Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/02—Well-drilling compositions
  • C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
  • C09K8/36—Water-in-oil emulsions

Definitions

• This invention relates to monoester-based drilling fluid compositions, their methods of preparation and methods for use in a subterranean formation in oil and gas recovery operations, wherein they are made from at least one biologically-derived precursor and/or Fischer-Tropsch product(s).
• Drilling fluids employing synthetic fluids (i.e., monoester-based drilling fluids) as the base fluid are capable of achieving 96 hour LC5 0 Mysid shrimp (Mysidopsis bahia) bioassay test results greater than 100,000 ppm. However, even with these bioassay test results their commercial use has been severely restricted.
• a drilling fluid which employs an inexpensive, nontoxic synthetic fluid as the base fluid.
• the present invention satisfies this need by providing a drilling fluid comprising: (a) at least one drilling fluid additive (e.g., an emulsifier, a viscosifier, a weighting agent, and an oil-wetting agent) and (b) an inexpensive, non-toxic base fluid composed of monoester(s).
• a drilling fluid additive e.g., an emulsifier, a viscosifier, a weighting agent, and an oil-wetting agent
• an inexpensive, non-toxic base fluid composed of monoester(s).
• the monoesters prepared from C6-C41 carboxylic acids and Cs-C84 olefins of the subject invention provide excellent properties for use in drilling fluids.
• the monoesters of this invention have a lower viscosity and excellent gel strength at high temperature and pressure than the current commercially available esters on the market today.
• the present invention is directed to a method for drilling a borehole in a subterranean formation comprising the steps of: a) rotating a drill bit at the bottom of the borehole; and b) introducing a drilling fluid into the borehole to pick up drill cuttings and to carry at least a portion of the drill cuttings out of the borehole, wherein the drilling fluid comprises: i) at least one additive selected from the group consisting of emulsifiers, wetting agents, viscosifiers, weighting agents, and fluid loss control agents; and ii) a quantity of at least one monoester of Formula I:
• Ri and R2 and are independently selected from Ci to Cs and R3 is C5 to C13.
• Figure 1 is a flow diagram illustrating a method of making monoesters for incorporation in monoester-based drilling fluid compositions.
• Figure 2(a) illustrates a generic monoester
• Figure 2(b) illustrates octyl hexanoate monoesters
• Figure 2(c) illustrates decyl hexanoate monoesters.
• the present invention is directed to a method for drilling a borehole in a subterranean formation comprising the steps of: a) rotating a drill bit at the bottom of the borehole; and b) introducing a drilling fluid into the borehole to pick up drill cuttings and to carry at least a portion of the drill cuttings out of the borehole, wherein the drilling fluid comprises: i) at least one additive selected from the group consisting of emulsifiers, wetting agents, viscosifiers, weighting agents, and fluid loss control agents; and ii) a quantity of at least one monoester of Formula I, wherein said steps are performed continually.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the monoester of Formula I is biodegradable and non-toxic.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the monoester of Formula I is derived from an isomerized olefin.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein Ri and I3 ⁇ 4 are independently selected from Ci
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein Ri and R2 are independently selected from Ci to C5 and R 3 is C5 to Cs.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein Ri and R2 are independently selected from Ci
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the kinematic viscosity of the monoester of Formula I at a temperature of 100 °C is between about 0.5 cSt to 2 cSt, a temperature of 40 °C is between about 2 cSt to 4 cSt and a temperature of 0 °C is between about 4 cSt to 12 cSt.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the monoester of Formula I has an Oxidator BN of greater than 30 hours.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the monoester of Formula I has an Oxidator BN of greater than 50 hours. In some embodiments, the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the monoester of Formula I has an Oxidator BN of greater than 60 hours.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the monoester of Formula I has a pour point less than about -20 °C.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the monoester of Formula I has a pour point less than about -60 °C.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the drilling fluid has a pour point less than about 10 °C and a viscosity at 40 °C between about 1 cSt to about 10 cSt.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the drilling fluid has a 10 second gel strength between about 2 lb/ 100 sq ft to about 15 lb/ 100 sq ft.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the drilling fluid has a 10 second gel strength of about 2 lb/100 sq ft at about 93.3 °C and about 1000 psig.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the drilling fluid has a 10 second gel strength of about 1 lb/100 sq ft at about 121.1 °C and about 15000 psig.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the drilling fluid produced a rheological property profile in the Fann 77 illustrated in Table 2A.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the drilling fluid produced a rheological property profile in the Fann 77 illustrated in Table 2B.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the drilling fluid has a 10 minute gel strength between about 1 lb/ 100 sq ft to about 17 lb/ 100 sq ft.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein R3 is C5. In some embodiments, the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein R 3 is C5 and Ri and R2 are C 2 .
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein R 3 is C5 and Ri and R2 are C3.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the at least one monoester of Formula I is an octyl hexanoate, its isomers, and mixtures thereof.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the at least one monoester of Formula I is decyl hexanoate, its isomers, and mixtures thereof.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the at least one monoester of Formula I is a mixture of an octyl hexanoate, its isomers, and a decyl hexanoate, its isomers, and mixtures thereof.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the drilling fluid of Step (b) comprises between about 20 wt% to 40 wt% of the monoester of Formula I.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the drilling fluid of Step (b) further comprises: a. between about 1.0 wt% to about 3.0 wt% of the emulsifier and wetting agent; b. between about 0.1 wt% to about 1.5 wt% of an organophilic clay;
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the drilling fluid comprises a monoester selected from the group consisting of hexanyl hexanoate and isomers, hexanyl octanoate and isomers, hexanyl decanoate and isomers, hexanyl laureate and isomers, hexanyl palmitate and isomers, hexanyl hexadecanoate and isomers, hexanyl stearate and isomers, octanyl hexanoate and isomers, octanyl octanoate and isomers, octanyl decanoate and isomers, octanyl laureate and isomers, octanyl palmitate and isomers, octanyl hexadecanoate and isomers, octanyl hexano
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the drilling fluid further comprises the components: (a) lime, (b) fluid loss control agent, (c) an aqueous solution comprising water and the shale inhibiting salt, (d) oil wetting agent, (e) non-sulfonated polymer, (f) sulfonated polymer and (g) non-organophilic clay.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the at least one monoester of Formula I has a molecular mass that is from at least about 144 a.m.u, to at most about 592 a.m.u.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the monoester of Formula I is derived from an internal olefin. In some embodiments, the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the monoester of Formula I is derived from a secondary alcohol.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the monoester of Formula I is secondary monoester.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the -0(CO)R 3 group of Formula I is not bound to the terminus of Ri or R2.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the monoester of Formula I does not comprise products derived from oligomerization.
• the present invention is directed to a method for drilling a borehole in a subterranean formation, wherein the monoester of Formula I does not comprise products derived from alpha olefins.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I:
• Ri and R2 and are independently selected from Ci to Cs and R 3 is C5 to C13.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the monoester of Formula I is biodegradable and non-toxic.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the monoester of Formula I is derived from an isomerized olefin.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein Ri and R2 and are independently selected from Ci to Cs and R 3 is C5 to C12. In some embodiments, the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein Ri and R2 are independently selected from Ci to C5 and R 3 is C5 to C 8 .
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein Ri and R2 are independently selected from Ci to C3 and R 3 is C5 to Ce.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the kinematic viscosity of the monoester of Formula I at a temperature of 100 °C is between about 0.5 cSt to 2 cSt, a temperature of 40 °C is between about 2 cSt to 4 cSt and a temperature of 0 °C is between about 4 cSt to 12 cSt.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the monoester of Formula I has an Oxidator BN of greater than 30 hours.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the monoester of Formula I has an Oxidator BN of greater than 50 hours.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the monoester of Formula I has an Oxidator BN of greater than 60 hours.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the monoester of Formula I has a pour point less than about -20 °C.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the monoester of Formula I has a pour point less than about -60 °C.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the drilling fluid has a pour point less than about 10 °C and a viscosity at 40 °C between about 1 cSt to about 10 cSt.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the drilling fluid has a 10 second gel strength between about 2 lb/100 sq ft to about 15 lb/100 sq ft. In some embodiments, the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the drilling fluid has a 10 second gel strength of about 2 lb/100 sq ft at about 93.3 °C and about 1000 psig.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the drilling fluid has a 10 second gel strength of about 1 lb/100 sq ft at about 121.1 °C and about 15000 psig.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the drilling fluid produced a rheological property profile in the Fann 77 illustrated in Table 2A.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the drilling fluid produced a rheological property profile in the Fann 77 illustrated in Table 2B.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the drilling fluid has a 10 minute gel strength between about 1 lb/ 100 sq ft to about 17 lb/ 100 sq ft.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein R 3 is C5.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein R 3 is C5 and Ri and R2 are C 2 .
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein R 3 is C5 and Ri and R2
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the at least one monoester of Formula I is an octyl hexanoate, its isomers, and mixtures thereof.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the at least one monoester of Formula I is decyl hexanoate, its isomers, and mixtures thereof.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the at least one monoester of Formula I is a mixture of an octyl hexanoate, its isomers, and a decyl hexanoate, its isomers, and mixtures thereof.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the drilling fluid of Step (b) comprises between about 20 wt% to 40 wt% of the monoester of Formula I.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the drilling fluid further comprises:
• a between about 1.0 wt% to about 3.0 wt% of the emulsifier and wetting agent; b. between about 0.1 wt% to about 1.5 wt% of an organophilic clay;
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the drilling fluid comprises a monoester selected from the group consisting of hexanyl hexanoate and isomers, hexanyl octanoate and isomers, hexanyl decanoate and isomers, hexanyl laureate and isomers, hexanyl palmitate and isomers, hexanyl hexadecanoate and isomers, hexanyl stearate and isomers, octanyl hexanoate and isomers, octanyl octanoate and isomers, octanyl decanoate and isomers, octanyl laureate and isomers, octanyl palmitate and isomers, octanyl hexadecanoate and isomers, o
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the drilling fluid further comprises the components: (a) lime, (b) fluid loss control agent, (c) an aqueous solution comprising water and the shale inhibiting salt, (d) oil wetting agent, (e) non- sulfonated polymer, (f) sulfonated polymer and (g) non-organophilic clay.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the at least one monoester of Formula I has a molecular mass that is from at least about 144 a.m.u, to at most about 592 a.m.u.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the monoester of Formula I is derived from an internal olefin.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the monoester of Formula I is derived from a secondary alcohol.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the monoester of Formula I is secondary monoester.
• the present invention is directed to a drilling fluid composition
• a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the -0(CO)R3 group of Formula I is not bound to the terminus of Ri or R2.
• the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the monoester of Formula I does not comprise products derived from oligomerization. In some embodiments, the present invention is directed to a drilling fluid composition comprising a quantity of at least one monoester of Formula I, wherein the monoester of Formula I does not comprise products derived from alpha olefins.
• the monoester-based drilling fluids of the present invention may comprise one or more of the following:
• Surfactants e.g., emulsifiers, wetting agents), viscosifiers, weighting agents, fluid loss control agents, and shale inhibiting salts are also optionally used in the drilling fluid of the present invention. Because the drilling fluids of the present invention are intended to be non-toxic, these optional ingredients, like the monoester, are preferably also non-toxic.
• Exemplary emulsifiers include, but are not limited to, fatty acids, soaps of fatty acids, and fatty acid derivatives including amido-amines, polyamides, polyamines, esters (such as sorbitan monoleate polyethoxylate, sorbitan dioleate polyethoxylate), imidaxolines, and alcohols.
• Typical wetting agents include, but are not limited to, lecithin, fatty acids, crude tall oil, oxidized crude tall oil, organic phosphate esters, modified imidazolines, modified amidoamines, alkyl aromatic sulfates, alkyl aromatic sulfonates, and organic esters of polyhydric alcohols.
• Exemplary weighting agents include, but are not limited to barite, iron oxide, gelana, siderite, and calcium carbonate.
• Common shale inhibiting salts are alkali metal and alkaline-earth metal salts. Calcium chloride and sodium chloride are the preferred shale inhibiting salts.
• Exemplary viscosifiers include, but are not limited to, organophilic clays (e.g., hectorite, bentonite, and attapulgite), non-organophilic clays (e.g., montmorillonite (bentonite), hectorite, saponite, attapulgite, and illite), oil soluble polymers, polyamide resins, and polycarboxylic acids and soaps.
• organophilic clays e.g., hectorite, bentonite, and attapulgite
• non-organophilic clays e.g., montmorillonite (bentonite), hectorite, saponite, attapulgite, and illite
• oil soluble polymers e.g., polyamide resins, and polycarboxylic acids and soaps.
• fluid loss control agents include, but are not limited to, asphaltics (e.g., asphaltenes and sulfonated asphaltenes), amine treated lignite, and gilsonite.
• asphaltics e.g., asphaltenes and sulfonated asphaltenes
• amine treated lignite e.g., amine treated lignite
• gilsonite e.g., g., g., amine treated lignite
• the fluid loss control agent is preferably a polymeric fluid loss control agent.
• Exemplary polymeric fluid loss control agents include, but are not limited to, polystyrene, polybutadiene, polyethylene, polypropylene, polybutylene, polyisoprene, natural rubber, butyl rubber, polymers consisting of at least two monomers selected from the group consisting of styrene, butadiene, isoprene, and vinyl carboxylic acid. Individual or mixtures of polymeric fluid loss control agents can be used in the drilling fluid of this invention.
• pour point depressants are employed in the synthetic fluids (i.e., monoester-based drilling fluids) of the present invention to lower their pour point.
• Typical pour point depressants include, but are not limited to, ethylene copolymers, isobutylane polymers, polyaklylnaphthalenes, wax-aromatic condensation products (e.g., wax-naphthalene condensation products, phenol-wax condensation products), polyalkylphenolesters, polyalkylmethacrylates, polymethacrylates, polyalkylated condensed aromatics, alkylaromatic polymers, iminodiimides, and polyalkylstyrene.
• the molecular weights for polyaklylnaphthalenes, polyalkylphenolesters, and polyalkylmethacrylates range from about 2,000 to about 10,000) Because they are non-toxic, ethylene copolymers and isobutylene polymers are the preferred pour point depressants.
• the weight percent of the pour point depressant is based upon the weight of the monoester, i.e., it is the weight of the pour point depressant divided by the weight of the monoester, the quotient being multiplied by 100%
• the pour point depressant is employed in a concentration of 0.005 to about 0.5, more preferably about 0.01 to about 0.4, and most preferably about 0.02 to about 0.3, weight percent.
• the pour point depressant is preferably mixed with the monoester and the resulting composition is then combined with any additional additives as described herein.
• the properties (e.g., monoester to water ratio, density, etc.) of the drilling fluids of the invention can be adjusted to suit any drilling operation.
• the drilling fluid is usually formulated to have a volumetric ratio of monoester to water of about 100:0 to about 40:60 and a density of about 0.9 kg/1 (7.5 pounds per gallon (ppg)) to about 2.4 kg/1 (20 ppg). More commonly, the density of the drilling fluid is about 1.1 kg/1 (9 ppg) to about 2.3 kg/1 (19 ppg).
• the drilling fluids are preferably prepared by mixing the constituent ingredients in the following order: (a) monoester, (b) emulsifier, (c) lime (when employed), (d) fluid loss control agent (when employed), (e) an aqueous solution comprising water and the shale inhibiting salt, (f) organophilic clay, (g) oil wetting agent, (h) weighting agent, (i) non- sulfonated polymer (when employed), (j) sulfonated polymer (when employed), and (k) non- organophilic clay (when employed).
• the present invention is additionally directed to methods of making the above-described lubricant compositions.
• the olefins disclosed here may be alpha olefins produced by gas to liquid processes (GTL) refining processes, petrochemical processes, pyrolysis of waste plastics and other processes, are isomerized into internal olefins followed by conversion into monoesters.
• the alpha olefins are isomerized into internal olefins using double bond isomerization catalyst including molecular sieves such as SAPO-39 and medium pore zeolites such as SSZ-32 and ZSM-23.
• processes for making the above-mentioned monoester species comprise the following steps: (Step 101) epoxidizing an internal olefin (or quantity of olefins) having a carbon number of from C6-Cs4 to form an epoxide or a mixture of epoxides; (Step 102) opening the epoxide rings via reduction methods to form the corresponding mono secondary alcohol; and (Step 103) esterifying (i.e., subjecting to esterification) the secondary alcohol with a C6-C41 carboxylic acid to form internal monoester species.
• lubricant compositions comprising such monoester species have a viscosity in the range from 0.5 centistokes to 2 centistokes at a temperature of 100° C.
• the quantity of monoester species can be substantially homogeneous, or it can be a mixture of two or more different such monoester species.
• the olefin used is a reaction product of a Fischer-Tropsch process.
• the carboxylic acid can be derived from alcohols generated by a Fischer-Tropsch process and/or it can be a bio- derived fatty acid.
• the olefin is an a-olefin (i.e., an olefin having a double bond at a chain terminus).
• a-olefin i.e., an olefin having a double bond at a chain terminus.
• isomerize the olefin so as to internalize the double bond.
• Such isomerization is typically carried out catalytically using a catalyst such as, but not limited to, crystalline aluminosilicate and like materials and aluminophosphates. (see, e.g., U.S. Patent No's.
• Fischer-Tropsch alpha olefins can be isomerized to the corresponding internal olefins followed by epoxidation.
• the epoxides can then be transformed to the corresponding secondary mono alcohols via epoxide ring reduction followed by esterifying (i.e., di-esterification) with the appropriate carboxylic acids or their acylating derivatives.
• esterifying i.e., di-esterification
• the ester groups with their polar character would further enhance the viscosity of the final product. Branching, introduced by internalizing the ester groups, will enhance the cold temperature properties such as pour and cloud points. Viscosity can be increased by increasing the carbon number of the internal olefin or the acid used in the esterification.
• the above-described olefin (preferably an internal olefin) can be reacted with a peroxide (e.g., H 2 O 2 ) or a peroxy acid (e.g., peroxyacetic acid) to generate an epoxide, (see, e.g., D. Swern, in Organic Peroxides Vol. II, Wiley-Interscience, New York, 1971, pp. 355-533; and B. Plesnicar, in Oxidation in Organic Chemistry, Part C, W. Trahanovsky (ed.), Academic Press, New York 1978, pp. 221-253).
• a peroxide e.g., H 2 O 2
• a peroxy acid e.g., peroxyacetic acid
• Olefins can be efficiently transformed to the corresponding diols by highly selective reagent such as osmium tetra-oxide (see M. Schroder, Chem. Rev. vol. 80, p. 187, 1980) and potassium permanganate (see Sheldon and Kochi, in Metal-Catalyzed Oxidation of Organic Compounds, pp. 162-171 and 294-296, Academic Press, New York, 1981).
• highly selective reagent such as osmium tetra-oxide (see M. Schroder, Chem. Rev. vol. 80, p. 187, 1980) and potassium permanganate (see Sheldon and Kochi, in Metal-Catalyzed Oxidation of Organic Compounds, pp. 162-171 and 294-296, Academic Press, New York, 1981).
• this step is done by epoxide ring reduction using metal hydrides reduction procedures or noble metal-catalyzed hydrogenations processes. Both procedures are very effective at making the needed secondary alcohols for internal epoxides.
• an acid is typically used to catalyze the esterification reaction of alcohols and carboxylic acids.
• Suitable acids for esterification include, but are not limited to, sulfuric acid (see Munch-Peterson, Org. Synth., V, p. 762, 1973), sulfonic acid (see Allen and Sprangler, Org Synth., Ill, p. 203, 1955), hydrochloric acid (see Eliel et al, Org Synth., IV, p. 169, 1963), and phosphoric acid (among others).
• the carboxylic acid used in this step is first converted to an acyl chloride (e.g., thionyl chloride or PCI 3 ).
• an acyl chloride could be employed directly.
• an acid catalyst is not needed and a base such as pyridine, 4-dimethylaminopyridine (DMAP) or triethylamine (TEA) is typically added to react with an HCl produced.
• DMAP 4-dimethylaminopyridine
• TAA triethylamine
• pyridine or DMAP it is believed that these amines also act as a catalyst by forming a more reactive acylating intermediate, (see, e.g., Fersh et al, J. Am. Chem. Soc, vol. 92, pp. 5432-5442, 1970; and Hofle et al, Angew. Chem. Int. Ed. Engl, vol. 17, p. 569, 1978).
• the carboxylic acid used in the above-described method is derived from biomass.
• this involves the extraction of some oil (e.g., triglyceride) component from the biomass and hydrolysis of the triglycerides of which the oil component is comprised so as to form free carboxylic acids.
• oil e.g., triglyceride
• Drilling Fluid refers to any of a number of liquid and gaseous fluids and mixtures of fluids and solids (as solid suspensions, mixtures and emulsions of liquids, gases and solids) used in operations to drill boreholes into the earth. Synonymous with “drilling mud” in general usage, although some prefer to reserve the term “drilling fluid” for more sophisticated and well-defined "muds.”
• Rheological measurements of a drilling fluid include plastic viscosity (PV), yield point (YP) and gel strengths. The information from these measurements can be used to determine hole cleaning efficiency, system pressure losses, equivalent circulating density, surge and swab pressures and bit hydraulics.
• PV plastic viscosity
• YP yield point
• gel strengths The information from these measurements can be used to determine hole cleaning efficiency, system pressure losses, equivalent circulating density, surge and swab pressures and bit hydraulics.
• Fluid Loss Control Agent includes, but are not limited to, asphaltics (e.g., asphaltenes and sulfonated asphaltenes), amine treated lignite, and gilsonite.
• asphaltics e.g., asphaltenes and sulfonated asphaltenes
• amine treated lignite e.g., amine treated lignite
• gilsonite e.g., amine treated lignite
• the fluid loss control agent is preferably a polymeric fluid loss control agent.
• Exemplary polymeric fluid loss control agents include, but are not limited to, polystyrene, polybutadiene, polyethylene, polypropylene, polybutylene, polyisoprene, natural rubber, butyl rubber, polymers consisting of at least two monomers selected from the group consisting of styrene, butadiene, isoprene, and vinyl carboxylic acid. Individual or mixtures of polymeric fluid loss control agents can be used in the drilling fluid of this invention.
• Organic Clay or “Viscosifiers” refers to CARBO-GEL® II (Baker-2).
• Bentonite and hectorite are platelet clays that will increase viscosity, yield point and build a thin filter cake to aid in reducing the fluid loss.
• a number of polymers are available for use in non-aqueous fluids. These polymers increase fluid carrying capacity and may also function as fluid loss control additives. They include: elastomeric viscosifiers, sulfonated polystyrene polymers, styrene acrylate, fatty acids and dimer-trimer acid combinations.
• Emsifiers and Wetting Agents refers to primary emulsifiers which are generally very powerful, fatty acid based surfactants. They usually require lime to activate and build a stable emulsion. Secondary emulsifiers, often called wetting agents, are typically based on imidazolines or amides (e.g., OMNI-MUL®, Baker-Hughes), and do not require lime to activate. They are designed to oil-wet solids and also emulsify oil. To formulate stable water in oil mixtures, the use of surfactants is required. Surfactants lower surface tension and emulsify the internal water phase and "oil wet" solids. In practice, emulsifiers are classified as either “primary” or “secondary”, depending on the desired application.
• Salt refers to CaC3 ⁇ 4 used to make drilling fluids or brines with a suitable density. CaC3 ⁇ 4 can be blended with other brines, including NaCl, CaBr 2 and ZnBr 2 . Emulsification of Ca(3 ⁇ 4 brine as the internal phase of synthetic -based mud is an important use because the brine provides osmotic wellbore stability while drilling water-sensitive shale zones.
• Weighting Agents refers to barite (barium sulfate) (e.g. MICROMAXTM) as used to increase the density of drilling fluids.
• Other weighting agents are hematite (iron oxide), managanese tetraoxide and calcium carbonate. These weighting materials increase the density of the external phase of the fluids.
• Latex Filtration Control Agent refers to Pliolite® (Goodyear) polymers.
• Simulated Drill Solids refers to powdered clay as used to simulate drilled formation particles.
• non-Organophilic Clay refers to a clay which has not been amine-treated to convert the clay from water-yielding to oil-yielding.
• Mud Weight refers to a mud fluid property for balancing and controlling downhole formation pressures and promoting wellbore stability. Mud densities are usually reported in pounds per gallon (lb/gal). As most drilling fluids contain at least a little air/gas, the most accurate way to measure the density is with a pressurized mud balance.
• Liquid lime refers to quicklime (CaO), quicklime precursors, and hydrated quicklime (e.g., slaked lime (Ca(OH) 2 ).
• the term "interface” indicates a boundary between any two immiscible phases and the term “surface” denotes an interface where one phase is a gas, usually air.
• Base oils used as motor oils are generally classified by the American Petroleum Institute as being mineral oils (Group I, II, and III) or synthetic oils (Group IV and V). See American Petroleum Institute (API) Publication Number 1509.
• Pour point refers to the lowest temperature at which a fluid will pour or flow, (see, e.g., ASTM International Standard Test Methods D 5950-96, D 6892-03, and D 97). The results are reported in degrees Celsius. Many commercial base oils have specifications for pour point. When base oils have low pour points, the base oils are also likely to have other good low temperature properties, such as low cloud point, low cold filter plugging point, and low temperature cranking viscosity.
• Cloud Point refers to the temperature at which a fluid begins to phase separate due to crystal formation. See, e.g., ASTM Standard Test Methods D 5773-95, D 2500, D 5551, and D 5771.
• cSt kinematic viscosity of a fluid
• centistoke e.g., a lubricant
• R n refers to a hydrocarbon group, wherein the molecules and/or molecular fragments can be linear and/or branched.
• C n where "n” is an integer, describes a hydrocarbon molecule or fragment (e.g., an alkyl group) wherein “n” denotes the number of carbon atoms in the fragment or molecule.
• Bio refers to an association with a renewable resource of biological origin, such as resource generally being exclusive of fossil fuels.
• Group I Base Oil refers to a base oil which contains less than 90 percent saturates and/or greater than 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the ASTM methods specified in Table E-l of American
• Group II Base Oil refers to a base oil which contains greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and has a viscosity index greater than or equal to 80 and less than 120 using the ASTM methods specified in Table E-l of American Petroleum Institute Publication 1509.
• Group 11+ Base Oil refers to a Group II base oil having a viscosity index greater than or equal to 1 10 and less than 120.
• Group III Base Oil refers to a base oil which contains greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and has a viscosity index greater than or equal to 120 using the ASTM methods specified in Table E-l of American Petroleum Institute Publication 1509.
• Fischer-Tropsch Derived refers to a product, fraction, or feed that originates from or is produced at some stage by a Fischer-Tropsch process.
• Petroleum Derived refers to a product, fraction, or feed originates from the vapor overhead streams from distilling petroleum crude and the residual fuels that are the non-vaporizable remaining portion.
• a source of the petroleum derived product, fraction, or feed can be from a gas field condensate.
• Highly Paraffinic Wax refers to a wax having a high content of n- paraffins, generally greater than 40 wt %, but can be greater than 50 wt %, or even greater than 75 wt %, and less than 100 wt % or 99 wt %.
• highly paraffinic waxes include slack waxes, deoiled slack waxes, refined foots oils, waxy lubricant raffinates, n- paraffin waxes, NAO waxes, waxes produced in chemical plant processes, deoiled petroleum derived waxes, microcrystalline waxes, Fischer-Tropsch waxes, and mixtures thereof.
• Representative examples include, but are not limited to, benzene, biphenyl, naphthalene, and the like.
• Molecules with Cycloparaffinic Functionality refers to any molecule that is, or contains as one or more substituents, a monocyclic or a fused multicyclic saturated hydrocarbon group.
• the cycloparaffinic group can be optionally substituted with one or more, such as one to three, substituents.
• Representative examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl, decahydronaphthalene, octahydropentalene, (pentadecan-6-yl)cyclohexane, 3,7,10-tricyclohexylpentadecane, decahydro-l-(pentadecan-6-yl)naphthalene, and the like.
• Molecules with Monocycloparaffinic Functionality refers to any molecule that is a monocyclic saturated hydrocarbon group of three to seven ring carbons or any molecule that is substituted with a single monocyclic saturated hydrocarbon group of three to seven ring carbons.
• the cycloparaffinic group can be optionally substituted with one or more, such as one to three, substituents. Representative examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl, (pentadecan-6- yl)cyclohexane, and the like.
• Molecules with Multicycloparaffinic Functionality refers to any molecule that is a fused multicyclic saturated hydrocarbon ring group of two or more fused rings, any molecule that is substituted with one or more fused multicyclic saturated hydrocarbon ring groups of two or more fused rings, or any molecule that is substituted with more than one monocyclic saturated hydrocarbon group of three to seven ring carbons.
• the fused multicyclic saturated hydrocarbon ring group often is of two fused rings.
• the cycloparaffinic group can be optionally substituted with one or more, such as one to three, substituents.
• Representative examples include, but are not limited to, decahydronaphthalene, octahydropentalene, 3,7,10-tricyclohexylpentadecane, decahydro- 1 -(pentadecan-6- yl)naphthalene, and the like.
• Kinematic Viscosity refers to a measurement of the resistance to flow of a fluid under gravity. Many base oils, lubricant compositions made from them, and the correct operation of equipment depends upon the appropriate viscosity of the fluid being used. Kinematic viscosity is determined by ASTM D445-06. The results are reported in mm 2 /s.
• Viscosity Index refers to an empirical, unitless number indicating the effect of temperature change on the kinematic viscosity of the oil. Viscosity index is determined by ASTM D2270-04.
• Oxidator BN refers to a measurement of the response of a base oil in a simulated application. High values, or long times to adsorb one liter of oxygen, indicate good stability. Oxidator BN can be measured via a Dornte-type oxygen absorption apparatus (see R. W. Dornte "Oxidation of White Oils," Industrial and Engineering Chemistry, Vol. 28, page 26, 1936), under 1 atmosphere of pure oxygen at 340 °F. The time, in hours, to absorb 1000 ml of O2 by 100 grams of oil is reported. In the Oxidator BN test, 0.8 ml of catalyst is used per 100 grams of oil. The catalyst is a mixture of soluble metal-naphthenates simulating the average metal analysis of used crankcase oil. The additive package is 80 millimoles of zinc bispolypropylenephenyldithiophosphate per 100 grams of oil.
• Example 1 is provided to demonstrate particular embodiments of the present invention. It should be appreciated by those of skill in the art that the methods disclosed in the examples which follow merely represent exemplary embodiments of the present invention. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments described and still obtain a like or similar result without departing from the spirit and scope of the present invention.
• Example 1 is provided to demonstrate particular embodiments of the present invention. It should be appreciated by those of skill in the art that the methods disclosed in the examples which follow merely represent exemplary embodiments of the present invention. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments described and still obtain a like or similar result without departing from the spirit and scope of the present invention.
• Example 1 is provided to demonstrate particular embodiments of the present invention. It should be appreciated by those of skill in the art that the methods disclosed in the examples which follow merely represent exemplary embodiments of the present invention. However, those of skill in the art
• the epoxy octanes with little residual hexane produced according to example 1 were reduced with lithium aluminum hydride in THF (Tetrahydrofuran) according to the procedure described below.
• the products from example 1 were divided into two equal portions and each portion was reduced separately with lithium aluminum hydride in anhydrous THF. Assuming full conversion of the octenes to epoxides in example 1 , each portion was assumed to contain 1.18 moles (151.3 grams) of epoxy octanes.
• reaction was then heated to reflux for an hour or so to ensure reduction completion.
• the reaction progress was monitored by NMR and IR analysis on small aliquots work-up.
• the heat source was replaced with an ice-bath and the reaction was worked up by first diluting with 500 ml THF and then adding 550 ml of 15% NaOH solution via a dropping funnel with vigorous stirring and not allowing the temperature of the reaction to rise above room temperature (very slow addition). The addition continued until all the grey solution transformed into a milky solution which was left to stir for addition 30 minutes. The stirring was stopped and the solution nicely separated into a clear liquid phase and a fine white precipitate.
• the mixture was cooled down by means of an ice-bath and left to stir at around 0 °C for 15 minutes.
• 148 grams (1.1 mol.) of hexanoyl chloride was added drop-wise via a dropping funnel over 45 minutes. Once all hexanoyl chloride was added the reaction was left to stir and warm slowly to room temperature. The reaction, then, was refluxed and monitored by NMR and IR analysis. Once the reaction was completed, the resulting milky creamy solution was worked up by adding water until all the solids disappeared and a clear solution formed (two phase solution). The two phase solution was separated in a separatory funnel and the organic phase was washed with water and brine and saved.
• the mixture of octanols was also esterified with hexanoic acid in toluene and using phosphoric acid as catalyst according to the procedure shown below.
• the reaction apparatus consisted of a 3 -neck 1L reaction flask equipped with an overhead stirrer, reflux condenser with a Dean-Stark trap and a heating mantle.
• the reaction vessel was charged with 50 gm (0.38 mol.) of octanols mixture, 66 gm (0.57 mol.) hexanoic acid, 5 gm of 85% phosphoric acid, and 250 ml toluene.
• the mixture was heated at reflux ( ⁇ 1 10 °C) for 6 hrs and left to stir at reflux overnight.
• N/A is defined as "not available”.
• the octyl hexanoate mixture was evaluated for oxidation stability by measuring how much time it takes for a given amount of the ester to absorb 1 liter of Oxygen using the Oxidator BN test.
• Octyl hexanoates exhibited superior oxidation stability with 64 hrs (see Table 1 above).
• An invert emulsion drilling fluid was prepared by (a) initially agitating 166.0 grams of the ester from Example 4 (Octyl Hexanoates) for about one minute using a blender and (b) then sequentially adding the following ingredients (with continuous mixing for about one minute after the addition of each material): (i) 16.0 grams of an emulsifier and wetting agent
• An invert emulsion drilling fluid was prepared by (a) initially agitating 168.076 grams of the ester from Example 4 (Octyl Hexanoates) for about one minute using a blender and (b) then sequentially adding the following ingredients (with continuous mixing for about one minute after the addition of each material): (i) 12.0 grams of an emulsifier and wetting agent
• the following materials were added in sequence, with about 5 minutes of mixing after the addition of each of the materials: (i) 300.3 grams of powdered barite (a non-toxic weighting agent); (ii) 17.2 grams of calcium chloride dehydrate (to provide salinity to the water phase without water wetting the barite); (iii) 2.0 grams of a latex filtration control agent (Pliolite®, Goodyear); and (iv) 40.0 grams of a powdered clay to simulate drilled formation particles. The final density of the drilling fluid was 14 pounds per gallon (about 1.7 kg/1).
• Example 7 The rheology of the drilling fluid of Example 7 was evaluated in a Fann ⁇ 77 instrument (Fann Instrument Company, Houston, TX), according to procedures described in Recommended Practice-Standard Procedure for Field Testing Drilling Fluids, API Recommended Practice 13B-2 (RP 13B-2), Second Edition, Dec. l, 1991, American Petroleum Institute, Washington, D.C. The measured results are given in Table 2A. These results show that the ester of Example 4 can be used to make an acceptable drilling fluid, and has exceptionally low gel strength at high temperature (200 °F and higher). Table 2A
• N/A is defined as "not available”.
• the rheology of the drilling fluid of Example 8 was evaluated in a Fann ⁇ 77 instrument (Fann Instrument Company, Houston, TX), according to procedures described in Recommended Practice-Standard Procedure for Field Testing Drilling Fluids, API Recommended Practice 13B-2 (RP 13B-2), Second Edition, Dec. l, 1991, American Petroleum Institute, Washington, D.C. The measured results are given in Table 2B. These results show that the ester of Example 4 can be used to make an acceptable drilling fluid, and has exceptionally low gel strength at high temperature (200 °F and higher).
• N/A is defined as "not available”.
• the monoester produced a rheological property profile in the Fann 77 test that is unique and different.
• the difference lies in the low gel strengths at 200 °F and 250 °F and high pressure.
• the formulation showed no indication of settling in the instrument.
• the gel strengths are very flat and non-progressive.
• the benefit itself would be the reduced pump pressure required to initiate circulation after a prolonged drilling cessation.

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