NO20120438A1 - Oil-based drilling fluids and mixture for use in oil-based drilling fluids - Google Patents
Oil-based drilling fluids and mixture for use in oil-based drilling fluids Download PDFInfo
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- 238000005553 drilling Methods 0.000 title claims abstract description 96
- 239000012530 fluid Substances 0.000 title claims abstract description 93
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 3
- 125000000129 anionic group Chemical group 0.000 claims description 13
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 description 55
- 239000003921 oil Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 12
- 238000000518 rheometry Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- -1 SG 4.7-4.9) Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 208000005156 Dehydration Diseases 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910052601 baryte Inorganic materials 0.000 description 3
- 239000010428 baryte Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 3
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910052923 celestite Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 229910052949 galena Inorganic materials 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000004164 Wax ester Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 235000019386 wax ester Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Lubricants (AREA)
Abstract
Den foreliggende oppfinnelse vedrører en oljebasert borevæske omfattende et vektmiddel hvor borevæsken inneholder alkoholetoksylater med en molekylvekt mellom 200 og 2000 Dalton som bionedbrytbart deflokkuleringsmiddel. Oppfinnelsen vedrører videre en tørr blanding for bruk i oljebaserte borevæsker omfattende et vektmiddel og et deflokkuleringsmiddel hvor deflokkuleringsmiddelet er alkoholetoksylat med en molekylvekt mellom 200 og 2000 Daltons.The present invention relates to an oil-based drilling fluid comprising a weight agent wherein the drilling fluid contains alcohol ethoxylates having a molecular weight between 200 and 2000 Dalton as biodegradable deflocculant. The invention further relates to a dry composition for use in oil-based drilling fluids comprising a weighting agent and a deflocculant, wherein the deflocculant is alcohol ethoxylate having a molecular weight between 200 and 2000 Daltons.
Description
Teknisk område Technical area
Den foreliggende oppfinnelse vedrører ikke-vanndige borevæsker (NDF) og en blanding for bruk i ikke-vanndige borevæsker. The present invention relates to non-aqueous drilling fluids (NDF) and a mixture for use in non-aqueous drilling fluids.
Bakgrunnsteknologi Background technology
Ved utvinning av olje og gass blir borevæsker generelt benyttet for å tjene bestemte funksjoner, slik som å løfte borepartikler til overflaten, smøring av boresegmenter, opprettholde trykket i brønnen, osv. When extracting oil and gas, drilling fluids are generally used to serve specific functions, such as lifting drilling particles to the surface, lubricating drill segments, maintaining pressure in the well, etc.
Det finnes to hovedklasser av borevæsker, vannbaserte og ikke-vanndige (oljebaserte) borevæsker. Oljebaserte borevæsker er også kjent som inverterte emulsjoner, og er basert på diesel eller mineralolje som kontinuerlig fase og inneholder viskositetsmodifiserende midler slik som organofil leire eller syntetiske polymerer, vanndig fase, normalt CaCfc brine, emulsifiserende midler og fuktemidler, fluid loss kontrollerende midler så som syntetiske hydrofobe polymerer eller gilsonitt eller asfalten og vektmidler, slik som et hvilket som helst partikulært materiale med en spesifikk vekt normalt >2g/cm<3>There are two main classes of drilling fluids, water-based and non-aqueous (oil-based) drilling fluids. Oil-based drilling fluids are also known as inverted emulsions, and are based on diesel or mineral oil as the continuous phase and contain viscosity modifying agents such as organophilic clay or synthetic polymers, aqueous phase, normally CaCfc brine, emulsifying agents and wetting agents, fluid loss controlling agents such as synthetic hydrophobic polymers or gilsonite or asphaltene and weighting agents such as any particulate material with a specific gravity normally >2g/cm<3>
De vanlig benyttede vektmidler for å kontrollere tettheten av borevæsker er baritt (BaS04, spesifikk vekt (SG) minimum 4,2) mangantetraoksid (Mn304, SG 4,7-4,9), kalsiumkarbonat (CaC03, SG 2,7-2,8), ilmenitt (FeTi03, SG 4,5-4,7) hematitt (Fe304, SG 4,9-5,2), sideritt (FeC03lSG 3,96), galena (PbS, SG 7,2-7,6), celestitt (SrS04, SG 3,96) og andre. The commonly used weights to control the density of drilling fluids are barite (BaS04, specific gravity (SG) minimum 4.2) manganese tetraoxide (Mn304, SG 4.7-4.9), calcium carbonate (CaC03, SG 2.7-2, 8), ilmenite (FeTi03, SG 4.5-4.7) hematite (Fe304, SG 4.9-5.2), siderite (FeC03lSG 3.96), galena (PbS, SG 7.2-7.6 ), celestite (SrSO4, SG 3.96) and others.
I oljebaserte borevæsker er vektmidlene dispergert i oljefasen ved hjelp av emulsifiserende middel og fuktemiddel. Vektmidler, særlig vektmidler med en gjennomsnittlig partikkelstørrelse <10u har en tendens til å agglomerere eller flokkulere og danne store agglomerater, særlig ved høye temperaturer over In oil-based drilling fluids, the weighting agents are dispersed in the oil phase using emulsifying agents and wetting agents. Weighting agents, especially weighting agents with an average particle size <10u have a tendency to agglomerate or flocculate and form large agglomerates, especially at high temperatures above
>150°C og høy tetthet >1,6 SG. Slike agglomerater er uønsket fordi de endrer væskeegenskapene slik som reologi, filtrering og settling. For eksempel tenderer dannelse av agglomerater til å øke den plastiske viskositeten, yield stress og gelstyrke av fluidene og øker tap av væske til formasjonen. Betydelig flokkulering kan videre forårsake mange operasjonelle utfordringer slik som fastkiling av borerør, økning av motstanden mot rotasjon av borerøret, reduksjon av borehastigheten, ustabilt borehull og tap av >150°C and high density >1.6 SG. Such agglomerates are undesirable because they change the liquid properties such as rheology, filtration and settling. For example, formation of agglomerates tends to increase the plastic viscosity, yield stress and gel strength of the fluids and increases loss of fluid to the formation. Significant flocculation can further cause many operational challenges such as wedging of drill pipe, increased resistance to rotation of the drill pipe, reduction of drilling speed, unstable borehole and loss of
sirkulasjon. Slike utfordringer har en direkte innvirkning på den totale borekostnad. For å unngå slik dannelse av agglomerater tilsettes vanligvis et kjemisk middel, normalt kalt deflokkuleringsmiddel, dispergeringsmiddel eller tynner til borevæsken for å minimalisere partikkel-partikkel interaksjon. circulation. Such challenges have a direct impact on the total drilling cost. To avoid such formation of agglomerates, a chemical agent, normally called a deflocculating agent, dispersing agent or thinner, is usually added to the drilling fluid to minimize particle-particle interaction.
Eksisterende deflokkuleringsmiddler slik som Omni_cote<®>fra Baker Hughes, Versathin™ HF fra Ml Swaco eller OMC™ fra Baroid har ulemper så som skadelig for miljøet eller at de ikke fungerer godt under varierende boreomstendigheter. Når det gjelder ekotoksitet har noen av disse produktene blitt identifisert som mulig miljøskadelige og disse deflokkuleringsmidlene er ikke eller tungt bionedbrytbare. Existing deflocculation agents such as Omni_cote<®> from Baker Hughes, Versathin™ HF from Ml Swaco or OMC™ from Baroid have disadvantages such as being harmful to the environment or not working well under varying drilling conditions. In terms of ecotoxicity, some of these products have been identified as potentially harmful to the environment and these deflocculation agents are not or hardly biodegradable.
US patent 7,638,466 B2 beskriver en metode for boring av borehull i en underjordisk formasjon ved en temperatur i området mellom 4°C og 121°C. US patent 7,638,466 B2 describes a method for drilling boreholes in an underground formation at a temperature in the range between 4°C and 121°C.
Patentet beskriver bruk av ikke-ionisk overflateaktivt middel som tynner hvilket er fremstilt ved reaksjon av karboksylsyre med etylenoksid, propylen eller butylenoksider. The patent describes the use of a non-ionic surfactant as a thinner, which is produced by the reaction of carboxylic acid with ethylene oxide, propylene or butylene oxides.
US patent 7,871,962 B2 beskriver en borevæske med flat reologi ved bruk av polykarboksylfettsyre som reologimodifiserende middel. US patent 7,871,962 B2 describes a drilling fluid with flat rheology using polycarboxylic fatty acid as rheology modifying agent.
I tillegg til å være bionedbrytbar må deflokkuleringsmiddelet oppfylle en rekke betingelser. Det må være kompatibelt med mineralolje, det må være stabilt ved en temperatur av opp til minst 200°C og gi en tilfredstillende reologi for borevæsker ved forskjellige temperaturer. In addition to being biodegradable, the deflocculating agent must fulfill a number of conditions. It must be compatible with mineral oil, it must be stable at a temperature of up to at least 200°C and provide a satisfactory rheology for drilling fluids at different temperatures.
Det er således et behov for oljebaserte borevæsker inneholdende deflokkuleringsmidler som er bionedbrytbare, er kompatible med mineralolje, fuktemidler og andre tilsetningsmidler som normalt anvendes i oljebaserte borevæsker og være termisk stabile opp til minst 200°C. There is thus a need for oil-based drilling fluids containing deflocculating agents that are biodegradable, are compatible with mineral oil, wetting agents and other additives normally used in oil-based drilling fluids and are thermally stable up to at least 200°C.
Beskrivelse av oppfinnelsen Description of the invention
Den foreliggende oppfinnelse vedrører således en oljebasert borevæske omfattende et vektmiddel, hvilken borevæske inneholder alkoholetoksylater med en molekylvekt mellom 200 og 2000 Dalton som et deflokkuleringmiddel. The present invention thus relates to an oil-based drilling fluid comprising a weighting agent, which drilling fluid contains alcohol ethoxylates with a molecular weight between 200 and 2000 Dalton as a deflocculation agent.
Alkoholetoksylatene har fortrinnsvis en molekylvekt mellom 300 og 600 Dalton. The alcohol ethoxylates preferably have a molecular weight between 300 and 600 Dalton.
Borevæsken inneholder fortrinnsvis 1 til 15 g/l av alkoholetoksylat og mer foretrukket mellom 1,5 og 9 g/l av alkoholetoksylat. The drilling fluid preferably contains 1 to 15 g/l of alcohol ethoxylate and more preferably between 1.5 and 9 g/l of alcohol ethoxylate.
Oppfinnelsen vedrører videre en tørr blanding for bruk i oljebaserte borevæsker omfattende et vektmiddel og et deflokkuleringsmiddel hvor deflokkuleringsmiddelet er alkoholetoksylat med en molekylvekt mellom 200 og 2000 Dalton. The invention further relates to a dry mixture for use in oil-based drilling fluids comprising a weighting agent and a deflocculating agent, where the deflocculating agent is alcohol ethoxylate with a molecular weight between 200 and 2000 Daltons.
Alkoholetoksylatet har fortrinnsvis en molekylvekt mellom 300 og 600 Dalton. The alcohol ethoxylate preferably has a molecular weight between 300 and 600 Daltons.
Alkoholetoksylatet kan være av ikke-ionisk, anionisk eller kationisk karakter og kan bli benyttet enten i en av de ovennevnte former eller som en blanding av forskjellige former, og kan benyttes i oljebaserte borevæsker inneholdende vektmidler så som mangantetraoksid, baritt, hematitt, ilmenitt og andre. The alcohol ethoxylate can be of a non-ionic, anionic or cationic nature and can be used either in one of the above-mentioned forms or as a mixture of different forms, and can be used in oil-based drilling fluids containing weighting agents such as manganese tetraoxide, barite, hematite, ilmenite and others .
Den tørre blandingen omfatter 0,02-2,0 vekt % alkoholetoksylat basert på vekten av vektmiddelet og mer foretrukket 0,02-1,0 vekt% alkoholetoksylat basert på vekten av vektmiddel. En mengde mellom 0,06 og 0,3 vekt% basert på vekten av vektmiddelet er særlig foretrukket. The dry mixture comprises 0.02-2.0% by weight of alcohol ethoxylate based on the weight of weight agent and more preferably 0.02-1.0% by weight of alcohol ethoxylate based on the weight of weight agent. An amount between 0.06 and 0.3% by weight based on the weight of the weighting agent is particularly preferred.
Ved bruk av den tørre blandingen i henhold til den foreliggende oppfinnelse er det enkelt å tilsette vektmiddel og deflokkuleringsmiddel til oljebaserte borevæsker og derved sikre at flokkulering og dannelse av agglomerater unngås. When using the dry mixture according to the present invention, it is easy to add weighting agent and deflocculating agent to oil-based drilling fluids and thereby ensure that flocculation and the formation of agglomerates are avoided.
Alkoholetoksylatene er bionedbrytbare, er stabile ved høye temperaturer opp til og over 200°C og gir tilfredstillende reologi og viser gode filtrerings- og settlingsegenskaper for de oljebaserte borevæskene. The alcohol ethoxylates are biodegradable, are stable at high temperatures up to and above 200°C and provide satisfactory rheology and show good filtering and settling properties for the oil-based drilling fluids.
Når alkoholetoksylat tilsettes separat under fremstilling av borevæsken er det ingen spesiell sekvens for tilsetning av alkoholetoksylat. Det kan tilsettes etter tilsetning av emulsiferende midler, vann, viskositetsregulerende middel og fluid loss regulerende middel og før tilsetning av vektmiddel. Det kan også tilsettes etter at borevæsken er ferdig blandet. When alcohol ethoxylate is added separately during the production of the drilling fluid, there is no particular sequence for adding alcohol ethoxylate. It can be added after the addition of emulsifiers, water, viscosity-regulating agent and fluid loss-regulating agent and before the addition of weighting agent. It can also be added after the drilling fluid has been mixed.
Ved fremstilling av den tørre blandingen av vektmiddel og alkoholetoksylat blir alkoholetoksylat fortrinnsvis sprayet på overflaten av vektmiddelpartiklene. When preparing the dry mixture of weighting agent and alcohol ethoxylate, alcohol ethoxylate is preferably sprayed onto the surface of the weighting agent particles.
Fremstilling av noen av alkoholetoksylatene som benyttes i den foreliggende oppfinnelse er beskrevet i WO2005/085321. Preparation of some of the alcohol ethoxylates used in the present invention is described in WO2005/085321.
De ikke-ioniske alkoholetoksylatene kan beskrives med den følgende generelle formel. The nonionic alcohol ethoxylates can be described by the following general formula.
RO kan fremstilles fra en blanding av alkoholer ROH og alkylgruppen (R) kan være lineær eller forgrenet. RO can be prepared from a mixture of alcohols ROH and the alkyl group (R) can be linear or branched.
R<1>og R<2>kan være H eller en alifatisk hydrokarbonkjede (lineær eller forgrenet). R<1> and R<2> can be H or an aliphatic hydrocarbon chain (linear or branched).
X,Y og Z er uavhengige og kan ha verdier fra 1 til 20. X,Y and Z are independent and can have values from 1 to 20.
En generell formel for anioniske alkoholetoksylater kan ilustreres som følger: A general formula for anionic alcohol ethoxylates can be illustrated as follows:
R=lineaær alkyl, forgrenet alkyl eller alkylaryl, x kan ha verdi fra 1 til 20 og R=linear alkyl, branched alkyl or alkylaryl, x can have a value from 1 to 20 and
R<1>= H eller CH3. R<1>= H or CH3.
Alkoholene som benyttes ved fremstilling av både alkoholetoksylater og karboksymetylert alkoholetoksylat kan være; 1) fettsyrealkoholer utvunnet fra fettsyretriglyserider eller voksestere; 2) alkoholer fremstilt ved hydroformylering av olefiner fremstilt ved Fischer-Tropsch prosessen fra karbonmonoksid (CO) og hydrogen (H2) gass; 3) alkoholer fremstilt fra petrokjemiske kilder ved bruk av Ziegler prosessen eller ved Shell høyere olefin prosess etc. The alcohols used in the production of both alcohol ethoxylates and carboxymethylated alcohol ethoxylate can be; 1) fatty acid alcohols extracted from fatty acid triglycerides or wax esters; 2) alcohols produced by hydroformylation of olefins produced by the Fischer-Tropsch process from carbon monoxide (CO) and hydrogen (H2) gas; 3) alcohols produced from petrochemical sources using the Ziegler process or the Shell higher olefin process etc.
Flere detlajer om ikke-ioniske og anioniske alkoholetoksylater kan finnes i US patentsøknad 2008/0207494. More details on nonionic and anionic alcohol ethoxylates can be found in US patent application 2008/0207494.
Bionedbrytningsgraden av alkoholetoksylater ved enden av 10-dagers vinduet i henhold til OECD 301B standard Biogradation Test Protocol bør være minst The degree of biodegradation of alcohol ethoxylates at the end of the 10-day window according to the OECD 301B standard Biogradation Test Protocol should be at least
>20%, fortrinnsvis mer enn 40% og mer foretrukket over 60%. >20%, preferably more than 40% and more preferably over 60%.
Eksempel 1. Example 1.
Fire oljebaserte borevæsker for bruk ved høyt trykk og høy temperatur (HPHT) ble fremstilt inneholdende forskjellige deflokkuleringsmidler. Sammensetningen av de fire borevæskene A,B,C og D er vist i Tabell 1. Alle fire borevæskene hadde en spesifikk vekt på 2,1. Four oil-based high pressure high temperature (HPHT) drilling fluids were prepared containing different deflocculating agents. The composition of the four drilling fluids A, B, C and D is shown in Table 1. All four drilling fluids had a specific gravity of 2.1.
Fremstilling og testing av borevæskene ble utført i henhold til API 13B standard. Production and testing of the drilling fluids was carried out in accordance with the API 13B standard.
Sammensetningen av borevæskene er identiske bortsett fra deflokkuleringsmiddelet som ble benyttet. I borevæske A ble det benyttet et konvensjonelt ikke-bionedbrytbar polyolefin/organisk sulfonat deflokkuleringsmiddel fra Baker Hughes som selges under varemerket Omni-Cote<®>. The composition of the drilling fluids are identical except for the deflocculating agent that was used. In drilling fluid A, a conventional non-biodegradable polyolefin/organic sulfonate deflocculating agent from Baker Hughes, sold under the brand name Omni-Cote<®>, was used.
I borevæske B ble det benyttet et bionedbrytbart alkoholetoksylat sammensatt av en alkohol med alkylkjede C12-C13 og en etylenoksid (EO) blokk med et gjennomsnittlig innhold av EO enheter på 6,5, en gjennomsnittlig molekylvekt på 479 Dalton og hydrofil/hydrofob balanse (HLB) på 12. Dette deflokkuleringsmiddelet er fra Sasol North America Inc og selges under varemerket Novel<®>23 E6,5. In drilling fluid B, a biodegradable alcohol ethoxylate composed of an alcohol with an alkyl chain C12-C13 and an ethylene oxide (EO) block was used with an average content of EO units of 6.5, an average molecular weight of 479 Dalton and hydrophilic/hydrophobic balance (HLB ) at 12. This deflocculating agent is from Sasol North America Inc and is sold under the trade name Novel<®>23 E6.5.
I borevæske C ble det benyttet en bionedbrytbar C13-alkohol polyetylenglykoleter karboksylsyre fra Sasol Germany GmbH som selges under varemerket Marlowet<®>4538. Dette er et anionisk deflokkuleringsmiddel og har en molekylvekt på 566 Dalton. I borevæske D ble det benyttet et bionedbrytbart alkoholetoksylat (isopropanol, etoksylert, propoksylert, karboksymetylert) fra Sasol Germany GmbH som selges under varemerket Marlowet<®>1072. Dette er et anionisk deflokkuleringsmiddel med en molekylvekt på 333 Dalton. De fire borevæskene A,B,C og D ble testet for reologi, filtrering, elektrisk stabilitet og statisk SAG faktor før statisk varmebehandling (BHA) og etter statisk varmebehandling (AHA) ved 150°C. In drilling fluid C, a biodegradable C13 alcohol polyethylene glycol ether carboxylic acid from Sasol Germany GmbH, which is sold under the brand name Marlowet<®>4538, was used. This is an anionic deflocculating agent and has a molecular weight of 566 Daltons. A biodegradable alcohol ethoxylate (isopropanol, ethoxylated, propoxylated, carboxymethylated) from Sasol Germany GmbH, which is sold under the brand name Marlowet<®>1072, was used in drilling fluid D. This is an anionic deflocculating agent with a molecular weight of 333 Daltons. The four drilling fluids A, B, C and D were tested for rheology, filtration, electrical stability and static SAG factor before static heat treatment (BHA) and after static heat treatment (AHA) at 150°C.
Følgende utstyr ble benyttet for å teste borevæskene: The following equipment was used to test the drilling fluids:
Fann rheometer med termokopp, høy temperatur og trykk filtreringsystem for måling av fluid loss ved HPHT, pH-meter, ovn, 250 og 500 ml varmebehandlingcelle og presisjonsvekt. Statisk sag test ble utført i henhold til følgende prosedyre; A) Fyll borevæsken som skal varmebehandles i en varmebehandlingcelle av rustfritt stål. Found rheometer with thermocup, high temperature and pressure filtration system for measuring fluid loss at HPHT, pH meter, oven, 250 and 500 ml heat treatment cell and precision scale. Static saw test was performed according to the following procedure; A) Fill the drilling fluid to be heat treated in a stainless steel heat treatment cell.
B) Lukk cellen og trykksett cellen med 20 bar N2-gass. B) Close the cell and pressurize the cell with 20 bar N2 gas.
C) Hold cellen opprett ved ønsket temperatur i 16 timer. C) Keep the cell upright at the desired temperature for 16 hours.
D) Når varmebehandlingstiden er over, ta cellen ut av ovnen og kjøl til romtemperatur. Cellen må holdes opprett. D) When the heat treatment time is over, remove the cell from the oven and cool to room temperature. The cell must be kept upright.
E) Ta forsiktig bort trykket før cellen åpnes. E) Carefully remove the pressure before opening the cell.
F) Sug opp den klare væsken fra toppen av væsken. Overfør den klare væsken til en målesylinder, noter volumet i ml. G) Sup opp 20 ml borevæske fra toppen av varmebehandlingcellen med en sprøyte og overfør til et pyknometer. Bestem tettheten av borevæsken ved å dele vekten av borevæsken i pyknometeret med 20. H) Sug opp 20 ml borevæske fra bunnen av varmebehandlingcellen med en sprøyte og overfør til et pyknometer. F) Aspirate the clear liquid from the top of the liquid. Transfer the clear liquid to a measuring cylinder, record the volume in ml. G) Sup up 20 ml of drilling fluid from the top of the heat treatment cell with a syringe and transfer to a pycnometer. Determine the density of the drilling fluid by dividing the weight of the drilling fluid in the pycnometer by 20. H) Aspirate 20 ml of drilling fluid from the bottom of the heat treatment cell with a syringe and transfer to a pycnometer.
Bestem vekten av borevæske i pyknometeret. Bestem tettheten av borevæsken ved å dividere vekten av borevæsken i pyknometeret med 20. Determine the weight of drilling fluid in the pycnometer. Determine the density of the drilling fluid by dividing the weight of the drilling fluid in the pycnometer by 20.
Sag faktor = tetthet bunn/(tetthet topp + tetthet bunn) Sag factor = density bottom/(density top + density bottom)
Resultatene av testene av de oljebaserte borevæskene A,B,C og D er vist i Tabell 2. The results of the tests of the oil-based drilling fluids A, B, C and D are shown in Table 2.
Resultatene i Tabell 2 viser at det ikke-ioniske deflokkuleringsmiddelet i henhold til oppfinnelsen er effektivt for å holde de reologiske egenskapene ganske stabile etter varmebehandling i 16 timer ved 150°C. Også de anioniske deflokkuleringsmiddlene i henhold til den foreliggende oppfinnelse slik som Marlowet<®>1072 og Marlowet<®>4538 reduserer viskositeten, men filtreringen var ganske høy med de anioniske deflokkuleringsmidlene. Dette kan skyldes interferens med fluid-loss midlene. Dette eksempelet viser at bionedbrytbare alkoholetoksylater kan erstatte de produkter som nå benyttes og som kan utgjøre en fare for omgivelsene. The results in Table 2 show that the non-ionic deflocculating agent according to the invention is effective in keeping the rheological properties fairly stable after heat treatment for 16 hours at 150°C. Also the anionic deflocculating agents of the present invention such as Marlowet<®>1072 and Marlowet<®>4538 reduce the viscosity, but the filtration was quite high with the anionic deflocculating agents. This may be due to interference with the fluid-loss agents. This example shows that biodegradable alcohol ethoxylates can replace the products that are currently used and which can pose a danger to the environment.
Eksempel 2. Example 2.
For å simulere virkningen på de oljebaserte borevæskene i henhold til oppfinnelsen av kollodiale fine partikler som kan dannes fra formasjonen under boring, ble malte montmorillonittpartikler tilsatt til oljebaserte borevæsker. Fire borevæsker E,F,G og H med sammensetninger som vist i tabell 3 ble blandet. To simulate the effect on the oil-based drilling fluids according to the invention of colloidal fine particles that can be formed from the formation during drilling, ground montmorillonite particles were added to oil-based drilling fluids. Four drilling fluids E, F, G and H with compositions as shown in Table 3 were mixed.
Borevæskene E.F.G og H ble testet for reologi, filtrering, dynamisk sag, og dynamisk filtrering. The drilling fluids E.F.G and H were tested for rheology, filtration, dynamic saw, and dynamic filtration.
Dynamisk sag ble bestemt som følger: Dynamic sag was determined as follows:
Sag tendens for borevæskene ble bestemt ved bruk av Viscometer Sag Shoe Test (VSST), som måler sag tendens ved dynamiske betingelser. Denne testen benytter Fann 35 viskosimeter og en sag sko, som samler sag vektmateriale i en samlebrønn i sag skoen hvor prøver tas ved slutten av testen for å bestemme sag tendensen for væsken. Sagging tendency of the drilling fluids was determined using the Viscometer Sag Shoe Test (VSST), which measures sag tendency under dynamic conditions. This test uses a Fann 35 viscometer and a saw shoe, which collects saw weight material in a collection well in the saw shoe where samples are taken at the end of the test to determine the saw tendency of the liquid.
VSST beregnes etter følgende formel 1: VSST is calculated according to the following formula 1:
Hvor WT2 = vekt av 10 ml av borevæske etter skjærbehandling i 30 minutter, og WT1=vekt av 10 ml av borevæske før skjærbehandling i 30 minutter. VSST er en forbedring av VST hvor sag sko ikke er innsatt i viskometerets termokopp, selv om resten av prosedyren er den samme. Aldea et al.(2001) fastslo at en væske vil ha en moderat til lav sagtendens når tetthetsendringen målt ved VST er mindre enn 1 Ibm/gal. Where WT2 = weight of 10 ml of drilling fluid after shear treatment for 30 minutes, and WT1 = weight of 10 ml of drilling fluid before shear treatment for 30 minutes. VSST is an improvement on VST where the saw shoe is not inserted into the viscometer's thermocup, although the rest of the procedure is the same. Aldea et al. (2001) determined that a liquid will have a moderate to low sag tendency when the density change measured by VST is less than 1 Ibm/gal.
Resultatene fra testene er vist i Tabell 4. The results from the tests are shown in Table 4.
Resultatene vist i tabell 4 viser at 10 min gel for borevæsken E (uten deflokkuleringsmiddel) blir sterkt økt etter varmebehandling mens gel for borevæskene F,G og H innholdende deflokkuleringsmidler i henhold til oppfinnelsen viste en vesentlig mindre økning enn prøven E. Eksempelet ovenfor viser også at alkoholetoksylat med 6,5 EO enheter er bedre enn et med 9EO enheter ettersom sag av væsken og det totale filtreringsvolumet med Novel 23 E6,5 var mindre enn væsken med Novel 23 E9. Dette betyr at det finnes en optimal kjedelengde for etylenoksidblokk som gir best adsoption av deflokkuleringmiddelet på Mn304 overflaten. Når kjeden når en viss lengde kan sterisk hindring forekomme noe som senker mengden av adsorberte molekyler. The results shown in table 4 show that the 10 min gel for the drilling fluid E (without deflocculating agent) is greatly increased after heat treatment, while the gel for the drilling fluids F, G and H containing deflocculating agents according to the invention showed a significantly smaller increase than sample E. The example above also shows that alcohol ethoxylate with 6.5 EO units is better than one with 9EO units as the amount of liquid and the total filtration volume with Novel 23 E6.5 was less than the liquid with Novel 23 E9. This means that there is an optimal chain length for the ethylene oxide block which provides the best adsorption of the deflocculating agent on the Mn304 surface. When the chain reaches a certain length, steric hindrance can occur, which lowers the amount of adsorbed molecules.
Eksempel 3 Example 3
For å simulere oljebaserte borevæsker forurenset med G-sement ble borevæskene l,J,K og L blandet. Borevæskene J, K og L er i henhold til den foreliggende oppfinnelse. Borevæske I inneholdt ikke deflokkuleringsmiddel. To simulate oil-based drilling fluids contaminated with G-cement, drilling fluids l, J, K and L were mixed. The drilling fluids J, K and L are according to the present invention. Drilling fluid I did not contain a deflocculating agent.
Flokkuleringsmiddelet benyttet i borevæske J er det samme som deflokkuleringsmiddelet benyttet i borevæske F i eksempel 2. Deflokkuleringsmiddelet benyttet i borevæske K er det samme som deflokkuleringsmiddelet benyttet i borevæske G i eksempel 2 og deflokkuleringsmidelet benyttet i borevæske L er det samme som deflokkuleringsmiddelet benyttet i borevæske D i eksempel 1. Borevæskene hadde en spesifikk tetthet på 1,9. The flocculating agent used in drilling fluid J is the same as the deflocculating agent used in drilling fluid F in example 2. The deflocculating agent used in drilling fluid K is the same as the deflocculating agent used in drilling fluid G in example 2 and the deflocculating agent used in drilling fluid L is the same as the deflocculating agent used in drilling fluid D in Example 1. The drilling fluids had a specific gravity of 1.9.
Sammensetningen av borevæskene er vist i tabell 5. The composition of the drilling fluids is shown in table 5.
De fire borevæskene l,J,K og L ble testet for reologi, geldannelse og dynamisk sag før og etter varmebehandling ved 200°C og 34,5 bar trykk. Resultatene er vist i tabell 6. The four drilling fluids l, J, K and L were tested for rheology, gel formation and dynamic shear before and after heat treatment at 200°C and 34.5 bar pressure. The results are shown in table 6.
Egenskapene for borevæskene J,K og L i henhold til oppfinnelsen forurenset med sement er i det ønskede området og er stabile etter varmebehandling, hvilket indikerer at alkoholetoksylater kan benyttes for å stabilisere borevæsker forurenset med sement. The properties of the drilling fluids J, K and L according to the invention contaminated with cement are in the desired range and are stable after heat treatment, which indicates that alcohol ethoxylates can be used to stabilize drilling fluids contaminated with cement.
Eksempel 4. Example 4.
I dette eksempelet ble det benyttet en kombinasjon av ikke-ionisk og anionisk alkoholetoksylat for å kontrollere reologi av oljebaserte borevæsker med en densitet på 2,1 SG. In this example, a combination of nonionic and anionic alcohol ethoxylate was used to control the rheology of oil-based drilling fluids with a density of 2.1 SG.
Tre oljebaserte borevæsker M,N,0 med en sammensetning som vist i tabell 7 ble fremstilt. Three oil-based drilling fluids M,N,0 with a composition as shown in table 7 were prepared.
Som vist i tabell 7, inneholdt borevæske M det ikke-ioniske deflokkuleringsmiddel Novel<®>23E6,5, borevæske N inneholdt en kombinasjon av ikke-ionisk (Novel<®>23E6,5) og anionisk deflokkuleringsmiddel (Marlowte<®>4561) i vektforhold 1:1 og borevæske O inneholdt det anioniske deflokkuleringsmiddelet Marlowet<®>4561. As shown in Table 7, drilling fluid M contained the nonionic deflocculating agent Novel<®>23E6.5, drilling fluid N contained a combination of nonionic (Novel<®>23E6.5) and anionic deflocculating agent (Marlowte<®>4561) in a 1:1 weight ratio and drilling fluid O contained the anionic deflocculating agent Marlowet<®>4561.
Egenskapene for de tre borevæskene ble testet og resultatene er vist i tabell 8. The properties of the three drilling fluids were tested and the results are shown in Table 8.
Som det kan ses fra tabell 8 ikke bare forbedrer kombinasjonen av ikke-ionisk alkoholetoksylat og anionisk alkoholetoksylat som deflokkuleringsmidler stabiliteten av borevæskene, men forbedrer også filtreringsegenskapene av væskene. Dette kan relateres til god dispergerbarhet av Mn304partiklene som fører til dannelse av en tynnere filterkake med lav porøsitet og permeabilitet. As can be seen from Table 8, the combination of nonionic alcohol ethoxylate and anionic alcohol ethoxylate as deflocculating agents not only improves the stability of the drilling fluids, but also improves the filtration properties of the fluids. This can be related to good dispersibility of the Mn3O4 particles, which leads to the formation of a thinner filter cake with low porosity and permeability.
Eksempel 5 Example 5
I dette eksempelet ble forskjellige vektmidler testet med alkoholetoksylat som deflokkuleringsmiddel. Deflokkuleringsmiddelet som ble benyttet i dette eksempelet er Novel<®>23E6,5. Vektmidlene er API baritt (BaS04), mangantetraoksid (Mn304) og mikronisert ilmenitt (Fe3Ti03) og spesifikk vekt av alle tre sammensetningene var 2,1. Sammensetningen av de tre oljebaserte borevæskene er vist i tabell 9. In this example, different weights were tested with alcohol ethoxylate as a deflocculating agent. The deflocculating agent used in this example is Novel<®>23E6.5. The weighting agents are API barite (BaS04), manganese tetraoxide (Mn304) and micronized ilmenite (Fe3Ti03) and the specific gravity of all three compositions was 2.1. The composition of the three oil-based drilling fluids is shown in table 9.
Reologi, filtrering, elektrisk stabilitet og statisk sag før og etter varmebehandling ved 150°C ble målt og resultatene er vist i tabell 10. Rheology, filtration, electrical stability and static sag before and after heat treatment at 150°C were measured and the results are shown in table 10.
Som det kan ses fra tabell 10 gir bruk av alkoholetoksylater meget gode resultater for borevæsker inneholdende forskjellige vektmidler. As can be seen from table 10, the use of alcohol ethoxylates gives very good results for drilling fluids containing different weighting agents.
Claims (10)
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| NO20120438A NO20120438A1 (en) | 2012-04-13 | 2012-04-13 | Oil-based drilling fluids and mixture for use in oil-based drilling fluids |
| PCT/NO2013/000011 WO2013154435A1 (en) | 2012-04-13 | 2013-03-26 | Oil based drilling fluids and mixture for use in oil based drilling fluids |
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| GB2550087A (en) * | 2015-03-16 | 2017-11-08 | Halliburton Energy Services Inc | Mud settlement detection technique by non-destructive ultrasonic measurements |
| US10351750B2 (en) | 2017-02-03 | 2019-07-16 | Saudi Arabian Oil Company | Drilling fluid compositions with enhanced rheology and methods of using same |
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| US3642623A (en) * | 1969-10-10 | 1972-02-15 | Oil Base | Oil base well drilling fluid composition and method |
| CA1136355A (en) * | 1979-03-23 | 1982-11-30 | Patrick A. Pickens | High concentration polymer slurries |
| GB8811574D0 (en) * | 1988-05-16 | 1988-06-22 | Sandoz Products Ltd | Improvements in/relating to organic compounds |
| US5283235A (en) * | 1992-03-17 | 1994-02-01 | The Lubrizol Corporation | Compositions containing esters of carboxy-containing interpolymers and methods of using the same |
| US5499677A (en) * | 1994-12-23 | 1996-03-19 | Shell Oil Company | Emulsion in blast furnace slag mud solidification |
| GB9601019D0 (en) * | 1996-01-18 | 1996-03-20 | Sofitech Nv | Wellbore fluid |
| US5955401A (en) * | 1996-05-17 | 1999-09-21 | Baroid Technology, Inc. | Clay-free biodegradable wellbore fluid and method for using same fluid |
| US5866517A (en) * | 1996-06-19 | 1999-02-02 | Atlantic Richfield Company | Method and spacer fluid composition for displacing drilling fluid from a wellbore |
| DE19727541A1 (en) * | 1997-06-28 | 1999-01-07 | Sueddeutsche Kalkstickstoff | Solid composition based on clay minerals and their use |
| US5904208A (en) * | 1998-01-21 | 1999-05-18 | Deep South Chemical | Method of cleaning a well bore prior to cementing |
| GB2345706B (en) * | 1999-01-16 | 2003-05-21 | Sofitech Nv | Electrically conductive invert emulsion wellbore fluid |
| US6534449B1 (en) * | 1999-05-27 | 2003-03-18 | Schlumberger Technology Corp. | Removal of wellbore residues |
| GB9923816D0 (en) * | 1999-10-11 | 1999-12-08 | Ici Plc | Polymeric surfactants |
| US6887832B2 (en) * | 2000-12-29 | 2005-05-03 | Halliburton Energy Service,S Inc. | Method of formulating and using a drilling mud with fragile gels |
| US6818596B1 (en) * | 2001-09-19 | 2004-11-16 | James Hayes | Dry mix for water based drilling fluid |
| US20040244978A1 (en) * | 2003-06-04 | 2004-12-09 | Sun Drilling Products Corporation | Lost circulation material blend offering high fluid loss with minimum solids |
| US7293609B2 (en) * | 2004-10-20 | 2007-11-13 | Halliburton Energy Services, Inc. | Treatment fluids comprising vitrified shale and methods of using such fluids in subterranean formations |
| US8357639B2 (en) * | 2007-07-03 | 2013-01-22 | Baker Hughes Incorporated | Nanoemulsions |
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