NO172501B - WATER-IN-OIL DRILLING CONTAINING SELECTED LOW CARBOXYLIC ACID ESSENTIALS AND MANUFACTURING THEREOF - Google Patents
WATER-IN-OIL DRILLING CONTAINING SELECTED LOW CARBOXYLIC ACID ESSENTIALS AND MANUFACTURING THEREOF Download PDFInfo
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- NO172501B NO172501B NO913239A NO913239A NO172501B NO 172501 B NO172501 B NO 172501B NO 913239 A NO913239 A NO 913239A NO 913239 A NO913239 A NO 913239A NO 172501 B NO172501 B NO 172501B
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- esters
- oil
- water
- drilling mud
- ester
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- -1 LOW CARBOXYLIC ACID Chemical class 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000003921 oil Substances 0.000 claims abstract description 79
- 238000005553 drilling Methods 0.000 claims abstract description 65
- 150000002148 esters Chemical class 0.000 claims abstract description 57
- 239000012071 phase Substances 0.000 claims abstract description 38
- 150000001298 alcohols Chemical class 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 17
- 150000002763 monocarboxylic acids Chemical class 0.000 claims abstract description 17
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 239000008346 aqueous phase Substances 0.000 claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003345 natural gas Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000003209 petroleum derivative Substances 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 44
- 239000010696 ester oil Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 22
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 21
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000004571 lime Substances 0.000 claims description 21
- 150000001735 carboxylic acids Chemical class 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 150000005846 sugar alcohols Polymers 0.000 claims description 10
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 9
- 238000007711 solidification Methods 0.000 claims description 9
- 230000008023 solidification Effects 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007762 w/o emulsion Substances 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000004067 bulking agent Substances 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002168 ethanoic acid esters Chemical class 0.000 claims 2
- 239000002585 base Substances 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 230000002110 toxicologic effect Effects 0.000 claims 1
- 231100000027 toxicology Toxicity 0.000 claims 1
- 239000012530 fluid Substances 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000945 filler Substances 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000010802 sludge Substances 0.000 description 9
- 238000007792 addition Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 7
- 241001465754 Metazoa Species 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 235000013311 vegetables Nutrition 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- HBNFJAUKNDPDBF-UHFFFAOYSA-N 11-methyldodecyl acetate Chemical compound CC(C)CCCCCCCCCCOC(C)=O HBNFJAUKNDPDBF-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 239000010428 baryte Substances 0.000 description 3
- 229910052601 baryte Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical class NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000010931 ester hydrolysis Methods 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000252203 Clupea harengus Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010480 babassu oil Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940013317 fish oils Drugs 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 235000019514 herring Nutrition 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
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
-
- 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
- C09K8/34—Organic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Lubricants (AREA)
- Treatment Of Sludge (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Earth Drilling (AREA)
- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
Foreliggende oppfinnelse angår vann-i-olje-emulsjonsboreslam (såkalte invert-boreslam) på basis av esteroljer som utmerker seg ved høy økologisk godtagbarhet ved samtidig gode lagrings- og bruksegenskaper, og den angår også en fremgangsmåte for fremstilling av slike boreslam. The present invention relates to water-in-oil emulsion drilling mud (so-called invert drilling mud) based on ester oils which are distinguished by high ecological acceptability with good storage and use properties at the same time, and it also relates to a method for producing such drilling mud.
Et viktig anvendelsesområde for de nye boreslamsystemer er offshore-boringer for utnytting av jordolje- og/eller jordgassforekomster, hvorved oppfinnelsen her spesielt tar sikte på å stille til disposisjon teknisk brukbare boreslam med høy økologisk fordragelighet. Anvendelsen av de nye boreslamsystemer har spesiell betydning på det maritime området, men finner generelt anvendelse også ved landbaserte boringer, for eksempel ved geotermiske boringer, vann-boringer, ved gjennomføring av geovitenskapelige boringer eller videre også i bergverkssektoren. Prinsipielt gjelder det imidlertid at de økotoksiske problemer sterkt forenkles ved hjelp av oppfinnelsens utvalgte boreslam på esterbasis. An important area of application for the new drilling mud systems is offshore drilling for the exploitation of oil and/or natural gas deposits, whereby the invention here particularly aims to make available technically usable drilling mud with a high ecological tolerability. The application of the new drilling mud systems has particular importance in the maritime area, but is generally also used in land-based drilling, for example in geothermal drilling, water drilling, when carrying out geoscientific drilling or further also in the mining sector. In principle, however, it applies that the ecotoxic problems are greatly simplified by means of the invention's selected ester-based drilling mud.
Boreslam på oljebasis anvendes generelt som såkalte invert-emulsjonsslam som består av et tre-fasesystem: olje, vann og finfordelte faststoffer. Det dreier seg herved om tilbered-ninger av typen vann-i-ol je-emulsjoner, det vil si at den vandige fase er heterogent, findispergert fordelt i den lukkede oljefase. For stabilisering av det totale system og for innstilling av de ønskede bruksegenskaper, tas det sikte på et antall tilsetningsstoffer, spesielt emulgatorer henholdsvis emulgatorsystemer, tyngdegivende midler, væsketapsadditiver, alkalireserver og viskositetsregulerende stoffer. Når det gjelder enkeltheter, skal det spesielt henvises til P.A. Boyd et al. i "New Base Oil Used in Low-Toxicity Oil Muds", "Journal of Petroleum Technology", 1985, 137-142 samt av R.B. Bennett, "New Drilling Fluid Technology - Mineral Oil Mud", "Journal of Petroleum Technology", 1984, 975-981, samt den deri nevnte litteratur. Oil-based drilling mud is generally used as so-called invert emulsion mud, which consists of a three-phase system: oil, water and finely divided solids. This refers to preparations of the water-in-oil emulsion type, that is to say that the aqueous phase is heterogeneous, finely dispersed and distributed in the closed oil phase. For stabilization of the overall system and for setting the desired usage properties, a number of additives are aimed at, especially emulsifiers or emulsifier systems, bulking agents, liquid loss additives, alkali reserves and viscosity-regulating substances. When it comes to details, special reference should be made to P.A. Boyd et al. in "New Base Oil Used in Low-Toxicity Oil Muds", "Journal of Petroleum Technology", 1985, 137-142 as well as by R.B. Bennett, "New Drilling Fluid Technology - Mineral Oil Mud", "Journal of Petroleum Technology", 1984, 975-981, and the literature cited therein.
Dagens teknologi har i lang tid erkjent betydningen av oljefaser på esterbasis for å løse denne problematikk. Således beskriver US-PS 4 374 737 og 4 481 121 oljebaserte boreslam i hvilke ikke-forurensende oljer skulle kunne finne anvendelse. Som ikke-forurensende oljer nevnes ved siden av hverandre og som likeverdige, aromatfrie mineraloljefraksjoner og planteoljer av typen jordnøttolje, soyabønneolje, linfrøolje, maisolje, risolje, eller også oljer av animalsk opprinnelse som hvalolje. Hele tiden dreier det seg ved de her nevnte esteroljer av vegetabilsk eller animalsk opprinnelse om triglycerider av naturlige fettsyrer som som kjent har en høy omgi vel sesf ordragelighet og som i forhold til hydrokarbonfraksjoner, også når disse er aromatfrie, har overlegne egenskaper med henblikk på økologiske betraktninger . Today's technology has long recognized the importance of ester-based oil phases to solve this problem. Thus, US-PS 4,374,737 and 4,481,121 describe oil-based drilling muds in which non-polluting oils could be used. Non-polluting oils are mentioned next to each other and as equivalent, aroma-free mineral oil fractions and vegetable oils of the type peanut oil, soybean oil, linseed oil, corn oil, rice oil, or also oils of animal origin such as whale oil. All the time, the ester oils mentioned here of vegetable or animal origin are triglycerides of natural fatty acids which, as is known, have a high environmental tolerance and which, in relation to hydrocarbon fractions, even when these are aroma-free, have superior properties with a view to ecological considerations.
Interessant nok er det imidlertid intet eksempel i de ovenfor nevnte TJS-patenter på anvendelse av slike naturlige esteroljer i invert-boreslam av den her nevnte type. Hele tiden nevnes det mineraloljefraksjoner som lukket oljefase. Interestingly, however, there is no example in the above-mentioned TJS patents of the use of such natural ester oils in invert drilling mud of the type mentioned here. All the time, mineral oil fractions are mentioned as closed oil phase.
Olje av vegetabilsk og/eller animalsk opprinnelse kommer ikke i betraktning av praktiske grunner. De reologiske egenskaper for slike oljefaser er for de brede i praksis krevede temperaturområder på 0 til 5°C på den ene side og opptil 250°C og derover på den annen side, ikke å forene. Oil of vegetable and/or animal origin is not considered for practical reasons. The rheological properties of such oil phases are for the wide practically required temperature ranges of 0 to 5°C on the one hand and up to 250°C and above on the other hand, not to be reconciled.
Esteroljer av den her beskrevne art oppfører seg i virkelig-heten ikke på samme måte som de til nu anvendte mineraloljefraksjoner på ren hydrokarbonbasis. Esteroljer undergår i praktisk bruk også, spesielt i vann-i-olje-invert-boreslam, en partiell hydrolyse. Derved dannes det frie karboksylsyrer. NO-171 562B og NO-171 601B beskriver de derved utløste problemer og gir forslag for løsning av problemene. In reality, ester oils of the type described here do not behave in the same way as the mineral oil fractions used until now on a pure hydrocarbon basis. In practical use, ester oils also undergo partial hydrolysis, especially in water-in-oil invert drilling mud. Thereby, free carboxylic acids are formed. NO-171 562B and NO-171 601B describe the resulting problems and give suggestions for solving the problems.
Gjenstand for disse eldre patenter er anvendelsen av esteroljer på basis av hver gang utvalgte monokarboksylsyrer henholdsvis monokarboksylsyreblandinger og enverdige alkoholer med minst 2, fortrinnsvis minst 4 C-atomer. De eldre søknader beskriver at man med de der beskrevne estere henholdsvis esterblandinger med enverdige reaktanter ikke bare kan innstille tilfredsstillende reologiske egenskaper i det friske boreslam, men at det også er mulig å arbeide under medanvendelse av utvalgte kjente alkalireserver i boreslammet og på denne måte å hindre uønsket korrosjon. Som alkalireserve tar man sikte på tilsetning av kalk (kalsium-hydroksyd henholdsvis kalk (lime)) og/eller medanvendelse av sinkoksyd eller sammenlignbare sinkforbindelser. Derved er det imidlertid hensiktsmessig med en ytterligere begrensning. Hvis man i praktisk bruk skal forhindre den uønskede fortykkelse av de oljebaserte invert-slamsystemer, må man begrense mengden av det alkaliserende tilsetningsstoff og spesielt kalkmengden. Den tilsiktede største mengde er i henhold til det som sies de nevnte eldre søknader satt til 5,706 g/l (2 lb/bbl). The subject matter of these older patents is the use of ester oils based on each time selected monocarboxylic acids or monocarboxylic acid mixtures and monohydric alcohols with at least 2, preferably at least 4 C atoms. The older applications describe that with the esters or ester mixtures with monovalent reactants described there, it is not only possible to set satisfactory rheological properties in the fresh drilling mud, but that it is also possible to work with the combined use of selected known alkali reserves in the drilling mud and in this way to prevent unwanted corrosion. As an alkali reserve, the aim is the addition of lime (calcium hydroxide or lime (lime)) and/or the combined use of zinc oxide or comparable zinc compounds. Thereby, however, a further restriction is appropriate. If in practical use the unwanted thickening of the oil-based invert mud systems is to be prevented, the amount of the alkalizing additive and especially the amount of lime must be limited. According to what is said in the aforementioned older applications, the intended maximum amount is set at 5.706 g/l (2 lb/bbl).
Foreliggende oppfinnelses lære tar spesielt sikte på å unngå den til slutt ovenfor beskrevne problematikk ved at det anvendes en klasse av esteroljer i boreslam av den nevnte art som ved den alltid opptredende, begrensede hydrolyse av esteren danner uproblematiske karboksylsyrer henholdsvis karboksylsyresalter. Den tekniske gjennomføring av denne tanke ligger i valget av esteroljer som går tilbake på lavere karboksylsyrer med 1-5 karbonatomer. Spesiell betydning kan her de tilsvarende estere av eddiksyre ha. De ved den partielle hydrolyse av esteroljene oppståtte acetatsalter har ingen emulgerende virkninger som kan forstyrre vann-i-olje-systemet i vesentlig grad. The teaching of the present invention specifically aims to avoid the above-described problem in the end by using a class of ester oils in drilling mud of the aforementioned kind which, by the always occurring, limited hydrolysis of the ester, form unproblematic carboxylic acids or carboxylic acid salts. The technical implementation of this idea lies in the choice of ester oils that revert to lower carboxylic acids with 1-5 carbon atoms. The corresponding esters of acetic acid can be of particular importance here. The acetate salts produced by the partial hydrolysis of the ester oils have no emulsifying effects that can disturb the water-in-oil system to a significant extent.
Foreliggende oppfinnelse angår i henhold til dette vann-i-ol je-boreslam som er egnet for miljøvennlig utnyttelse av jordolje- henholdsvis jordgassforekomster og som i en lukket oljefase inneholder en dispergert, vandig fase sammen med emulgatorer, tyngdegivende midler, væsketapsadditiver og eventuelt ytterligere vanlige tilsetningsstoffer, og disse slam karakteriseres ved at oljefasen inneholder estere av C^g-monokarboksyl syrer med en- og/eller flerverdige alkoholer som er hellbare ved romtemperatur og som har flammepunkt over 80°C, eventuelt i blanding med andre økologisk forenelige forbindelser, spesielt ikke-forurensende oljer. According to this, the present invention relates to water-in-oil drilling mud which is suitable for the environmentally friendly exploitation of oil and natural gas deposits and which in a closed oil phase contains a dispersed, aqueous phase together with emulsifiers, weighting agents, liquid loss additives and possibly further common additives, and these sludges are characterized by the fact that the oil phase contains esters of C^g-monocarboxylic acids with mono- and/or polyhydric alcohols which are pourable at room temperature and which have a flash point above 80°C, possibly in a mixture with other ecologically compatible compounds, especially non-polluting oils.
Oppfinnelsen angår som antydet innledningsvis også en fremgangsmåte for fremstilling av vann-i-olje-emulsjonsboreslam som er egnet for miljøvennlig utnyttelse av jordolje- henholdsvis jordgassforekomster og som i en lukket oljefase inneholder en dispers vandig fase sammen med emulgatorer, tyngdegivende midler, væsketapsadditiver og eventuelt ytterligere vanlige tilsetningsstoffer, og denne fremgangsmåte karakteriseres ved at det anvendes estere av C1_g-monokarboksylsyrer og en- og/eller flerverdige alkoholer som er helledyktige ved romtemperatur og som har flammepunkt over 80°C, som oljefase eller bestanddel av oljefasen. As indicated at the outset, the invention also relates to a method for the production of water-in-oil emulsion drilling mud which is suitable for environmentally friendly exploitation of oil and natural gas deposits and which in a closed oil phase contains a dispersed aqueous phase together with emulsifiers, weighting agents, liquid loss additives and possibly further common additives, and this method is characterized by the use of esters of C1_g-monocarboxylic acids and mono- and/or polyhydric alcohols which are pourable at room temperature and which have a flash point above 80°C, as oil phase or component of the oil phase.
Monokarboksylsyreestere av den her beskrevne type kan, hva angår materialegenskapene styres via valget av de for forestring anvendte alkoholkomponenter slik at de kan anvendes for den ifølge oppfinnelsen tilsiktede bruk. Fortrinnsvis anvender man de tilsvarende estere eller esterblandinger som er hell- og pumpbare også i temperaturområdet 0-5°C. Det er videre foretrukket, som oljefase, å anvende C.j_5-monokarboksylsyreestere eller deres blandinger med økologisk forenelige komponenter fra klassen såkalte ikke-forurensende oljer og som i temperaturområdet fra 0 til 5°C oppviser en Brookfield-RVT-viskositet på ikke over 50 mPas og fortrinnsvis ikke over 40 mPas. Fortrinnsvis ligger de angitte viskositetsverdier i oljefasen ved maksimalt 30 mPas. Monocarboxylic acid esters of the type described here can, with regard to the material properties, be controlled via the choice of the alcohol components used for esterification so that they can be used for the intended use according to the invention. Preferably, the corresponding esters or ester mixtures are used which are pourable and pumpable also in the temperature range 0-5°C. It is further preferred, as the oil phase, to use C.j_5-monocarboxylic acid esters or their mixtures with ecologically compatible components from the class of so-called non-polluting oils and which in the temperature range from 0 to 5°C exhibit a Brookfield-RVT viscosity of no more than 50 mPas and preferably not over 40 mPas. Preferably, the stated viscosity values in the oil phase are at a maximum of 30 mPas.
De i oppfinnelsens boreslam anvendte C^_g-karboksylsyreestere har derved hensiktsmessige størkningsverdier (flyte- og stivnepunkt) under 0°C, fortrinnsvis under -5°C og spesielt under —10°C. Samtidig bør flammepunktene for disse estere velges høyest mulig, spesielt av sikkerhetsgrunner, slik at de foretrukne grenseverdier for flammepunktet ligger ved ca. 90°C og fortrinnsvis over 100°C. The C 1 -g carboxylic acid esters used in the drilling mud of the invention thereby have appropriate solidification values (pour and solidification points) below 0°C, preferably below -5°C and especially below -10°C. At the same time, the flash points for these esters should be chosen as high as possible, especially for safety reasons, so that the preferred limit values for the flash point are at approx. 90°C and preferably above 100°C.
De estere av de lavere karboksylsyrer som er egnet i slammet ifølge oppfinnelsen kan deles i to underklasser. I en første klasse foreligger de lavere monokarboksylsyrer som omset-ningsprodukter av enverdige alkoholer. I dette tilfellet utgjør C-tallet i alkoholen minst 6, ligger dog fortrinnsvis høyere og helst ved 8-10 C-atomer. Den andre underklasse av de her angjeldende esteroljer anvender flerverdige alkoholer som esterdannende komponenter. I betraktning kommer her spesielt to- til fireverdige alkoholer hvorved lavere alkoholer av denne type med fortrinnsvis 2-6 C-atomer, er spesielt egnet. Typiske eksempler på slike flerverdige alkoholer er glykol og/eller propandioler. Både etylenglykol og også propandiol og/eller 1,3-propandiol har spesiell betydning. Foretrukket er i det her beskrevne tilfellet estere av flerverdige alkoholer, fullforestrede reaksjons-produkter, selv om også oppfinnelsen, spesielt når det gjelder høyereverdige alkoholer, ikke er begrenset dertil. Spesielt kan i det sistnevnte tilfellet også anvendelsen av partialestere av slike høyereverdige alkoholer med de nevnte lavere karboksylsyrer, komme i betraktning. The esters of the lower carboxylic acids which are suitable in the sludge according to the invention can be divided into two subclasses. In a first class, the lower monocarboxylic acids exist as conversion products of monohydric alcohols. In this case, the C number in the alcohol is at least 6, but is preferably higher and preferably at 8-10 C atoms. The second subclass of the ester oils concerned here uses polyhydric alcohols as ester-forming components. In particular, di- to tetrahydric alcohols come into consideration here, whereby lower alcohols of this type with preferably 2-6 C atoms are particularly suitable. Typical examples of such polyhydric alcohols are glycol and/or propanediols. Both ethylene glycol and also propanediol and/or 1,3-propanediol are of particular importance. Preferred in the case described here are esters of polyhydric alcohols, fully esterified reaction products, although the invention is also not limited thereto, especially when it comes to higher alcohols. In particular, in the latter case, the use of partial esters of such higher alcohols with the mentioned lower carboxylic acids can also be considered.
De viktigste estere for oppfinnelsens lære avledes fra monokarboksylsyrer med 2-4 C-atomer hvorved den allerede nevnte eddiksyre har spesiell betydning som esterdannende bestanddel. The most important esters for the teachings of the invention are derived from monocarboxylic acids with 2-4 C atoms whereby the already mentioned acetic acid has special importance as an ester-forming component.
En viktig tanke ved valget av de angjeldende alkoholer er basert på følgende ytterligere betraktninger: Ved praktisk anvendelse av esteroljene kan den partielle forsåpning av estrene som regel ikke utelukkes. Ved siden av de derved dannede frie karboksylsyrer henholdsvis de karboksylsyresalter som dannes sammen med alkalireserven, oppstår de frie alkoholer. Deres valg bør treffes slik at det også efter en partiell hydrolyse sikres økologisk og toksikologisk risikofrie arbeidsbetingelser hvorved man her spesielt skal ta hensyn til inhalasjons-toksikologiske betraktninger. De for esterdannelsen anvendte alkoholer bør spesielt ha en så lav flyktighet at de i fri tilstand og under de ventede arbeidsbetingelser ikke fører til noen belastning på arbeidsplattformen. For oppfinnelsens valgte klasse av esteroljer på basis av meget kortkjedede monokarboksylsyrer gir det seg allerede innledningsvis en nødvendighet å anvende sammenligningsvis langkjedede, enverdige alkoholer for å komme frem til en tilstrekkelig reduksjon av esteroljenes flyktighet. Viktig er de her diskuterte betraktninger i de tilfeller der esteroljene av oppfinnelsens definerte type benyttes blandet med andre blandingskomponenter, spesielt andre karboksylsyreestere. Oppfinnelsen tar spesielt og i den foretrukne utførelsesform sikte på at det også efter en i bruk oppståtte partiell hydrolyse, ikke er forbundet med risiki, hverken økologisk eller toksikologisk, spesielt inhalasjons-toksikologisk, å anvende boreslammene. An important consideration in the selection of the relevant alcohols is based on the following additional considerations: In practical use of the ester oils, the partial saponification of the esters cannot, as a rule, be ruled out. Next to the resulting free carboxylic acids or the carboxylic acid salts formed together with the alkali reserve, free alcohols occur. Their choice should be made so that even after partial hydrolysis, ecologically and toxicologically risk-free working conditions are ensured, whereby inhalation-toxicological considerations must be taken into account here. The alcohols used for the ester formation should in particular have such a low volatility that, in their free state and under the expected working conditions, they do not lead to any strain on the work platform. For the invention's chosen class of ester oils based on very short-chain monocarboxylic acids, it is already initially necessary to use comparatively long-chain, monovalent alcohols in order to arrive at a sufficient reduction of the volatility of the ester oils. The considerations discussed here are important in cases where the ester oils of the type defined by the invention are used mixed with other mixture components, especially other carboxylic acid esters. The invention particularly and in the preferred embodiment aims to ensure that, even after a partial hydrolysis has occurred in use, there is no risk, either ecologically or toxicologically, especially inhalation-toxicologically, of using the drilling muds.
Egnede alkoholer og spesielt egnede enverdige alkoholer kan være av naturlig og/eller syntetisk opprinnelse. Det kan derved anvendes rette og/eller forgrenede alkoholer. Kjedelengden når det foreligger overveiende alifatisk mettede alkoholer ligger fortrinnsvis i området cg_i5* Egnet er imidlertid også en- og/eller flere ganger olefinisk umettede alkoholer, slik de for eksempel kan oppnås ved reduksjon av naturlig tilgjengelig umettede fettsyrer henholdsvis fettsyreblandinger. Den slags en- og/eller flere ganger olefinisk umettede alkoholer kan da nå også høyere karbontall i oppfinnelsens esteroljer og for eksempel ligge ved ca. Cg^. Suitable alcohols and particularly suitable monohydric alcohols can be of natural and/or synthetic origin. Straight and/or branched alcohols can thereby be used. The chain length when predominantly aliphatic saturated alcohols are present is preferably in the range cg_i5* However, mono- and/or multiple olefinically unsaturated alcohols are also suitable, as they can for example be obtained by reducing naturally available unsaturated fatty acids or fatty acid mixtures. Such mono- and/or multiple olefinically unsaturated alcohols can then also reach higher carbon numbers in the ester oils of the invention and, for example, lie at approx. Cg^.
Esteroljer av den her beskrevne art kan helt og holdent danne den lukkede oljefase i vann-i-olje-invert-slammet. På den annen side ligger det innenfor oppfinnelsens tekniske lære at de karboksylsyreestere som anvendes i slammet Ifølge oppfinnelsen kun er en blandingsbestanddel av oljefasen. Som ytterligere oljekomponenter er i praksis hvilke som helst tidligere kjente og/eller ovenfor beskrevne oljekomponenter på det her angjeldende anvendelsesområdet, egnet. I det følgende skal det gås nærmere inn på spesielle egnede blandingskomponenter. Ester oils of the type described here can completely form the closed oil phase in the water-in-oil invert sludge. On the other hand, it is within the technical teachings of the invention that the carboxylic acid esters used in the sludge According to the invention are only a mixture component of the oil phase. As additional oil components, any previously known and/or above-described oil components in the area of application in question are suitable in practice. In the following, special suitable mixture components will be discussed in more detail.
De esteroljer som anvendes i slammet ifølge oppfinnelsen er som regel homogent blandbare med blandingskomponentene i hvilke som helst blandingsforhold. Hensiktsmessig foreligger, innenfor oppfinnelsens ramme, i det minste 25% og aller helst minst en tredjedel av oljefasen, i form av c^_ 5~ esteroljer. I viktige utførelsesformer av oppfinnelsen utgjør esteroljene hovedandelen av oljefasen. The ester oils used in the sludge according to the invention are generally homogeneously miscible with the mixture components in any mixing ratio. Appropriately, within the scope of the invention, at least 25% and most preferably at least one third of the oil phase is present in the form of c^_ 5~ ester oils. In important embodiments of the invention, the ester oils form the main part of the oil phase.
Egnede oljekomponenter for blanding med monokarboksylsyre-estrene i slammet ifølge oppfinnelsen er de i dagens praksis i boreslam anvendte mineraloljer og derved fortrinnsvis i det vesentlige aromatfrie, alifatiske og/eller cykloalifatiske hydrokarbonfraksjoner med de krevede helleegenskaper. Det skal her henvises til den foreliggende teknikk på området og til i handelen foreliggende produkter. Suitable oil components for mixing with the monocarboxylic acid esters in the mud according to the invention are the mineral oils used in current practice in drilling mud and thereby preferably essentially aromatic-free, aliphatic and/or cycloaliphatic hydrocarbon fractions with the required pouring properties. Reference must be made here to the available technology in the area and to commercially available products.
Spesielt viktige blandingskomponenter er imidlertid ifølge oppfinnelsen de miljøvennlige esteroljer slik de spesielt beskrives i NO-171 562B og NO-171 601B. For å fullføre oppfinnelsens beskrivelse skal det nedenfor gåes nærmere inn på karakteristiske data for slike estere henholdsvis esterblandinger. According to the invention, however, especially important mixture components are the environmentally friendly ester oils as they are particularly described in NO-171 562B and NO-171 601B. In order to complete the description of the invention, characteristic data for such esters and ester mixtures will be discussed below.
I en første utførelsesform blir i temperaturområdet fra 0 til 5°C, hell- og pumpbare estere av enverdige alkoholer med 2-12 og spesielt med 6-12 C-atomer og alifatisk mettede monokarboksylsyrer med 12-16 C-atomer eller deres blandinger med høyst omtrent like mengder andre monokarboksylsyrer, anvendt som oljefase. Foretrukket er herved esteroljer som i en mengde av ca. 60$, beregnet på karboksylsyreblandingen, er estere av alifatiske C^g_^^-monokarboksylsyrer og eventuelt hva resten angår, avledes fra underordnede mengder kortere-kjedede alifatiske og/eller lengrekjedede og da spesielt en-og/eller flere ganger olefinisk, umettede monokarboksylsyrer. Foretrukket anvendes det estere som, i temperaturområdet fra 0 til 5°C, oppviser en Brookfield-RVT-viskositet i området ikke over 50 mPas, fortrinnsvis ikke over 40 mPas, og spesielt aller helst høyst ca. 30 mPas. De i boreslammet anvendte estere oppviser størkningsverdier (helle- og stivningspunkt) under -10°C, fortrinnsvis under -15°C, og har derved spesielt flammepunkter over 100°C, fortrinnsvis over 150°C. De i esteren henholdsvis esterblandingen foreliggende karboksylsyrer er rettkjedede og/eller forgrenede og også av vegetabilsk og/eller syntetisk opprinnelse. De kan stamme fra tilsvarende triglycerider som kokosolje, palmekjerneolje og/eller babassuolje. Alkoholresten fra de anvendte estere stammer spesielt fra rettkjedede og/eller forgrenede, mettede alkoholer med fortrinnsvis 6-10 C-atomer. Også disse alkoholkomponenter kan være av vegetabilsk og/eller animalsk opprinnelse og derved være oppnådd ved reduktiv hydrering av tilsvarende karboksylsyreestere. In a first embodiment, in the temperature range from 0 to 5°C, pourable and pumpable esters of monohydric alcohols with 2-12 and especially with 6-12 C atoms and aliphatically saturated monocarboxylic acids with 12-16 C atoms or their mixtures with at most approximately equal amounts of other monocarboxylic acids, used as oil phase. Preference is hereby given to ester oils which in an amount of approx. 60$, calculated on the carboxylic acid mixture, are esters of aliphatic C^g_^^-monocarboxylic acids and possibly, as far as the remainder is concerned, derived from subordinate amounts of shorter-chained aliphatic and/or longer-chained and then especially mono- and/or multiple-times olefinically unsaturated monocarboxylic acids . Preferably, esters are used which, in the temperature range from 0 to 5°C, exhibit a Brookfield-RVT viscosity in the range of not more than 50 mPas, preferably not more than 40 mPas, and especially most preferably no more than approx. 30 mPas. The esters used in the drilling mud exhibit solidification values (pouring and solidification points) below -10°C, preferably below -15°C, and thereby particularly have flash points above 100°C, preferably above 150°C. The carboxylic acids present in the ester or the ester mixture are straight-chain and/or branched and also of vegetable and/or synthetic origin. They can originate from similar triglycerides such as coconut oil, palm kernel oil and/or babassu oil. The alcohol residue from the esters used originates in particular from straight-chain and/or branched, saturated alcohols with preferably 6-10 C atoms. These alcohol components can also be of vegetable and/or animal origin and thereby be obtained by reductive hydration of corresponding carboxylic acid esters.
En ytterligere klasse spesielt egnede esteroljer avledes fra olefinisk en- og/eller flere ganger umettede monokarboksylsyrer med 16-24 C-atomer eller deres blandinger med underordnede mengder andre, spesielt mettede monokarboksylsyrer og enverdige alkoholer med fortrinnsvis 6-12 C-atomer. Også disse esteroljer er hell- og pumpbare i temperaturområdet fra 0 til 5°C. Egnet er spesielt estere av denne type som i en mengde av mer enn 70 vekt-%, fortrinnsvis mer enn 80 vekt-# og aller helst mer enn 90 vekt-#, avledes fra olefinisk umettede karboksylsyrer innen området ^^. 6- 2^' A further class of particularly suitable ester oils are derived from olefinically mono- and/or polyunsaturated monocarboxylic acids with 16-24 C atoms or their mixtures with minor amounts of other, especially saturated monocarboxylic acids and monohydric alcohols with preferably 6-12 C atoms. These ester oils are also pourable and pumpable in the temperature range from 0 to 5°C. Particularly suitable are esters of this type which in an amount of more than 70% by weight, preferably more than 80% by weight and most preferably more than 90% by weight, are derived from olefinically unsaturated carboxylic acids within the range ^^. 6- 2^'
Også her ligger størkningsverdiene (helle- og stivnepunkt) under —10°C, fortrinnsvis under —15°C, mens flammepunktet ligger over 100°C og fortrinnsvis over 160°C. De i boreslammet anvendte estere oppviser 1 temperaturområdet 0-5°C en Brookfield-RVT-viskositet på ikke mer enn 55 mPas, fortrinnsvis ikke mer enn 45 mPas. Here, too, the solidification values (pour and solidification points) are below -10°C, preferably below -15°C, while the flash point is above 100°C and preferably above 160°C. The esters used in the drilling mud exhibit in the temperature range 0-5°C a Brookfield-RVT viscosity of no more than 55 mPas, preferably no more than 45 mPas.
Ved esteroljer av den her beskrevne type kan man definere to underklasser. I den første avledes den i esteren foreliggende umettede C^^g^-monokarboksylsyrerest i en mengde av ikke mer enn 35 vekt-# fra to- og flere ganger olefinisk umettede syrer hvorved fortrinnsvis minst 60 vekt-# av syreresten er enkelt olefinisk umettet. I den andre utførelsesform avledes de i esterblandingen foreliggende C16_24-monokarboksylsyrer i en mengde av mer enn 45 vekt-#, fortrinnsvis mer enn 55 vekt-#, fra to- og/eller ganger olefinisk umettede syrer. I esterblandingen foreliggende mettede karboksylsyrer i området <c>16—18 utgjør hensiktsmessig ikke mer enn 20 vekt-5é og spesielt ikke mer enn ca. 10 vekt-#. Fortrinnsvis ligger umettede karboksylsyreestere i området lavere C-tall i syrerestene. De foreliggende karboksylsyrerester kan være av vegetabilsk og/eller animalsk opprinnelse. Vegetabilske utgangsmaterialer er for eksempel palme-, jordnøtt-, ricinus-og spesielt beteolje. Karboksylsyrer av animalsk opprinnelse er spesielt tilsvarende blandinger av fiskeoljer som sildeolje. For ester oils of the type described here, two subclasses can be defined. In the first, the unsaturated C^^g^-monocarboxylic acid residue present in the ester is derived in an amount of no more than 35 wt-# from doubly or more olefinically unsaturated acids whereby preferably at least 60 wt-# of the acid residue is singly olefinically unsaturated. In the second embodiment, the C16-24 monocarboxylic acids present in the ester mixture are derived in an amount of more than 45% by weight, preferably more than 55% by weight, from doubly and/or doubly olefinically unsaturated acids. In the ester mixture present saturated carboxylic acids in the range <c>16-18 conveniently amount to no more than 20% by weight and in particular no more than approx. 10 weight #. Unsaturated carboxylic acid esters are preferably in the area of lower C numbers in the acid residues. The present carboxylic acid residues can be of vegetable and/or animal origin. Vegetable starting materials are, for example, palm, peanut, castor oil and especially beet oil. Carboxylic acids of animal origin are particularly similar to mixtures of fish oils such as herring oil.
Egnede blandingskomponenter er til slutt imidlertid de i N0-B (P913290) beskrevne estere av monokarboksylsyrer av syntetisk og/eller naturlig opprinnelse med 6-11 C-atomer og en- og/eller flerverdige alkoholer, som fortrinnsvis er hell- og pumpbar også i temperaturområdet 0-5°C. For å fullføre oppfinnelsens beskrivelse henvises det til dette patent. Finally, however, suitable mixture components are the esters of monocarboxylic acids of synthetic and/or natural origin described in N0-B (P913290) with 6-11 C atoms and mono- and/or polyhydric alcohols, which are preferably pourable and pumpable also in temperature range 0-5°C. To complete the description of the invention, reference is made to this patent.
I betraktning kommer som ytterligere blandingskomponent i invert-boreslammet alle vanlige blandingsbestanddeler for kondisjonering og for den praktiske anvendelse av invert-boreslammene slik de i dagens praksis kommer til anvendelse med mineraloljer som lukket oljefase. Ved siden av den disperse vandige fase kommer her i betraktning spesielt emulgatorer, tyngdegivende midler, væsketapsadditiv, viskositetsdannere og alkalireserver. All common mixture components for conditioning and for the practical use of the invert drilling mud as they are used in current practice with mineral oils as closed oil phase are taken into consideration as additional mixing components in the invert drilling mud. Alongside the dispersed aqueous phase, emulsifiers, weighting agents, liquid loss additives, viscosity formers and alkali reserves are particularly taken into account here.
I en spesielt viktig utførelsesform av oppfinnelsen gjør man også her bruk av videreutviklingen av slike invert-boreslam på esteroljebasis som er gjenstand for NO- (P913041). In a particularly important embodiment of the invention, use is also made here of the further development of such ester oil-based invert drilling muds which are subject to NO- (P913041).
Læren i denne eldre søknad går altså ut fra det konsept, i invert-boreslam på basis av esteroljer å anvende et ytterligere additiv som er egnet til å holde de ønskede reologiske data i boreslammet innen det krevede området også når det i bruk dannes tiltagende større mengder frie karboksylsyrer på grunn av partiell esterhydrolyse. Disse friblivende karboksylsyrer skal ikke bare fanges opp i en uskadelig form, det skal i tillegg til dette være mulig hvis ønskelig, å omdanne disse frie karboksylsyrer til verdifulle komponenter med stabiliserende henholdsvis emulgerende egenskaper for det totale system. Tilsiktet efter denne lære er medanvendelse av basiske og for saltdannelse med karboksylsyre brukbare aminforbindelser av utpreget oleofil art og høyst begrenset vannoppløselighet som additiv i oljefasen. De oleofile aminforbindelser kan samtidig i det minste delvis tjene som alkalireserve for invert-boreslammet, det kan imidlertid også anvendes i kombinasjon med konvensjonelle alkalireserver, spesielt sammen med kalk. Foretrukket er anvendelsen av oleofile aminforbindelser som i det minste overveiende er frie for aromatiske bestanddeler. I betraktning kommer spesielt eventuelt olefinisk umettede alifatiske, cykloalifatiske og/eller heterocykliske oleofile basiske aminforbindelser som inneholder en eller også flere N—grup-peringer som kan danne salter med karboksylsyrer. Vann-oppløseligheten ved romtemperatur for disse aminforbindelser utgjør i en foretrukket utførelsesform høyst 5 vekt-# og ligger hensiktsmessig under 1 vekt-#. The teaching in this older application is therefore based on the concept, in invert drilling mud based on ester oils, to use an additional additive which is suitable to keep the desired rheological data in the drilling mud within the required range, even when increasingly large amounts are formed in use free carboxylic acids due to partial ester hydrolysis. These free carboxylic acids must not only be captured in a harmless form, it must also be possible, if desired, to convert these free carboxylic acids into valuable components with stabilizing or emulsifying properties for the overall system. The intention according to this teaching is the co-use of basic amine compounds usable for salt formation with carboxylic acid of a distinctly oleophilic nature and with very limited water solubility as an additive in the oil phase. The oleophilic amine compounds can at the same time at least partially serve as an alkali reserve for the invert drilling mud, however, it can also be used in combination with conventional alkali reserves, especially together with lime. The use of oleophilic amine compounds which are at least predominantly free of aromatic components is preferred. In particular, possibly olefinically unsaturated aliphatic, cycloaliphatic and/or heterocyclic oleophilic basic amine compounds which contain one or more N groups which can form salts with carboxylic acids come into consideration. The water solubility at room temperature for these amine compounds amounts in a preferred embodiment to no more than 5 wt-# and is suitably below 1 wt-#.
Typiske eksempler på slike aminforbindelser er i det minste i utstrakt grad vannuoppløselige primære, sekundære og/eller tertiære aminer som også kan være begrenset alkoksylert og/eller spesielt være substituert med hydroksylgrupper. Ytterligere eksempler er tilsvarende aminoamider og/eller heterocykliske forbindelser som inneholder nitrogen som ringbestanddel. Egnet er for eksempel basiske aminforbindelser som oppviser minst en langkjedet hydrokarbonrest med fortrinnsvis 8-36 C-atomer, spesielt med 10-24 C-atomer, som også kan være en- eller flere ganger olefinisk umettet. De oleofile basiske aminforbindelser kan tilsettes til boreslammet i mengder på opp til 10 lb/bbl, fortrinnsvis i mengder på ca. 5 lb/bbl og spesielt i området 0,1-2 lb/bbl (Omregningsfaktor: 1 lb/bbl = 2,8530 g/l). Typical examples of such amine compounds are at least to a large extent water-insoluble primary, secondary and/or tertiary amines which may also be limited alkoxylated and/or especially be substituted with hydroxyl groups. Further examples are corresponding amino amides and/or heterocyclic compounds containing nitrogen as a ring component. Suitable are, for example, basic amine compounds which exhibit at least one long-chain hydrocarbon residue with preferably 8-36 C atoms, especially with 10-24 C atoms, which can also be one or more times olefinically unsaturated. The oleophilic basic amine compounds can be added to the drilling mud in amounts of up to 10 lb/bbl, preferably in amounts of approx. 5 lb/bbl and especially in the range 0.1-2 lb/bbl (Conversion factor: 1 lb/bbl = 2.8530 g/l).
Det har vist seg at medanvendelsen av slike oleofile basiske aminforbindelser på virkningsfull måte kan hindre for-tykninger i slamsystemet, som sannsynligvis er å føre tilbake til en forstyrrelse i vann-i-olje-invert-systemet og dannelse av frie karboksylsyrer ved esterhydrolyse. It has been shown that the co-use of such oleophilic basic amine compounds can effectively prevent thickening in the sludge system, which is likely to lead back to a disturbance in the water-in-oil invert system and formation of free carboxylic acids by ester hydrolysis.
Hvis det innenfor oppfinnelsens lære anvendes estere av lengrekjedede karboksylsyrer som blandingskomponenter og som ved hydrolytisk spalting fører til fettsyrer henholdsvis fettsyresalter med utpreget olje-i-vann-emulgeringsvirkning, må man også innenfor foreliggende oppfinnelses ramme ta hensyn til forholdsregler med henblikk på alkalireserven slik det i enkelhet er beskrevet i NO-171 562B og NO-171 601B. Når det gjelder slike esterblandinger gjelder det følgende: I en foretrukket utførelsesform av oppfinnelsen passer man på at det i oljeslammet ikke medanvendes vesentlige mengder sterkt hydrofile baser av uorganisk og/eller organisk art. Spesielt gir man avkall på medanvendelse av alkalihydroksyder eller sterkt hydrofile aminer av typen dietanolamin og/eller trietanolamin. Kalk kan på virkningsfull måte medanvendes som alkalireserve. Det er da imidlertid hensiktsmessig å begrense den maksimal anvendte kalkmengde til ca. 2 lb/bbl hvorved det kan være å foretrekke å arbeide med tilsetninger av kalk som ligger noe derunder, for eksempel altså i området 1-1,8 lb/bbl (kalk/boreslam). Ved siden av eller i stedet for kalken kan man anvende andre alkalireserver av kjent type. Nevnes her skal spesielt de mindre basiske metalloksyder av typen sinkoksyd. Også ved anvendelse av slike syreoppfangere må det imidlertid ikke anvendes for store mengder for derved å forhindre en uønsket for tidlig aldring av boreslammet, forbundet med en viskositetsstlgning og dermed også en forringelse av de reologiske egenskaper. På grunn av det her diskuterte særpreg ved oppfinnelsen forhindrer og/eller begrenser man dannelsen av uønskede mengder av sterkt virksomme olje-i-vann-emulgatorer på en slik måte at man kan opprettholde de gode reologiske anvendelsesverdier også ved termisk aldring i drift i tilstrekkelig lang tid. If, within the scope of the invention, esters of longer-chain carboxylic acids are used as mixture components and which, by hydrolytic cleavage, lead to fatty acids or fatty acid salts with a pronounced oil-in-water emulsifying effect, precautions must also be taken within the framework of the present invention with regard to the alkali reserve, as in simplicity is described in NO-171 562B and NO-171 601B. When it comes to such ester mixtures, the following applies: In a preferred embodiment of the invention, care is taken that significant amounts of strongly hydrophilic inorganic and/or organic bases are not co-used in the oil sludge. In particular, the co-use of alkali hydroxides or strongly hydrophilic amines of the type diethanolamine and/or triethanolamine is waived. Lime can be used effectively as an alkali reserve. However, it is then appropriate to limit the maximum amount of lime used to approx. 2 lb/bbl, whereby it may be preferable to work with additions of lime that are slightly below that, for example in the range of 1-1.8 lb/bbl (lime/drilling mud). Next to or instead of the lime, other alkali reserves of a known type can be used. Particular mention should be made here of the less basic metal oxides of the zinc oxide type. Even when using such acid scavengers, however, excessive amounts must not be used in order to thereby prevent an unwanted premature aging of the drilling mud, associated with a reduction in viscosity and thus also a deterioration of the rheological properties. Due to the distinctive features of the invention discussed here, the formation of unwanted amounts of highly effective oil-in-water emulsifiers is prevented and/or limited in such a way that the good rheological application values can be maintained even with thermal aging in operation for a sufficiently long time time.
I tillegg gjelder følgende: In addition, the following applies:
Invert-boreslam av den her beskrevne art inneholder vanligvis, sammen med den lukkede oljefase, den findispergerte vandige fase i mengder på 5 til 45 vekt-# og fortrinnsvis i mengder på 5 til 25 vekt-56. Området 10 til 25 vekt-Sé dispergert vandig fase kan ha spesiell betydning. Invert drilling muds of the type described herein usually contain, together with the closed oil phase, the finely dispersed aqueous phase in amounts of 5 to 45 wt-# and preferably in amounts of 5 to 25 wt-56. The range of 10 to 25 wt-Sé dispersed aqueous phase can be of particular importance.
For reologien til invert-boreslam innenfor oppfinnelsens ramme gjelder følgende reologiske data: Plastisk viskositet (PV) i området 10-60 mPas, foretrukket 15-40 mPas; flytgrense (Yield Point YP) i området 5-40 lb/100 ft2 , fortrinnsvis 10-25 lb/ft2 , alt bestemt ved 50°C (omregningsfaktor 1 lb/100 ft<2> = 2,0885 Pa). For bestemmelse av denne para-meter, for de derved anvendte målemetoder samt for de forøvrig vanlige sammensetninger av de her beskrevne invert-boreslam, gjelder i detalj det som angis i den kjente teknikk som nevnt innledningsvis og som utførlig for eksempel beskrives i håndboken "Manual Of Drilling Fluids Technology" fra firma NL-Baroid, London, GB, der spesielt under kapitlet "Mud Testing - Tools and Techniques" samt "Oil Mud Technology", som er fritt tilgjengelig for den interesserte fagverden. Som en oppsummering kan man for å fullføre oppfinnelsens beskrivelse, si følgende: I praksis brukbare emulgatorer er systemer som er egnet for dannelse av de krevede vann-i-olje-emulsjoner. I betraktning kommer spesielt utvalgte oleofile fettsyresalter, for eksempel slike på basis av amidoaminforbindelser. Eksempler på disse er beskrevet i det allerede nevnte XJS-PS 4 374 737 og den der angitte litteratur. En spesielt egnet emulgator-type er den som markedsføres av firma NL Baroid under navnet "EZ-mul". For the rheology of invert drilling mud within the framework of the invention, the following rheological data apply: Plastic viscosity (PV) in the range 10-60 mPas, preferably 15-40 mPas; yield point YP in the range 5-40 lb/100 ft2 , preferably 10-25 lb/ft2 , all determined at 50°C (conversion factor 1 lb/100 ft<2> = 2.0885 Pa). For the determination of this parameter, for the measuring methods used thereby as well as for the otherwise common compositions of the invert drilling mud described here, what is stated in detail in the known technique as mentioned at the beginning and which is described in detail, for example, in the manual "Manual Of Drilling Fluids Technology" from the company NL-Baroid, London, GB, there especially under the chapter "Mud Testing - Tools and Techniques" as well as "Oil Mud Technology", which is freely available to the interested professional world. As a summary, to complete the description of the invention, the following can be said: Practically usable emulsifiers are systems which are suitable for forming the required water-in-oil emulsions. Specially selected oleophilic fatty acid salts, for example those based on amidoamine compounds, come into consideration. Examples of these are described in the already mentioned XJS-PS 4 374 737 and the literature indicated there. A particularly suitable type of emulsifier is that marketed by the company NL Baroid under the name "EZ-mul".
Emulgatorer av den her beskrevne type kan oppnås kommersielt som høykonsentrerte aktiv-bestanddeltilberedninger og kan for eksempel finne anvendelse i mengder på 2,5-5 vekt-#, spesielt i mengder på 3-4 vekt-#, alt beregnet på ester-oljefasen. Emulsifiers of the type described here can be obtained commercially as highly concentrated active ingredient preparations and can, for example, find use in amounts of 2.5-5 wt-#, especially in amounts of 3-4 wt-#, all intended for the ester-oil phase.
Som væsketapsadditiv og derved spesielt for dannelse av et tykt belegg på boreveggene med en i utstrakt grad vaeske-ugjennomtrengelig film, anvendes det i praksis spesielt hydrofobert lignitt. Egnede mengder ligger for eksempel i området 15-20 lb/bbl eller i området 5-7 vekt-#, beregnet på esteroljefasen. As a liquid loss additive and thereby especially for the formation of a thick coating on the drill walls with a largely liquid-impermeable film, particularly hydrophobic lignite is used in practice. Suitable amounts are, for example, in the range of 15-20 lb/bbl or in the range of 5-7 wt-#, calculated for the ester oil phase.
I boreslam av den her beskrevne art er den vanligvis anvendte viskositetsdanner en kationisk modifisert, finfordelt bentonitt som spesielt kan anvendes i mengder fra 8 til 10 lb/bbl eller i området 2-4 vekt-5é. De i praksis vanligvis anvendte tyngdegivende middel for innstilling av den nødvendige trykkutjevning er barytt, hvis tilsetningsmengde tilpasses ventede betingelser i borehullet. Ved tilsetning av barytt er det for eksempel mulig å heve den spesifikke vekt for boreslammet til verdier i området ca. 2,5, fortrinnsvis innen området 1,3-1,6. In drilling mud of the type described here, the commonly used viscosity former is a cationically modified, finely divided bentonite which can especially be used in quantities from 8 to 10 lb/bbl or in the range of 2-4 weight-5é. The generally used weighting agent for setting the necessary pressure equalization is baryte, the amount of which is added to the expected conditions in the borehole. By adding baryte, for example, it is possible to raise the specific weight of the drilling mud to values in the range of approx. 2.5, preferably within the range 1.3-1.6.
Den dispergerte vandige fase blir i invert-boreslam av den her angjeldende type, fylt med oppløselige salter. Overveiende anvendes her kalsiumklorid og/eller kaliumklorid, hvorved metning av den vandige fase med det oppløselige salt ved romtemperatur, er foretrukket. The dispersed aqueous phase is filled with soluble salts in invert drilling mud of the type in question here. Predominantly calcium chloride and/or potassium chloride are used here, whereby saturation of the aqueous phase with the soluble salt at room temperature is preferred.
De tidligere nevnte emulgatorer henholdsvis emulgatorsystemer tjener eventuelt også til å forbedre oljefuktbarheten for det uorganiske tyngdegivende middel. Ved siden av de allerede nevnte aminoamider skal som ytterligere eksempel også nevnes alkylbenzensulfonater samt imidazolinforbindelser. Ytterligere opplysninger om den gjeldende kjente teknikk finnes i GB 2 158 437, EP 229 912 samt DE 32 47 123. The previously mentioned emulsifiers or emulsifier systems may also serve to improve the oil wettability of the inorganic bulking agent. Alongside the already mentioned amino amides, alkylbenzene sulphonates and imidazoline compounds should also be mentioned as further examples. Further information on the current known technique can be found in GB 2 158 437, EP 229 912 and DE 32 47 123.
De på medanvendelse av esteroljer av den beskrevne type oppbygde boreslam utmerker seg i tillegg til de allerede skildrede fordeler ved en tydelig forbedret smøreevne. Viktig er dette spesielt når boringen for eksempel på store dyp avviker fra det loddrette. Den roterende borestreng kommer her lett i kontakt med borehullveggen og graver seg ved drift inn i denne. Esteroljer av den ifølge oppfinnelsen som oljefase anvendte type har en tydelig bedre smørevirkning enn de til nu anvendte mineraloljer. Her ligger en ytterligere viktig fordel som oppnås ifølge oppfinnelsen. In addition to the already described advantages, the built-up drilling muds of the type described with the combined use of ester oils are distinguished by a clearly improved lubrication ability. This is particularly important when, for example, drilling at great depths deviates from the vertical. The rotating drill string here easily comes into contact with the borehole wall and digs into it during operation. Ester oils of the type used as the oil phase according to the invention have a clearly better lubricating effect than the mineral oils currently used. Here lies a further important advantage which is achieved according to the invention.
Oppfinnelsen skal illustreres nærmere under henvisning til de ledsagende eksempler: The invention shall be illustrated in more detail with reference to the accompanying examples:
EKSEMPLER EXAMPLES
I de efterfølgende eksempler fremstilles det invert-boreslam på konvensjonell måte under anvendelse av den følgende rammesammensetning: In the following examples, the invert drilling mud is produced in a conventional manner using the following framework composition:
230 ml esterolje 230 ml ester oil
26 ml vann 26 ml of water
6 g organofil bentonltt ("Geitone II" fra firma NL Baroid) 12 g organofil lignitt ("Duratone" fra firma NL Baroid) 6 g organophilic bentonite ("Geitone II" from the company NL Baroid) 12 g organophilic lignite ("Duratone" from the company NL Baroid)
x g kalk (x = 1 eller 2) x g lime (x = 1 or 2)
6 g vann/olje-emulgator ("EZ-mul NT" fra firma NL Baroid) 6 g water/oil emulsifier ("EZ-mul NT" from the company NL Baroid)
346 g barytt 346 g baryte
9,2 g CaCl2 x 2E20 9.2 g of CaCl2 x 2E2O
I denne sammensetning tilsvarer ca. 1,35 g kalk verdien 2 lb/bbl. In this composition, approx. 1.35 g lime value 2 lb/bbl.
Efter at man på i og for seg kjent måte fra de anvendte komponenter tildannet et vann-i-olje-invert-boreslam under variasjon av esteroljefasen bestemte man viskositetsverdiene på ikke-aldret og så på aldret materiale: Måling av viskositeten ved 50°C ble gjennomført i et Fann-35-viskosimeter fra firma NL Baroid. Man bestemte på i og for seg kjent måte den plastiske viskositet (PV), flytgrensen (YP) samt gelstyrken (1 lb/100 ft<2> = 2,0885 Pa) efter 10 sekunder og efter 10 minutter. After a water-in-oil invert drilling mud was formed in a known manner from the components used while varying the ester oil phase, the viscosity values were determined on non-aged and then on aged material: Measurement of the viscosity at 50°C was carried out in a Fann-35 viscometer from the company NL Baroid. The plastic viscosity (PV), yield strength (YP) and gel strength (1 lb/100 ft<2> = 2.0885 Pa) were determined in a manner known per se after 10 seconds and after 10 minutes.
Aldringen skjedd ved behandling i autoklav i en såkalt "Roller-oven" i et tidsrom på 16 timer ved 125°C. The aging took place by treatment in an autoclave in a so-called "Roller oven" for a period of 16 hours at 125°C.
Som ester anvender man isotridecylacetat med de følgende reologiske karakteristika: viskositet ved 20°C lik 5 mPas; viskositet ved 50°C lik 2,1 mPas; størkningspunkt under -10°C. As ester, isotridecyl acetate is used with the following rheological characteristics: viscosity at 20°C equal to 5 mPas; viscosity at 50°C equal to 2.1 mPas; freezing point below -10°C.
I det følgende eksempel 1 utgjør den i rammesammensetningen anvendte kalkmengde 2 g, i eksempel 2 reduseres mengden til 1 g. In the following example 1, the amount of lime used in the frame composition is 2 g, in example 2 the amount is reduced to 1 g.
De på ikke-aldret og aldret materiale bestemte karakteristiske data er sammenfattet i de følgende tabeller: The characteristic data determined on unaged and aged material are summarized in the following tables:
Eksempel 1 Example 1
Eksempel 2 Example 2
Rammesammensetningen i disse eksempler 1 og 2 tilsvarer i vektforhold oljefase:vann med tallverdiene 90:10. I ytterligere forsøk ble det foretatt undersøkelser ved endring av esterolje:vann-forhold til verdiene 80:20. The frame composition in these examples 1 and 2 corresponds in weight ratio to oil phase:water with the numerical values of 90:10. In further experiments, investigations were carried out by changing the ester oil:water ratio to the values 80:20.
I de følgende eksempler 3 og 4 ble det fremstilt invert-boreslam under anvendelse av esteroljer på basis av isotridecylacetat under anvendelse av følgende rammesammensetning: Som i eksemplene 1 og 2 bestemmer man først på ikke-aldret og så på aldret materiale (16 timer ved 125°C i "Roller-oven") viskositetsverdiene (eksempel 3). In the following examples 3 and 4, invert drilling mud was produced using ester oils based on isotridecyl acetate using the following framework composition: As in examples 1 and 2, one determines first on non-aged and then on aged material (16 hours at 125 °C in the "Roller-oven") the viscosity values (Example 3).
I en ytterligere forsøkssats, eksempel 4, blir den angitte rammesammensetning i eksempel 3 endret ved tilsetning av et sterkt oleofilt amin i en mengde av 2 g (kommersielt tilgjengelig "Araphen G2D" fra firma Henkel, omsetnings-produktet av et epoksydert C^g^^-cx-olef in og dietanolamin). Derefter blir som ovenfor nok en gang viskositetsverdiene målt på ikke-aldret og så på aldret materiale. In a further experimental batch, example 4, the specified framework composition in example 3 is changed by the addition of a strong oleophilic amine in an amount of 2 g (commercially available "Araphen G2D" from the company Henkel, the reaction product of an epoxidized C^g^ ^-cx-olef in and diethanolamine). Then, as above, once again the viscosity values are measured on non-aged and then on aged material.
Eksempel 3 Example 3
Eksempel 5 Example 5
Som esterolje anvendes esterblandingen av eddlksyre og et C^_10-alkoholsnitt (kommersielt tilgjengelig "Lorol" fra firma Henkel), fremstilt ved reduksjon av det tilsvarende forløpsfettsyresnitt av naturlig opprinnelse. Rammesammensetningen tilsvarer den innledningsvis nevnte formulering for eksempel 2. As ester oil, the ester mixture of acetic acid and a C 10 alcohol cut (commercially available "Lorol" from the company Henkel), produced by reduction of the corresponding precursor fatty acid cut of natural origin, is used. The frame composition corresponds to the initially mentioned formulation for example 2.
Bestemmelse av viskositetsdata og aldring skjer som angitt tidligere. Man oppnådde følgende viskositetsverdier. Determination of viscosity data and aging takes place as stated earlier. The following viscosity values were obtained.
Eksemplene 6 til 8 Examples 6 to 8
I parallelle satser ble det fremstilt tre boreslam på basis isotridecylacetat i henhold til rammesammensetningen ifølge eksemplene 1 og 2 med et forhold oljefase:vann på 90:10. Som i de tidligere eksempler bestemte man de reologiske data tuni dde lb art efter fremstilling samt efter en aldring i "Roller-oven" ved 125°C i et tidsrom på 16 timer. In parallel batches, three drilling muds were produced based on isotridecyl acetate according to the framework composition according to examples 1 and 2 with an oil phase:water ratio of 90:10. As in the previous examples, the rheological data was determined for each species after manufacture and after aging in the "Roller-oven" at 125°C for a period of 16 hours.
Derved arbeidet man i et første slam uten tilsetning av kalk, eksempel 6, i et andre slam, eksempel 7, ble det tilsatt 2 g kalk, mens det i det tredje slam, eksempel 8, ble tilsatt 2 g kalk sammen med 1 g av det sterkt oleofile amin "Araphen G2D" . Thereby one worked in a first sludge without the addition of lime, example 6, in a second sludge, example 7, 2 g of lime was added, while in the third sludge, example 8, 2 g of lime was added together with 1 g of the strongly oleophilic amine "Araphen G2D".
De i hvert tilfelle bestemte reologiske data er som følger: The rheological data determined in each case are as follows:
Eksempel 6 Example 6
Eksempel 7 Eksempel 8 Example 7 Example 8
Eksemplene 9 til 11 Examples 9 to 11
I en ytterligere sammenlignende forsøksserie ble det fremstilt boreslam på basis av isotridecylacetat i rammesammensetningen i eksemplene 6 til 8 som følger: Eksempel 9-tilsetning av 1 g kalk; Eksempel 10 - tilsetning av 2 g kalk; Eksempel 11 - tilsetning av 2 g kalk + 1 g "Araphen G2D". In a further comparative test series, drilling mud was produced on the basis of isotridecyl acetate in the framework composition in examples 6 to 8 as follows: Example 9 - addition of 1 g of lime; Example 10 - addition of 2 g of lime; Example 11 - addition of 2 g lime + 1 g "Araphen G2D".
Aldringen med disse slam ble dog foretatt i "Roller-oven" ved 125"C i et tidsrom på 72 timer. De på ikke-aldret og aldret materiale fastslåtte reologiske data er som følger: The aging with these sludges was, however, carried out in the "Roller-oven" at 125"C for a period of 72 hours. The rheological data determined on non-aged and aged material are as follows:
Eksempel 9 Example 9
Eksempel 10 Example 10
Eksempel 11 Example 11
Claims (23)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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NO930158A NO930158D0 (en) | 1989-03-08 | 1993-01-18 | APPLICATION OF SELECTED LOW CARBOXYL ACID EASTER OILS IN WATER-IN-OIL DRILL |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3907391A DE3907391A1 (en) | 1989-03-08 | 1989-03-08 | USE OF SELECTED ESTER OILS OF LOW CARBONIC ACIDS IN DRILL RINSING |
PCT/EP1990/000342 WO1990010682A1 (en) | 1989-03-08 | 1990-03-01 | Use of selected low carboxylic acid ester oils in drilling muds |
Publications (3)
Publication Number | Publication Date |
---|---|
NO913239D0 NO913239D0 (en) | 1991-08-19 |
NO913239L NO913239L (en) | 1991-08-19 |
NO172501B true NO172501B (en) | 1993-04-19 |
Family
ID=6375780
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO913239A NO172501B (en) | 1989-03-08 | 1991-08-19 | WATER-IN-OIL DRILLING CONTAINING SELECTED LOW CARBOXYLIC ACID ESSENTIALS AND MANUFACTURING THEREOF |
Country Status (15)
Country | Link |
---|---|
EP (2) | EP0386638B2 (en) |
JP (1) | JP2834319B2 (en) |
AT (1) | ATE87020T1 (en) |
AU (1) | AU624926B2 (en) |
BR (1) | BR9007192A (en) |
CA (1) | CA2047697C (en) |
DE (2) | DE3907391A1 (en) |
DK (1) | DK0386638T3 (en) |
ES (1) | ES2042101T3 (en) |
IE (1) | IE63931B1 (en) |
MX (1) | MX174249B (en) |
NO (1) | NO172501B (en) |
TR (1) | TR24748A (en) |
WO (1) | WO1990010682A1 (en) |
ZA (1) | ZA901759B (en) |
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US5083622A (en) * | 1988-03-14 | 1992-01-28 | Shell Oil Company | Method for drilling wells |
US5085282A (en) * | 1988-03-14 | 1992-02-04 | Shell Oil Company | Method for drilling a well with emulsion drilling fluids |
US5072794A (en) * | 1988-09-30 | 1991-12-17 | Shell Oil Company | Alcohol-in-oil drilling fluid system |
DE3842659A1 (en) * | 1988-12-19 | 1990-06-28 | Henkel Kgaa | USE OF SELECTED ESTEROILS IN DRILLING RINSING, IN PARTICULAR FOR THE OFF-SHORE DEVELOPMENT OF PETROLEUM OR. NATURAL GAS DEPOSIT (I) |
DE3903784A1 (en) * | 1989-02-09 | 1990-08-16 | Henkel Kgaa | MONOCARBONIC ACID METHYL ESTER IN INVERT DRILLING CLOSURE |
DE3911299A1 (en) * | 1989-04-07 | 1990-10-11 | Henkel Kgaa | USE SELECTED ETHER MONOFUNCTIONAL ALCOHOLS IN DRILLING |
DE3915876A1 (en) * | 1989-05-16 | 1990-11-22 | Henkel Kgaa | USE OF SELECTED ESTEROILS IN WATER-BASED DRILLING RINSES OF THE O / W EMULSION TYPE AND CORRESPONDING DRILLING LIQUIDS WITH IMPROVED ECOLOGICAL TOLERABILITY |
US5260269A (en) * | 1989-10-12 | 1993-11-09 | Shell Oil Company | Method of drilling with shale stabilizing mud system comprising polycyclicpolyetherpolyol |
US5423379A (en) * | 1989-12-27 | 1995-06-13 | Shell Oil Company | Solidification of water based muds |
US5058679A (en) * | 1991-01-16 | 1991-10-22 | Shell Oil Company | Solidification of water based muds |
US5076364A (en) * | 1990-03-30 | 1991-12-31 | Shell Oil Company | Gas hydrate inhibition |
US5076373A (en) * | 1990-03-30 | 1991-12-31 | Shell Oil Company | Drilling fluids |
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US5508258A (en) * | 1990-08-03 | 1996-04-16 | Henkel Kommanditgesellschaft Auf Aktien | Use of surface-active alpha-sulfo-fatty acid di-salts in water and oil based drilling fluids and other drill-hole treatment agents |
DE4024658A1 (en) * | 1990-08-03 | 1992-04-16 | Henkel Kgaa | USE OF SURFACE-ACTIVE ALKYL GLYCOSIDE COMPOUNDS IN WATER- AND OIL-BASED DRILLING AND OTHER DRILLING TREATMENT AGENTS |
DE4024892A1 (en) * | 1990-08-06 | 1992-02-13 | Henkel Kgaa | USE OF SURFACE-ACTIVE ESTERSULFONATE SALTS IN WATER- AND OIL-BASED DRILLING AND OTHER DRILLING TREATMENT AGENTS |
US5338870A (en) * | 1991-03-19 | 1994-08-16 | Shell Oil Company | Thermal condensation of polyhydric alcohols to form polyethercyclicpolyols |
US5233055A (en) * | 1991-03-19 | 1993-08-03 | Shell Oil Company | Copolymerization of polyethercyclicpolyols with epoxy resins |
US5371244A (en) * | 1991-03-19 | 1994-12-06 | Shell Oil Company | Polycondensation of dihydric alcohols and polyhydric alcohols and thermal condensation to form polyethercyclicpolyols |
US5302728A (en) * | 1991-03-19 | 1994-04-12 | Shell Oil Company | Polycondensation of phenolic hydroxyl-containing compounds and polyhydric alcohols and thermal condensation to form polyethercyclipolyols |
US5302695A (en) * | 1991-03-19 | 1994-04-12 | Shell Oil Company | Polycondensation of epoxy alcohols with polyhydric alcohols and thermal condensation to form polyethercyclicpolyols |
DE4120041A1 (en) * | 1991-06-18 | 1992-12-24 | Henkel Kgaa | USE OF SELECTED OLEOPHILIC COMPOUNDS WITH GREATER BIODEGRADILITY TO IMPROVE THE OILABILITY OF FINE-PARTICULAR SOLIDS AND THEIR USE AS FLUID-LOSS ADDITIVES |
DE4200502A1 (en) * | 1992-01-13 | 1993-07-15 | Henkel Kgaa | IMPROVED DISPOSAL OF CONTAMINATED DRILL SMALL FROM GEOLOGICAL HOLES WITH MINERAL OIL CONTAINING DRILL RINSING SYSTEMS |
GB9210578D0 (en) * | 1992-05-18 | 1992-07-01 | Exxon Chemical Patents Inc | Functional fluid |
DE4218243C2 (en) * | 1992-06-03 | 1994-04-28 | Cognis Bio Umwelt | Improved nutrient mixtures for the bioremediation of polluted soils and waters |
US5286882A (en) * | 1992-10-13 | 1994-02-15 | Shell Oil Company | Polyethercyclicpolyols from epihalohydrins, polyhydric alcohols and metal hydroxides or epoxy alcohol and optionally polyhydric alcohols with addition of epoxy resins |
US5428178A (en) * | 1992-10-13 | 1995-06-27 | Shell Oil Company | Polyethercyclipolyols from epihalohydrins, polyhydric alcohols, and metal hydroxides or epoxy alcohols and optionally polyhydric alcohols with thermal condensation |
US5371243A (en) * | 1992-10-13 | 1994-12-06 | Shell Oil Company | Polyethercyclicpolyols from epihalohydrins, polyhydric alcohols, and metal hydroxides |
GB9324834D0 (en) * | 1993-12-03 | 1994-01-19 | Exxon Chemical Patents Inc | Drilling fluid |
DE4420455A1 (en) * | 1994-06-13 | 1995-12-14 | Henkel Kgaa | Flowable borehole treatment compositions containing linear alpha-olefins, in particular corresponding drilling fluids |
DE4436764A1 (en) * | 1994-10-14 | 1996-04-18 | Henkel Kgaa | Use of guanidinium salts of unsaturated fatty acids as an anti-corrosion agent |
DE19546911A1 (en) | 1995-12-15 | 1997-06-19 | Henkel Kgaa | New aqueous-swellable preparations of guar and guar derivatives in oleophilic liquids and their use |
US6589917B2 (en) * | 1996-08-02 | 2003-07-08 | M-I Llc | Invert emulsion drilling fluids and muds having negative alkalinity and elastomer compatibility |
TW354352B (en) * | 1996-10-30 | 1999-03-11 | Henkel Kgaa | A process for easier cleaning on the basis of water/oil inversion emulifier |
US6022833A (en) * | 1996-10-30 | 2000-02-08 | Henkel Kommanditgesellschaft Auf Aktien | Multicomponent mixtures for use in geological exploration |
DE19647598A1 (en) | 1996-11-18 | 1998-05-20 | Henkel Kgaa | Use of selected fatty alcohols and their mixtures with carboxylic acid esters as a lubricant component in water-based drilling fluid systems for excavating soil |
DE19647565A1 (en) | 1996-11-18 | 1998-05-20 | Henkel Kgaa | Multi-phase lubricant concentrates for use in water-based systems in the field of earth drilling |
US6100223A (en) * | 1997-12-30 | 2000-08-08 | Chevron Chemical Company Llc | Method of converting olefins into mixtures of secondary esters, products and uses thereof |
US6405809B2 (en) * | 1998-01-08 | 2002-06-18 | M-I Llc | Conductive medium for openhold logging and logging while drilling |
FR2773816B1 (en) * | 1998-01-19 | 2001-05-04 | Inst Francais Du Petrole | FLUID AND METHOD FOR RELEASING STUCK TUBULAR ELEMENTS FROM A WELL |
AU1616900A (en) * | 1998-11-12 | 2000-05-29 | M-I L.L.C. | Invert emulsion drilling fluids having negative alkalinity |
DE19852971A1 (en) | 1998-11-17 | 2000-05-18 | Cognis Deutschland Gmbh | Lubricants for drilling fluids |
US6828279B2 (en) | 2001-08-10 | 2004-12-07 | M-I Llc | Biodegradable surfactant for invert emulsion drilling fluid |
DE10334441A1 (en) | 2003-07-29 | 2005-02-17 | Cognis Deutschland Gmbh & Co. Kg | Borehole treatment agents containing ether carboxylic acids |
EP2053111B1 (en) | 2007-10-24 | 2016-12-07 | Emery Oleochemicals GmbH | Drilling composition, process for its preparation and applications thereof |
DE102009060865A1 (en) | 2009-12-30 | 2011-07-07 | Emery Oleochemicals GmbH, 40589 | Esters of solid polyols and unsaturated carboxylic acids |
DE102012003224A1 (en) * | 2012-02-20 | 2013-08-22 | Sasol Germany Gmbh | Drilling fluid, use and method using the drilling fluid |
EP2848720B1 (en) | 2013-09-12 | 2016-03-02 | 3M Innovative Properties Company | Use of a lubricant in a mounting mat and method for making such a mat |
GB2553949B (en) | 2015-05-14 | 2021-10-20 | Halliburton Energy Services Inc | Downhole fluids with high dielectric constant and high dielectric strength |
WO2019147515A1 (en) | 2018-01-29 | 2019-08-01 | Exxonmobil Chemical Patents Inc. | Anaerobically biodegradable fluids for drilling applications |
EP3763922A1 (en) | 2019-07-09 | 2021-01-13 | 3M Innovative Properties Company | Mounting mat for use in pollution control devices |
US11396620B2 (en) | 2020-07-30 | 2022-07-26 | Saudi Arabian Oil Company | Epoxidized alpha olefin based anti-bit balling additive for water-based drilling fluids |
US11214724B1 (en) | 2020-07-30 | 2022-01-04 | Saudi Arabian Oil Company | Epoxidized alpha olefin based lubricant for water-based drilling fluids |
EP4379197A1 (en) | 2022-11-30 | 2024-06-05 | 3M Innovative Properties Company | Zero binder polycrystalline mounting mat with improved production handing |
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US3728277A (en) * | 1970-01-12 | 1973-04-17 | Witco Chemical Corp | Stable water-in-oil emulsions |
DE2843473A1 (en) * | 1978-10-05 | 1980-04-17 | Bayer Ag | LACTONE MODIFIED ESTER OILS |
DE3903784A1 (en) * | 1989-02-09 | 1990-08-16 | Henkel Kgaa | MONOCARBONIC ACID METHYL ESTER IN INVERT DRILLING CLOSURE |
DE3907392A1 (en) * | 1989-03-08 | 1990-09-13 | Henkel Kgaa | ESTER OF CARBONIC ACIDS, MEDIUM CHAIN LENGTH, AS THE BEST NEEDLE PART OF THE OIL PHASE IN INVERT DRILL RINSE |
-
1989
- 1989-03-08 DE DE3907391A patent/DE3907391A1/en not_active Ceased
-
1990
- 1990-03-01 BR BR909007192A patent/BR9007192A/en not_active IP Right Cessation
- 1990-03-01 AT AT90104027T patent/ATE87020T1/en not_active IP Right Cessation
- 1990-03-01 AU AU51823/90A patent/AU624926B2/en not_active Expired
- 1990-03-01 JP JP2504168A patent/JP2834319B2/en not_active Expired - Fee Related
- 1990-03-01 WO PCT/EP1990/000342 patent/WO1990010682A1/en not_active Application Discontinuation
- 1990-03-01 EP EP90104027A patent/EP0386638B2/en not_active Expired - Lifetime
- 1990-03-01 CA CA002047697A patent/CA2047697C/en not_active Expired - Lifetime
- 1990-03-01 ES ES199090104027T patent/ES2042101T3/en not_active Expired - Lifetime
- 1990-03-01 DK DK90104027.9T patent/DK0386638T3/en active
- 1990-03-01 DE DE9090104027T patent/DE59001025D1/en not_active Expired - Lifetime
- 1990-03-01 EP EP90904323A patent/EP0462160A1/en active Pending
- 1990-03-06 TR TR90/0217A patent/TR24748A/en unknown
- 1990-03-06 MX MX019774A patent/MX174249B/en unknown
- 1990-03-07 ZA ZA901759A patent/ZA901759B/en unknown
- 1990-03-07 IE IE80290A patent/IE63931B1/en not_active IP Right Cessation
-
1991
- 1991-08-19 NO NO913239A patent/NO172501B/en unknown
Also Published As
Publication number | Publication date |
---|---|
IE900802L (en) | 1990-09-08 |
CA2047697A1 (en) | 1990-09-09 |
AU624926B2 (en) | 1992-06-25 |
EP0386638A1 (en) | 1990-09-12 |
ATE87020T1 (en) | 1993-04-15 |
EP0386638B2 (en) | 2003-12-03 |
ES2042101T3 (en) | 1993-12-01 |
BR9007192A (en) | 1991-12-10 |
EP0462160A1 (en) | 1991-12-27 |
DK0386638T3 (en) | 1993-07-26 |
DE59001025D1 (en) | 1993-04-22 |
CA2047697C (en) | 2001-07-31 |
EP0386638B1 (en) | 1993-03-17 |
MX174249B (en) | 1994-05-02 |
ZA901759B (en) | 1990-11-28 |
JPH04503965A (en) | 1992-07-16 |
AU5182390A (en) | 1990-10-09 |
NO913239D0 (en) | 1991-08-19 |
NO913239L (en) | 1991-08-19 |
JP2834319B2 (en) | 1998-12-09 |
IE63931B1 (en) | 1995-06-28 |
WO1990010682A1 (en) | 1990-09-20 |
DE3907391A1 (en) | 1990-09-13 |
TR24748A (en) | 1992-03-01 |
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