentrated to afford the product as a white powder (50%). 1H NMR (500 MHz, DMSO-d6) δ=14.29 (broad (br), 1H), 8.55 (s, 2H), 3.95 (s, 6H).
To a cooled solution of dimethyl 4-hydroxymethylpyridine-2,6-dicarboxylate (2.15 g, 9.56 mmol) in dichloromethane (20 ml) was added dropwise a solution of tosyl chloride (2.37 g, 12.4 mmol), after which the resulting solution was stirred for 20 min at 0° C. Triethylamine (6 ml) was then added dropwise in three portions at 20 min intervals. After the addition was complete, the solution was allowed to stir at 0° C. for an additional 15 min, followed by 15 min at room temperature. The resulting solution was diluted with EtOAc (40 ml), washed with water (2×20 ml) and 3M HCl (2×20 ml). The organic phase was then dried over MgSO4, filtered, and the solvent removed in vacuo to yield a brown powder, which was washed with diethyl ether (3×10 ml) to give the product as a tan powder (2.52 g, 70%). 1H NMR (500 MHz, CDCl3) δ=8.17 (s, 2H), 7.82 (d, 2H), 7.35 (d, 2H), 5.18 (s, 2H), 4.02 (s, 6H), 2.45 (s, 3H).
To a solution of dimethyl 4-hydroxymethylpyridine-2,6-dicarboxylate (3.0 g, 13.3 mmol) in anhydrous CHCl3 was added SOCl2 (2.4 g, 20 mmol) dropwise under argon atmosphere at −5° C. with continuous stirring for 40 min. Excess solvent was removed in vacuo and the crude product was recrystallized from EtOH (50 ml) to give the product as a yellow solid after drying in vacuum (2.8 g, 86%). 1H NMR (500 MHz, CDCl3) δ=8.30 (s, 2H), 4.67 (s, 2H), 4.50 (q, 4H), 1.47 (t, 6H).
To a solution of NaI (4.50 g, 30 mmol) in acetone (250 ml) was added dimethyl 4-tosyloxylmethylpyridine-2-6-dicarboxylate (7.58 g, 20 mmol). The reaction mixture was then heated at reflux for 2.5 h, after which the cooled solution was diluted with EtOAc (550 ml), and the organic phase was washed with water (3×150 ml), 3% HCl (3×120 ml), and 5% w/w Na2SO3 (2×50 ml). The organic phase was dried over Na2SO4 in darkness and concentrated in vacuo to give the product (5.23 g, 78%). 1H NMR (500 MHz, CDCl3) δ=8.27 (s, 2H), 4.44 (s, 2H), 4.03 (s, 6H).
Mixtures of dimethyl 4-chloropyridine-2,6-dicarboxylate (1 equivalent (eq.)) and imidazole/4-methylimidazole/4-ethylimidazole (5 (eq.)) were heated to 130° C. for 3.5 h in the absence of solvent. Upon cooling the dark reaction mixture was diluted with water and acidified to pH 3-4 using 1M HCl, precipitating the product as a brown powder (70-80%).
4-(1H-imidazol-1-yl)pyridine-2,6-dicarboxylic acid: 1H NMR (500 MHz, DMSO-d6) δ=13.63 (br, 2H), 8.76 (s, 1H), 8.5 (s, 2H), 8.19 (s, 1H), 7.19 (s, 1H).
4-(4-methyl-1H-imidazol-1-yl)pyridine-2,6-dicarboxylic acid: 1H NMR (500 MHz, DMSO-d6) δ=13.56 (br, 2H), 8.63 (s, 1H), 8.41 (s, 2H), 7.86 (s, 1H), 2.17 (s, 3H). 4-(4-ethyl-1H-imidazol-1-yl)pyridine-2,6-dicarboxylic acid: 1H NMR (500 MHz, DMSO-d6) δ=13.59 (br, 2H), 8.65 (s, 1H), 8.44 (s, 2H), 7.89 (s, 1H), 2.53 (quadruplet (q), 2H), 1.21 (t, 3H).
The pyridine dicarboxylic acids were first esterified to their methyl esters according to the procedure outlined below. A mixture of the resultant product (1 eq.) and 1,3-propanesultone (3 eq.) was then heated at 130° C. for 2 h. Upon cooling, the crude reaction was washed with MeOH and the resulting precipitate was filtered to give the desired product as a brown powder. Subsequent acid catalyzed hydrolysis was carried out as follows: compounds (dimethyl ester form) were suspended in 2 M HCl and heated at 80° C. for 2.5 h. Upon cooling, the desired product formed as a precipitate. The mixture was then filtered and washed with acetone to afford the product as a tan to brown powder. 1-[2,6-bis(methoxycarbonyl)-4-pyridyl]-3-(3-sulfopropyl)-4-methyl-1H-imidazolium: 1H NMR (500 MHz, D2O) δ=9.59 (s, 1H), 8.57 (s, 2H), 7.89 (s, 1H), 4.38 (t, 2H), 3.98 (s, 6H), 2.96 (t, 2H), 2.39 (s, 3H), 2.31 (sext, 2H).
1-[2,6-bis(methoxycarbonyl)-4-pyridyl]-3-(3-sulfopropyl)-1H-imidazolium: 1H NMR (500 MHz, D2O) δ=9.69 (s, 1H), 8.62 (s, 2H), 8.13 (s, 1H), 7.81 (s, 1H), 4.48 (t, 2H), 3.99 (s, 6H), 2.93 (t, 2H), 2.36 (sext, 2H).
The dicarboxylic acid (1 eq.) was charged with methanol (50 ml) and concentrated sulfuric acid (3 eq.) and subsequently refluxed for 16 h. The methanol was then concentrated in vacuo and the residue was triturated with saturated NaHCO3, then water. The combined organic layers were dried over Na2SO4 and then the solvent was removed under reduced pressure to afford the desired ester as a tan solid.
General Procedure for the Hydrolysis of Dipicolinic Acids:
The following procedure was used to hydrolyze most 4-substituted dimethyl 2,6-pyridine dicarboxylate derivatives in addition to dimethyl 4-carboxypyridine-2,6-dicarboxylate. To a stirred solution of dimethyl ester in MeOH (10 ml) was added an equal volume of NaOH (20% weight/volume (w/v)). The reaction mixture was stirred overnight at room temperature and concentrated in vacuo. The residue was dissolved in the minimum required amount of water and acidified with conc. HCl. If a precipitate was obtained at this stage, the solution was cooled on ice and the precipitate was isolated by filtration and dried in vacuo to afford the desired carboxylic acid. If no precipitation occurred at this stage, the aqueous phases were repeatedly extracted with EtOAc, the organic layers were combined, dried (Na2SO4) and concentrated in vacuo to afford the desired carboxylic acid.
Compounds of Formula (II)
A variety of complexing agents of Formula (II), each having a unique distinguishing moiety, were prepared through the derivatization of bathocuproine (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) as shown in Scheme 3a. Chlorination of bathocuproine followed by subsequent oxidation yields 4,7-diphenyl-1,10-phenanthroline-2,9-dicarboxylic acid (DPPDA), an intermediate product which undergoes treatment with HClSO3 to ultimately give 4,7-diphenyl-1,10-phenanthroline-2,9-dicarboxylic acid disulfonate (BCPDCA). As shown in Scheme 3b, DPPDA may also undergo nitration to afford 4,7-bis(nitrophenyl)-1,10-phenanthroline-2,9-dicarboxylic acid, which may undergo further reduction to yield 4,7-bis(aminophenyl)-1,10-phenanthroline-2,9-dicarboxylic acid.
A mixture composed of bathocuproine (1.5 g, 4.13 mmol), N-chlorosuccinimide (3.375 g, 25.1 mmol), benzoyl peroxide (4.1 mg) and 36 ml chloroform was stirred and refluxed for 6 hrs in an oil bath at 90° C. The mixture was refrigerated overnight to allow precipitation of succinimide crystals, which were removed by vacuum filtration. The filtrate was then washed/extracted with 100 ml (2×50 ml) of saturated potassium carbonate solution (112 g/100 ml) and the organic layer was then dried over anhydrous MgSO4. Removal of solvent yielded the pale yellow solid product. Yield=81-93%. 1H NMR (500 MHz, CDCl3) δ=8.27 (s, 2H), 8.0 (s, 2H), 7.57 (m, 10H).
A 25 mL microwave vial was charged with 2,9-bis(trichloromethyl)-4,7-diphenyl-1,10-phenanthroline (1.612 g, 2.848 mmol) and 4 mL of concentrated H2SO4. The solution was stirred in a 90° C. oil bath for 2 h. After cooling to room temperature, 11 ml of deionized (DI) water was added dropwise to the continuously stirred reaction mixture. The resulting suspension was heated for an additional hour at 90° C. Upon cooling to room temperature, the solution was quenched into a 40 mL mixture of crushed ice and water. The resulting precipitate was collected via vacuum filtration. Yield=95% (hydrated). 1H NMR (500 MHz, DMSO-d6) δ=13.7 (br, 2H), 8.29 (s, 2H), 8.04 (s, 2H), 7.65 (m, 10H).
To a 25 mL microwave vial was added 5 mL of 97% ClSO3H. The solution was cooled by placing in an ice bath. Cautiously, small aliquots of 4,7-diphenyl-1,10-phenanthroline-2,9-dicarboxylic acid was added to the stirred mixture until a total of 1 g was added. The mixture was then heated to 80° C. for 4 h. Upon cooling to room temperature, the solution was quenched into 100 mL of ice water in a drop wise fashion (Caution—this process is extremely exothermic). The resulting light yellow/beige powder was collected via vacuum filtration and lyophilized. Yield=79%. 1H NMR (500 MHz, DMSO-d6) δ=8.29 (s, 2H), 8.05 (s, 2H), 7.58-7.9 (multiplet (m), 8H), 5.7 (br, 2H).
Hydrolysis of 4,7-bis(chlorosulfonylphenyl)-1,10-phenanthroline-2,9-dicarboxylic acid was carried out using dilute NaOH (aqueous (aq)) pH 10 solutions. The chlorosulfonyl compound was suspended in pH 10 solution and mechanically stirred at room temperature until fully dissolved. The pH of the resulting solution was adjusted using dilute HCl solution until a final value of pH 6 was obtained.
To 3 ml of cold 90% HNO3 was added DPPDA (0.42 g, 1 mmol) in small portions, after which the mixture was stirred for 4.5 h in an ice bath. The reaction mixture was then poured over 100 ml crushed ice, yielding a yellow solid, and subsequently filtered and lyophilized to give the final product (96%). 1H NMR (500 MHz, DMSO-d6) δ=13.8 (br, 2H), 8.54-7.56 (m, 12H).
Compounds of Formula (III)
A variant of complexing agents of Formula (III), each having distinguishing moieties, was prepared through the derivatization of 1,10-phenanthroline-2,9-dicarboxylic acid as depicted in forthcoming Scheme 4. First, precursor a was synthesized; subsequent reactions using a as a precursor yielded compound b, identified as 4,7-dichloro-2,9-dimethyl-1,10-phenanthroline. Compound b then underwent further transformations to yield 4,7-dichloro-1,10-phenanthroline-2,9-dicarboxylic acid.
Trimethyl orthoformate (500 mL, 3.83 mol) and Meldrum's acid (20.0 g, 139 mmol) was brought to a gentle reflux for 15 min. The resulting yellow solution was cooled (80° C.) and o-phenylenediamine (6.90 g, 63.1 mmol) was added portionwise (exothermic reaction). The resulting mixture was refluxed for 2 h, and left under stirring at rt for 16 h, where a white precipitate formed. The precipitate was filtered off, washed with diethyl ether (4×100 mL) and dried to afford the product as a flaky white solid.
To diphenyl ether (500 mL) at 240° C. was added a (17.5 g, 38.7 mmol) in small portions, resulting in vigorous gas evolution. The resulting orange solution was brought to reflux for 30 min, and was then allowed to cool to 70° C., where a dark-brown solid precipitated. The formed precipitate was washed with acetone (2×90 mL), hexane (2×90 mL) and Et2O (2×90 mL) and dried to afford a fine dark-brown powder.
To phosphoryl chloride (220 mL) under nitrogen was added 2,9-dimethyl-1,10-phenanthroline-4,7(1H,10H)-dione (8.50 g, 35.4 mmol) and the resulting solution was stirred at 90° C. for 3.5 h. The hot solution was slowly added to a well-stirred mixture of ice (700 g) in water (300 mL). After stirring for 15 min, chloroform (200 mL) was added and the resulting two-layer system was carefully brought to pH 13-14 by adding NaOH solution (42.5%, ca. 450 mL). The organic layer was separated and the aqueous layer was extracted four times with 200 mL of chloroform. The combined organic layers were washed with NaOH solution (42.5%, 200 mL) and dried over MgSO4. Evaporation of the brown colored solvent afforded b as light tan crystals.
A stirred solution of b (9.00 g, 32.5 mmol), N-chlorosuccinimide (31.2 g, 234 mmol) and a catalytic amount of benzoyl peroxide (20 mg) in chloroform (700 mL) was refluxed overnight. The reaction mixture was washed with saturated aqueous K2CO3 (2×200 mL), dried over MgSO4 and concentrated to afford a solid, which was purified by flash-chromatography (2% EtOAc in petroleum ether) to give the product as white crystals.
A stirred mixture of 4,7-dichloro-2,9-bis(trichloromethyl)-1,10-phenanthroline (13.00 g, 26.9 mmol) in concentrated H2SO4 (16 mL) was heated to 95° C. for 2 h. After cooling, H2O (50 mL) was slowly added with rapid stirring. The resulting mixture was heated to reflux for 1 h. The mixture was cooled and the formed precipitate was washed with H2O (5×40 mL) and Et2O (2×30 mL) and dried to afford the product as a light tan solid.
One advantageous feature of molecular tracers for reservoir characterization is relatively uniform physical and chemical properties across a broad range of (1) salinity (for example, from about 60,000 ppm to about 250,000 ppm total dissolved salts) and (2) temperature (for example, from about 60° C. to about 105° C.), over relatively long periods of time, for example, while the tracer traverses a path from the injection well to the producing well. To evaluate properties of the disclosed tracers, the BCPDCA ligand was subjected to thermal stability tests in synthetic seawater at reservoir-like temperature. The composition of the synthetic seawater used is shown in Table 1.
200 ppb of BCPDCA, complexed with europium (III) using a 10−5M solution of europium ions, was maintained at 103° C. in synthetic seawater over 11 days to determine whether its fluorescence intensity had changed.
Photophysical characterizations of the complexes including lanthanide ions and complexing agents were performed under experimental conditions that favored the formation of a 1:1 complex between a ligand and a lanthanide ion by including an excess of the lanthanides in solution.
Next, formation of the complex in produced water (which is oil contaminant-containing water) from a hydrocarbon reservoir, in which there existed excess calcium ions in solution, was performed.
As shown in
To determine the retention of BCPDCA materials in reservoir rocks under simulated reservoir conditions, mobility experiments were performed with parameters and results tabulated in Table 2, and described in forthcoming detail.
Coreflood Device and Conditions
A CoreTest Systems Inc. BPS-805Z Permeability System was used as a coreflood device. For the carbonates studied, values of confinement pressure Pconf=4,400 psi, pore pressure Ppore=3,200 psi, and temperature T=90° C. were used to replicate conditions in parts of the Ghawar reservoir in Saudi Arabia.
Saturation and Injection Brines
To reduce variables from transient salinity, the salinity of both the saturation fluid and injection fluid were matched for each respective experiment (for synthetic seawater, the core was saturated and flooded in seawater and the subsequent tracer ligand injection and flushes were all performed with seawater). The seawater used was intended to mimic the ionic composition of the injected fluid used throughout Saudi Arabia during water-flooding operations.
Tracer Injection and Analysis
The experiments were conducted at displacement velocities of 0.5 mL/min in Indiana Limestone. The brine flushing phase was conducted at the same displacement velocities as the tracer injections to avoid mobilization resulting from advection gradients. A tandem injection scheme was used. For the DPA and FBA comparison experiment, first FBA (˜3 PV) was injected, followed by a flush of 5 pore volume of seawater before the DPA tracers are injected as a slug (˜3 PV). A similar injection scheme was adopted for the BCPDCA & NaBr coreflood experiment.
For determining the tracer concentration, an Agilent spectrophotometer was used to measure the UV-VIS absorbance at a wavelength of 270 nm for DPA, and 290 nm for BCPDCA. For the ideal non-reactive ionic tracer NaBr, a bromine ion selective electrode was used to measure the eluents. A new 5-point calibration curve was made for each experiment measured. By comparing the effluent sample absorbance to the known values of the standards, a normalized concentration was derived for each fraction collected, annotated as C/C0 (fraction of effluent sample concentration divided by input concentration; a value of 1.0 indicates the effluent solution is equal to the injected concentration). The fraction collector vials were weighed before and after sample collection to determine a collected mass from each vial. The known mass along with the known densities of the injection fluids allowed for volume calculations and validation of the injection rates.
Coreflood Tests using BCPDCA
BCPDCA in synthetic seawater was injected into a core at 200 mg/L at 90° C. Another test using an ionic tracer known to not attach to the rock matrix (0.1M NaBr in this case) in the same core was performed as well.
A similar test was conducted using DPA, and a fluorinated benzoic acid (FBA) as the inert reference.
Derivatives substituted with imidazolyl, 4-methylimidazolyl, and 4-ethylimidazolyl substituents at the 4-position of DPA were synthesized as shown in Scheme 2c. A mixture of DPA and three DPA derivatives substituted with imidazol-1-yl (DPA-im), 4-methylimidazol-1-yl (DPA-Mim) and 4-ethylimidazol-1-yl (DPA-Eim) groups at concentrations of 10 ppm each in water was chromatographically separated by UHPLC.
Fluorescence intensities of DPA, imidazol-1-ylDPA, and 4-methylimidazol-1-yl DPA at the same molar concentrations were measured after complexation with terbium ions.
To assess the mobility of the molecular tracers through carbonate rocks under simulated reservoir conditions, coreflood experiments were performed. A one-foot long limestone core (permeability ˜200 mDarcy, other properties shown in Table 3) was flooded with synthetic seawater, then flooded with Arabic medium crude (API ˜30°) and aged for three weeks at 100° C. At the end of aging, the core was oil flooded again and initial oil saturation, Soi, was calculated by mass balance. Then, the core was waterflooded with seawater to obtain residual oil saturation, Sorw, by mass balance. For the tracer flood, both the ideal ionic tracer, potassium chloride (KCl), and one of the molecular tracers described above were injected at the same pulse width of 0.5 pore volume (PV). The concentration of KCl was 1000 ppm in seawater, whereas the molecular tracer concentration was 100 ppm. Injection was followed by several PV chase of synthetic seawater. The concentration of potassium ions in the effluent was determined using ion chromatography while the concentration of the molecular tracer was measured by UV-Vis spectrophotometry.
Coreflood experimental conditions are summarized in Table 4.
To assess the detectability of the molecular tracers in the field, a study was performed using a specific well pair.
A total of 5 kg of the first molecular tracer was first dissolved in approximately 200 L of deionized water. At the well site, a pre-flush of 4 barrels of treated seawater was administered at a rate of 0.35 bbl/min. Then, the molecular tracer was injected at I3 at a rate of 0.40 bbl/min. After the injection, a post flush with 10 barrels of treated seawater was injected at 0.5 bbl/min. Seawater injection at 3000 psi at a rate of approximately 8000 bbl/day resumed immediately post flush.
Produced water samples from producer well P3 were collected twice weekly. A cursory clean-up procedure involving solid phase extraction and fraction collection on a high performance liquid chromatograph was performed before the addition of lanthanide ions for the fluorescence measurements. With these additional steps, the cycle time for sample work up was still comparatively shorter than tracer detection methodologies for FBAs using quadrupole GC/MS.
The recovery curve of the first molecular tracer is shown in
Reservoir modeling methodologies have shown that active rate management is an effective way to augment productivity, particularly in mature fields. Although the value of tracer data in elucidating reservoir heterogeneity and reducing uncertainties is undeniable, its utility in fortifying the fidelity of reservoir history matching and enhancing production optimization algorithms does not appear to have been studied systematically.
Using reservoir history matching and production optimization algorithms, it was recently demonstrated that tracer data can improve field production net present values (NPVs) by +0.3% to +9.4% for non-homogeneously flooded reservoirs. The present example shows results of further feasibility studies for scaled-up reservoir models.
Permeability fields of the scaled-up reference reservoir models with five-spot waterflood patterns are shown in
A number of embodiments have been described. Nevertheless, it will be understood that various modifications may be made without departing from the scope of the disclosure. Accordingly, other embodiments are within the scope of the following claims.
This application is a divisional of and claims the benefit of priority to U.S. patent application Ser. No. 17/551,598, filed on Dec. 15, 2021, which is a divisional of U.S. patent application Ser. No. 16/252,228, filed on Jan. 18, 2019, now issued as U.S. Pat. No. 11,230,919 on Jan. 25, 2022, which claims priority to U.S. Provisional Application No. 62/619,000, filed on Jan. 18, 2018, and to U.S. Provisional Application No. 62/758,046, filed on Nov. 9, 2018, the entire contents of each of which are incorporated herein by reference.
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| 20230184099 A1 | Jun 2023 | US |
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| 62758046 | Nov 2018 | US | |
| 62619000 | Jan 2018 | US |
| Number | Date | Country | |
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| Parent | 17551598 | Dec 2021 | US |
| Child | 18162495 | US | |
| Parent | 16252228 | Jan 2019 | US |
| Child | 17551598 | US |
