NO874616L - CARBOXYMETYLETERS CONTAINING TENSID MIXTURES AND THEIR USE FOR EXTRACTION OF OIL OIL. - Google Patents
CARBOXYMETYLETERS CONTAINING TENSID MIXTURES AND THEIR USE FOR EXTRACTION OF OIL OIL.Info
- Publication number
- NO874616L NO874616L NO874616A NO874616A NO874616L NO 874616 L NO874616 L NO 874616L NO 874616 A NO874616 A NO 874616A NO 874616 A NO874616 A NO 874616A NO 874616 L NO874616 L NO 874616L
- Authority
- NO
- Norway
- Prior art keywords
- oil
- surfactant
- sulphonates
- extraction
- flotation
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 13
- 238000000605 extraction Methods 0.000 title claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 29
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- -1 carboxyalkyl ether Chemical compound 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 29
- 238000005188 flotation Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000005755 formation reaction Methods 0.000 description 10
- 235000002639 sodium chloride Nutrition 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000008398 formation water Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-N methyl hydrogen carbonate Chemical compound COC(O)=O CXHHBNMLPJOKQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940089960 chloroacetate Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000003643 water by type Substances 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Detergent Compositions (AREA)
- Fats And Perfumes (AREA)
Description
Det er kjent at ved utvinning av olje fra oljeførende formasjoner er det bare å utvinne en liten del av den opprinnelige tilstedeværende olje det primære og sekundære utvinningsforholdsregler. En ytterligere oljeutbyttet lykkes ved tertiære forholdsregler. Herunder forstår man fremgangsmåte hvor enten oljens viskositet senkes eller viskositeten av det etterfloterende vann økes, eller det dreier seg om tensidfIotasjonsfremgangsmåter som beror på en sterk senkning av grenseflatespenningen mellom olje og formasjonsvann resp. formasj onssten. It is known that when extracting oil from oil-bearing formations, extracting only a small part of the original oil present is the primary and secondary extraction precautions. A further oil yield succeeds by tertiary precautions. This is understood as a process where either the viscosity of the oil is lowered or the viscosity of the post-flotation water is increased, or it is a question of tension flotation methods which depend on a strong lowering of the interfacial tension between oil and formation water resp. formation onstens.
I monografien av D.O. Shah og R.S. Schechter "Improved Oil Recovery by Surfactant and Polymerflooding, Academic Press Inc.", samt i tallrike patentskrifter anføres et flertall av tensider som kan finne anvendelse ved tensidflotasjonsproses-sen. Som tensider beskrives derved frem for alt sulfonater som f.eks. syntetiske og naturlige petrolsulfonater MG 350-500, alkylsulfonater som f.eks.<C>13<-C>2o-sec•-alkansulfonat-Na MG 328, Å-olefinsulfonat-NA(C15-<C>3o)/ alkylarylsulfonater, som f.eks. dodecylbenzensulfonat-Na, alkyltoluensulfonater eller alkylxylensulfonater. Disse sulfonater har imidlertid en meget lav toleransegrense i forhold til formasjonsvannets saltinnhold. Således er f.eks. petrolsulfonater bare oppløslig i et vann med et saltinnhold på 1,5% NaCl. Sulfonatene er frem for alt også meget følsomme mot de i formasjonsvannet inneholdte jordalkalier. Ved høyere saltkonsentrasjoner danner det seg ved anvendelse av disse tensider utfellingsprodukter som kan føre til tilstopning av formasjonens porøse rom. Mange formasjonsvann har imidlertid høyere saliniteter, i Nord-Tyskland f.eks. inntil 25%. In the monograph by D.O. Shah and R.S. Schechter "Improved Oil Recovery by Surfactant and Polymerflooding, Academic Press Inc.", as well as in numerous patent documents, a majority of surfactants that can be used in the surfactant flotation process are listed. Surfactants are described above all as sulfonates such as e.g. synthetic and natural petrolsulfonates MG 350-500, alkylsulfonates such as <C>13<-C>2o-sec•-alkanesulfonate-Na MG 328, Å-olefinsulfonate-NA(C15-<C>3o)/ alkylarylsulfonates, like for example. dodecylbenzenesulfonate-Na, alkyltoluenesulfonates or alkylxylenesulfonates. However, these sulphonates have a very low tolerance limit in relation to the salt content of the formation water. Thus, e.g. petrol sulphonates only soluble in water with a salt content of 1.5% NaCl. Above all, the sulphonates are also very sensitive to the alkaline earths contained in the formation water. At higher salt concentrations, when these surfactants are used, precipitation products form which can lead to clogging of the porous space of the formation. However, many formation waters have higher salinities, in northern Germany, e.g. up to 25%.
Anvendelsen av karboksymetyleteren alene som hjelpemiddel ved utvinning av olje er likeledes allerede kjent (EP 47 369, EP 47 370, DE 31 05 913, DE 31 34 530, DE 32 08 206, DE 32 08 208). Som uheldig ble det ved denne stoffklasse fastslått en spesiell sterk adsorbsjon til stenoverflaten. Dessuten bevirker karboksymetyleter i nærheten av inversjonstempera- turpunktet, hvor disse tensider anvendes og er virksomme, en sterk fortykning av oljen. Dette fører selv ved realtivt høypermeable kunstige formasjoner, til høye trykkgradienter (H. Murtada, M. Burkowsky, ErdÉl Erdgas Zeitschrift 93, 303 The use of the carboxymethyl ether alone as an aid in the extraction of oil is also already known (EP 47 369, EP 47 370, DE 31 05 913, DE 31 34 530, DE 32 08 206, DE 32 08 208). Unfortunately, a particularly strong adsorption to the stone surface was determined for this substance class. In addition, carboxymethyl ether near the inversion temperature point, where these surfactants are used and are effective, causes a strong thickening of the oil. This leads even in relatively highly permeable artificial formations to high pressure gradients (H. Murtada, M. Burkowsky, ErdÉl Erdgas Zeitschrift 93, 303
(1977)) . (1977)).
Overraskende ble det nå funnet at kombinasjoner av karboksyalkyletere med sulfonater ikke har ovennevnte ulemper og viser synergistiske effekter ved oljemobiliseringen. Surprisingly, it was now found that combinations of carboxyalkyl ethers with sulfonates do not have the above-mentioned disadvantages and show synergistic effects in the oil mobilization.
Oppfinnelsens gjenstand er således tensidblandinger som består av en karboksyalkyleter med formel The object of the invention is thus surfactant mixtures consisting of a carboxyalkyl ether with formula
hvori R betyr Cg-C2o~/fortrinnsvis C^-C^g-alkyl, C^- C^ q-, fortrinnsvis C8-<C>12~<a>lkYlfenyl, C4-<C>18-, fortrinnsvis Cg-<C>12<->dialkylfenyl eller C2-C8-, fortrinnsvis C4-trialkylfenyl, x betyr et tall på 1 til 50, fortrinnsvis på 2 til 10, n betyr et tall fra 1 til 3, fortrinnsvis 1 og M betyr natrium, kalium, ammonium, mono-, di- eller tri-etanolamin, in which R means Cg-C2o~/preferably C^-C^g-alkyl, C^-C^q-, preferably C8-<C>12~<a>lkYlphenyl, C4-<C>18-, preferably Cg- <C>12<->dialkylphenyl or C2-C8-, preferably C4-trialkylphenyl, x means a number from 1 to 50, preferably from 2 to 10, n means a number from 1 to 3, preferably 1 and M means sodium, potassium, ammonium, mono-, di- or tri-ethanolamine,
og et anionisk tensid fra grupen av sulfonater,and an anionic surfactant from the group of sulfonates,
i det vektsforholdet mellom karboksalkyletere og sulfonat utgjør 1:1 til 10:1. in which the weight ratio between carboxyalkyl ethers and sulfonate amounts to 1:1 to 10:1.
Karboksyalkyleterene kan fremstilles enten ved omsetning av oksalkylerte alkoholer eller fenoler med Na-kloracetat (DE 24 18 144) eller ved platinakatalysert oksydasjon av de oksalkylerte alkoholer resp. fenoler (EP 206054). The carboxyalkyl ethers can be prepared either by reaction of oxalkylated alcohols or phenols with Na-chloroacetate (DE 24 18 144) or by platinum-catalyzed oxidation of the oxalkylated alcohols or phenols (EP 206054).
Som sulfonater kommer det eksempelvis på tale sek. alkansul-fonater, alkylbenzensulfonater, alkyltoluensulfonter eller alkylxylensulfonater, hvis alkylgruppe resp. inneholder 10 til24, fortrinnsvis 12 til 20 C-atomer, Å- eller interne olefinsulfonater med en kjedelengde på 10 til 30, fortrinnsvis14 til 28 C-atomer eller petrolsulfonater med en molekyl-vekt på ca. 280 til 520, fortrinnsvis 330 til 500. Man kan blande karboksylalkyleterene med bare en av disse sulfonater, i mange tilfeller har det imidlertid vist seg fordelaktig å anvende karboksyalkyleterene sammen med flere av de omtalte sulfonater. Blandingsforholdet mellom karboksyalkyletere og sulfonat utgjør 1:10 til 10:1. As sulphonates, sec. alkanesulfonates, alkylbenzenesulfonates, alkyltoluenesulfonates or alkylxylenesulfonates, whose alkyl group resp. contains 10 to 24, preferably 12 to 20 C atoms, Å or internal olefin sulphonates with a chain length of 10 to 30, preferably 14 to 28 C atoms or petrol sulphonates with a molecular weight of approx. 280 to 520, preferably 330 to 500. The carboxyl alkyl ethers can be mixed with just one of these sulphonates, however, in many cases it has proved advantageous to use the carboxy alkyl ethers together with several of the mentioned sulphonates. The mixing ratio between carboxyalkyl ethers and sulphonate amounts to 1:10 to 10:1.
Til fremstilling av disse tensidblandinger kan det være av fordel å medanvende oppløsningsmidler som eksempelvis sec-butanol, etylenglykol, dietylenglykol, butyldiglykol eller heksanolpolyglykoleter. Mengden av disse oppløsningsmidler velges hensiktsmessig således at vektsforholdet mellom summen av tensidene og oppløsningsmidlet utgjør 1:10 til 10:1. Konsentrasjonen av den omtalte tensidblanding i flotasjons-vannet utgjør vanligvis 0,1 til 5, fortrinnsvis 0,4 til 3 vekt-%, når det dreier seg om fortynnede vandige oppløsnin-ger. Fremstiller man emulsjoner med disse tensidblandinger, så ligger konsentrasjonen av den samlede mengde av tensid mellom 5 og 10 vekt-%. Ved tilsetning av polymere som f.eks. hydroksyetylcellulose, polysakkarider, polyacrylamider og kopolymere på basis av acrylamid kan dessuten flotasjons-vannets viskositet økes. For the production of these surfactant mixtures, it may be advantageous to co-use solvents such as sec-butanol, ethylene glycol, diethylene glycol, butyl diglycol or hexanol polyglycol ether. The amount of these solvents is suitably chosen so that the weight ratio between the sum of the surfactants and the solvent amounts to 1:10 to 10:1. The concentration of the described surfactant mixture in the flotation water usually amounts to 0.1 to 5, preferably 0.4 to 3% by weight, when it concerns dilute aqueous solutions. If you prepare emulsions with these surfactant mixtures, the concentration of the total amount of surfactant is between 5 and 10% by weight. By adding polymers such as e.g. hydroxyethyl cellulose, polysaccharides, polyacrylamides and copolymers based on acrylamide can also increase the viscosity of the flotation water.
Til bestemmelsen av virkningen av de synergistiske tensidkom-binasjoner ifølge oppfinnelsen anvendes den i US-PS 4 008 165 omtalte mikrokapillaravoljingsmetoden, bestemmelsen av grenseflatespenningen ifølge Spinning-Drop-Interfacial-tensiometermetoden, faseforholdet ifølge Winsor og laborato-rieflotasjonsforsøk i med sand fylte glassrør. To determine the effect of the synergistic surfactant combinations according to the invention, the microcapillary deoiling method mentioned in US-PS 4 008 165, the determination of the interfacial tension according to the Spinning-Drop-Interfacial tensiometer method, the phase relationship according to Winsor and laboratory flotation tests in sand-filled glass tubes are used.
Ved mikrokapillaravoljingen anvendes som modell for porerom-met av formasjonen mikrokapillarer av glass fra fa. Drummond Scientific Co./USA, som ved et volum på 5 ±1 har en lengde på 3 0 mm og en diameter på 0,4 5 mm. In the case of microcapillary deoiling, glass microcapillaries from fa. Drummond Scientific Co./USA, which at a volume of 5 ±1 has a length of 3 0 mm and a diameter of 0.4 5 mm.
Mikrokapillarene tilsmeltes ved en ende, evakueres i en eksikator og fylles med råolje. Kapillarene innbringes loddrett med åpningen oppad i tensidoppløsninger (reagensg lass), som tempereres i vannbad og fortrengningen av olje registreres visuelt i avhengighet av tiden. The microcapillaries are fused at one end, evacuated in a desiccator and filled with crude oil. The capillaries are introduced vertically with the opening upwards into surfactant solutions (reagents), which are tempered in a water bath and the displacement of oil is recorded visually as a function of time.
Ved hjelp av følgende vurderingsskjerna kan det bestemmes virkningen av tensidene i avhengighet av deres konsentrasjon, saltkonsentrasjon, pH-verdi, temperatur og oljesammensetning. Using the following assessment criteria, the effectiveness of the surfactants can be determined depending on their concentration, salt concentration, pH value, temperature and oil composition.
VerdiValue
9 tom (30 mm) etter 10 minutter meget god virkning9 empty (30 mm) after 10 minutes very good effect
8 tom etter 1 time8 empty after 1 hour
7 tom etter 3 timer7 empty after 3 hours
6 tom etter 2 0 timer god virkning6 empty after 20 hours good effect
5 16-55 mm tømming etter 2 0 timer5 16-55 mm emptying after 2 0 hours
4 9-15 mm tømming etter 2 0 timer4 9-15 mm emptying after 2 0 hours
3 4-8 mm tømming etter 20 timer3 4-8 mm emptying after 20 hours
2 1-3 mm tømming etter 2 0 timer2 1-3 mm emptying after 2 0 hours
1 Spor av tømming etter 2 0 timer1 Trace of emptying after 20 hours
0 Uendret etter 2 0 timer0 Unchanged after 2 0 hours
Denne metode byr på den fordel, at ved mikrokapillarenes lille diamter utøver viskositet og tetthet av oljen ingen stor innvirkning på avoljingsvirkningen og det er mulig å arbeide med formasjonsolje og formasjonsvann. This method offers the advantage that due to the small diameter of the microcapillaries, the viscosity and density of the oil do not have a major impact on the deoiling effect and it is possible to work with formation oil and formation water.
Ifølge Taber J. Petr. Techn. 3 (1969), side 3-12, er tensider bare egnet for den tertiære jordoljeutvinning, når grenseflatespenningen ved fasegrensen olje/saltvann senkes til verdier mindre enn 10~<2>mNm-<1>. For denne bestemmelse av grenseflatespenningen på fasegrensen olje/vann anvendes det av Wade og Burkowsky utviklede Spinning-Drop-Interfacial-tensiometer (M. Burkowsky og C. Marx: tilber den Mechanismus des Tensidflutens in hochsalinaren Systemen; ErdÉl-Erdgas-Zeitschrift 95 (1979), s. 17-25). According to Taber J. Petr. Technology 3 (1969), page 3-12, surfactants are only suitable for tertiary petroleum extraction, when the interfacial tension at the oil/salt water phase boundary is lowered to values less than 10~<2>mNm-<1>. For this determination of the interfacial tension at the oil/water phase boundary, the Spinning-Drop-Interfacial tensiometer developed by Wade and Burkowsky is used (M. Burkowsky and C. Marx: tilber den Mechanismus des Tensidflutens in hochsalinaren Systemen; ErdÉl-Erdgas-Zeitschrift 95 (1979 ), pp. 17-25).
Metoden beror på at en oljedråpe som bringes i et rundt den horisontale akse roterende kapillar, som inneholder en væske (saltvann og tensid) med høyere tetthet. Dråpens strekkes inntil det oppnås en likevekt av de deformerende krefter og grenseflatespenningen. The method relies on an oil drop being brought into a capillary rotating around the horizontal axis, which contains a liquid (salt water and surfactant) with a higher density. The droplet is stretched until an equilibrium is reached between the deforming forces and the interfacial tension.
Grenseflatespenningen beregner seg ifølge Vonnegut (B. Vonnegut, Rev. Sei. Instruments 13 (1942 ), s. 6-9) av den målte oljedråpediameter R, rotasjonshastigheten W og tett-hetsforskjellen Ad etter følgende formel: The interface tension is calculated according to Vonnegut (B. Vonnegut, Rev. Sei. Instruments 13 (1942), p. 6-9) from the measured oil droplet diameter R, the rotation speed W and the density difference Ad according to the following formula:
Etter dagens stand oppklaring av mekanismen av avoljing ved tensidflotasjon er dannelsen av en 3. fase (midtfase), av en mikroemulsjon forutsetningen for et optimalt tensidflota-sjonsresultat [Rieckmann M. , Tertiare Erdolgewinnung, Erdol und Kohle-Erdgas-Petrochemie 36 (1983) 281-282) Healy R.N. og Reed, R.L. Soc. Petr. Eng. I. 10 (1979) 492-501), Obah, B. og Neumann, H.J. tlber die Bildung von Mikroemulsionen, Tenside Detergents 20 (1983) 145-151]. Denne søkte tredje fase oppstår i systemet, når grenseflatespenningen på fasegrensen olje/saltvann senkes sterkt. According to the current state of elucidation of the mechanism of de-oiling by surfactant flotation, the formation of a 3rd phase (middle phase), of a microemulsion, is the prerequisite for an optimal surfactant flotation result [Rieckmann M., Tertiare Erdolgewinnung, Erdol und Kohle-Erdgas-Petrochemie 36 (1983) 281-282) Healy R.N. and Reed, R.L. Soc. Petr. Meadow. I. 10 (1979) 492-501), Obah, B. and Neumann, H.J. tlber die Bildung von Mikroemulsionen, Tenside Detergents 20 (1983) 145-151]. This sought-after third phase occurs in the system, when the interfacial tension at the oil/saltwater phase boundary is greatly lowered.
Ved fastslåelse av midtfasen bringes 5 ml tensidoppløsning (med saltvann) og 5 ml olje (formasjonsolje eller modellolje) i et reagensglass, reagensglasset tilsmeltes, ristes kraftig og lagres i et tørkeskap ved konstant valgt temperatur. Etter 1 times lagringstid ristes igjen kraftig og reagens-glassene lagres deretter uten ytterligere gjennomblanding. Etter en lagringstid på 1 dag og 7 dager, fastslås dannelsen av fasene (midtfasen) og volumprosenten av de dannede faser fastholdes. When determining the middle phase, 5 ml surfactant solution (with salt water) and 5 ml oil (formation oil or model oil) are placed in a test tube, the test tube is fused, shaken vigorously and stored in a drying cabinet at a constant selected temperature. After 1 hour's storage time, shake vigorously again and the reagent tubes are then stored without further mixing. After a storage time of 1 day and 7 days, the formation of the phases (middle phase) is determined and the volume percentage of the formed phases is maintained.
Et ytterligere viktig utvelgelsesskriterium er den oljemo-biliserende virkning av tensidkombinasjonene, som undersøkes i laboratorieflotasjonsforsøk. Egnede forsøksbetingelser er flotasjonsforsøk med kunstig lagringer av sand, sandstein eller kalkstein, som er ifylt i glassrør. Ved gjennomførin-gen av forsøkene innristes i glassrørene fra fa. Quickfit A further important selection criterion is the oil-mobilizing effect of the surfactant combinations, which is investigated in laboratory flotation experiments. Suitable test conditions are flotation tests with artificial deposits of sand, sandstone or limestone, which are filled in glass tubes. When carrying out the experiments, the glass tubes from fa. Quickfit
(lengde: 15-50 cm, indre diameter: 2-3,8 cm) ved hjelp av en vibrator, kvartssand av bestemte kornstørrelser. Det med sand fylte fIotasjonsrør utstyres med fritte, tetning og avlukningsplate og undersøkes på tetthet. Rørene fylles med avgasset formasjonsvann, de fysikalske data, porøsitet og permeabilitet fastslås etter den Darcy1 ske lov, deretter impregneres med olje. Rørene tempereres og etter vurdering av trykkopptager og undersøkelse av utvinningsgraden av injeksjonspumpene, kan det injiseres innpresningsvann. Begynnelsen av tensid- resp. polymerfIotasjonen starter, når oljeutbyttet forblir konstant over et lengre tidsrom (ca. 1,5 til 2,0 PV). I tilknytning til kjemikalieoppslemningen, hvis mengde retter seg etter konsentrasjon, viskositet, økonomi osv., injiseres igjen fIotasjonsvann. Flotasjonsforsøket avsluttes når det ikke resp. bare floteres litt olje. De utbragte (utvunnede) vann- og oljemengder bestemmes volume-trisk og oppføres grafisk mot porevolumet (PV) avoljings-kurve. (length: 15-50 cm, inner diameter: 2-3.8 cm) using a vibrator, quartz sand of specific grain sizes. The sand-filled flotation tube is fitted with a frit, seal and shut-off plate and is checked for tightness. The pipes are filled with degassed formation water, the physical data, porosity and permeability are determined according to Darcy's law, then impregnated with oil. The pipes are tempered and after assessment of the pressure recorder and examination of the recovery rate of the injection pumps, injection water can be injected. The beginning of surfactant or polymer flotation starts when the oil yield remains constant over a longer period of time (about 1.5 to 2.0 PV). In connection with the chemical slurry, the quantity of which depends on concentration, viscosity, economy etc., flotation water is again injected. The flotation test is terminated when there is no resp. just float a little oil. The released (extracted) quantities of water and oil are determined by volume and plotted graphically against the pore volume (PV) deoiling curve.
De med disse metoder målte verdier er oppstilt i de følgende tabeller. I alle tilfelle ble det anvendt 1%-ig vandige oppløsninger av tensidene. The values measured with these methods are listed in the following tables. In all cases, 1% aqueous solutions of the surfactants were used.
I de følgende eksempler ble det benyttet følgende formasjonsolje: In the following examples, the following formation oil was used:
Virkningen av blandingen ifølge oppfinnelsen ble bekreftet med følgende laboratoriefIotasjonsforsøk med sandpakninger: The effect of the mixture according to the invention was confirmed with the following laboratory flotation tests with sand packs:
Syntetisk formasjonsvann: Synthetic formation water:
34,7 g salt/l (NaCl, CaCl2, MgCl2, Na2S04)34.7 g salt/l (NaCl, CaCl2, MgCl2, Na2SO4)
Temperatur: 80?CTemperature: 80?C
Avoljingen etter en vannfIotasjon med ca. 4,4 ganger mengden av porevolumet utgjør ca. 65%. Gjenblivende olje ansettes som restoljemetning SR = 100%. The de-oiling after a water flotation with approx. 4.4 times the amount of the pore volume amounts to approx. 65%. Remaining oil is considered residual oil saturation SR = 100%.
Meravoljingen er gjengitt i den tilknyttede tabell. The additional voting is shown in the attached table.
Tensidsystemer:Surfactant systems:
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863638160 DE3638160A1 (en) | 1986-11-08 | 1986-11-08 | CARBOXYMETHYL ETHER CONTAINING SURFACTANT BLENDS AND THE USE THEREOF FOR PRODUCING PETROLEUM |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO874616D0 NO874616D0 (en) | 1987-11-05 |
| NO874616L true NO874616L (en) | 1988-05-09 |
Family
ID=6313509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO874616A NO874616L (en) | 1986-11-08 | 1987-11-05 | CARBOXYMETYLETERS CONTAINING TENSID MIXTURES AND THEIR USE FOR EXTRACTION OF OIL OIL. |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE3638160A1 (en) |
| GB (1) | GB2197365A (en) |
| NO (1) | NO874616L (en) |
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| EP3000862A1 (en) * | 2015-04-24 | 2016-03-30 | Shell Internationale Research Maatschappij B.V. | Surfactant composition and use thereof in enhanced oil recovery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2165281B (en) * | 1984-10-05 | 1988-01-20 | Shell Int Research | Surfactant composition and process for the production of oil using such a composition |
| DE3523355A1 (en) * | 1985-06-29 | 1987-01-08 | Huels Chemische Werke Ag | METHOD FOR PRODUCING OIL FROM UNDERGROUND STORAGE STONE |
-
1986
- 1986-11-08 DE DE19863638160 patent/DE3638160A1/en not_active Withdrawn
-
1987
- 1987-11-05 NO NO874616A patent/NO874616L/en unknown
- 1987-11-06 GB GB08726081A patent/GB2197365A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| GB2197365A (en) | 1988-05-18 |
| GB8726081D0 (en) | 1987-12-09 |
| DE3638160A1 (en) | 1988-05-11 |
| NO874616D0 (en) | 1987-11-05 |
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