NO171062B - PROCEDURE FOR THE PREPARATION OF COLD-STABLE ALKANOLIC-Aqueous SOLUTIONS OF POLYETER SULPHONATES - Google Patents
PROCEDURE FOR THE PREPARATION OF COLD-STABLE ALKANOLIC-Aqueous SOLUTIONS OF POLYETER SULPHONATES Download PDFInfo
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- NO171062B NO171062B NO904131A NO904131A NO171062B NO 171062 B NO171062 B NO 171062B NO 904131 A NO904131 A NO 904131A NO 904131 A NO904131 A NO 904131A NO 171062 B NO171062 B NO 171062B
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- cold
- stable
- alkanol
- aqueous solutions
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- 239000007864 aqueous solution Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract 4
- 239000000243 solution Substances 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 239000008346 aqueous phase Substances 0.000 claims abstract description 7
- 150000004820 halides Chemical class 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 claims abstract description 4
- 125000005037 alkyl phenyl group Chemical group 0.000 claims abstract description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Chemical group 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 238000004391 petroleum recovery Methods 0.000 abstract 1
- -1 sodium chloride Chemical class 0.000 description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- LCZQPVZZCAKDAJ-UHFFFAOYSA-N 1-[1-chloro-2,2,2-tris(2-chloroethoxy)ethoxy]tridecane Chemical compound C(CCCCCCCCCCCC)OC(C(OCCCl)(OCCCl)OCCCl)Cl LCZQPVZZCAKDAJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 239000004285 Potassium sulphite Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 125000005644 linolenyl group Chemical group 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 239000004293 potassium hydrogen sulphite Substances 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CSABAZBYIWDIDE-UHFFFAOYSA-N sulfino hydrogen sulfite Chemical class OS(=O)OS(O)=O CSABAZBYIWDIDE-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (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 Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Fremgangsmåte for fremstilling av kuldestabile alkanolisk-vandige lesninger av polyetersulfonater med den generelle formel I. hvor. R står for en alkyl- eller alkylengruppe med 8 til 25 C-atomer eller en alkylfenylgruppe med 8 til 18 C-atomer i. alkylresten,. A betegner en,2-alkylengruppe med 2 til 4 C-atomer,. n har en verdi mellomog5, og hvor M betyr et alkalimetall- eller et ammoniumkation, som kan være substituert med C-^- C^-alkylgrupper eller C-C-hydr-oksyalkylgrupper,. ved omsetning a-v polyeterhalogenider med den generelle formel II. R-(0-A)-x II. hvor X står for klor eller brom, med en vandig løsning av et alkalimetall- eller ammoniumsulfitt og fortynning av reaksjons-losningen med en C^Cg-alkanol, idet man etter reaksjonen varmer opp reaksjonsblandingen til 60 til 150C ved 1 til 5 bar og skiller fra den i hovedsak vandige fase som danner seg.De kuldestabile lesninger av polyetersulfonatene I finner anvendelse som tensid-løsninger ved tertiær jordolje-utvinning.Process for the preparation of cold-stable alkanolic aqueous readings of polyether sulfonates of the general formula I. wherein. R represents an alkyl or alkylene group having 8 to 25 carbon atoms or an alkylphenyl group having 8 to 18 carbon atoms in the alkyl radical. A represents a 2-alkylene group having 2 to 4 carbon atoms. n has a value between and 5, and wherein M represents an alkali metal or an ammonium cation, which may be substituted by C 1 -C 4 alkyl groups or C 1 -C 4 hydroxyalkyl groups. by reacting a-v polyether halides of the general formula II. R- (0-A) -x II. wherein X represents chlorine or bromine, with an aqueous solution of an alkali metal or ammonium sulphite and diluting the reaction solution with a C from the substantially aqueous phase which forms. The cold-stable readings of the polyether sulfonates I are used as surfactant solutions in tertiary petroleum recovery.
Description
Foreliggende oppfinnelse angår en forbedret fremgangsmåte for fremstilling av kuldestabile alkanolisk-vandige løsninger av polyetersulfonater med den generelle formel I The present invention relates to an improved process for the production of cold-stable alkanol-aqueous solutions of polyethersulfonates with the general formula I
hvor where
R står for en alkyl- eller alkenylgruppe med 8 til 25 C-atomer eller en alkylfenylgruppe med 8 til 18 C-atomer i R stands for an alkyl or alkenyl group with 8 to 25 C atoms or an alkylphenyl group with 8 to 18 C atoms in
alkylresten, the alkyl residue,
A betegner en 1,2-alkylengruppe med 2 til 4 C-atomer, A denotes a 1,2-alkylene group with 2 to 4 C atoms,
n har en verdi mellom 1 og 15, og hvor n has a value between 1 and 15, and where
M betyr et alkalimetall- eller et ammoniumkation, som kan være substituert med Ci-C4-alkylgrupper eller Ci-C4-hydr-oksyalkylgrupper, M means an alkali metal or an ammonium cation, which may be substituted with C1-C4 alkyl groups or C1-C4 hydroxyalkyl groups,
ved omsetning av polyeterhalogenider med den "generelle formel II by reacting polyether halides with the "general formula II
hvor X står for klor eller brom, med en vandig løsning av et alkalimetall- eller ammoniumsulfitt og fortynning av reaksjons-løsningen med en C4-C8-alkanol. where X stands for chlorine or bromine, with an aqueous solution of an alkali metal or ammonium sulphite and dilution of the reaction solution with a C4-C8 alkanol.
Videre angår oppfinnelsen anvendelsen av de på denne måte fremstilte løsninger av polyetersulfonater I som tensid-løs-ninger ved tertiær oljeutvinning. Furthermore, the invention relates to the use of the solutions of polyethersulfonates I prepared in this way as surfactant solutions in tertiary oil extraction.
Konsentrerte vandige løsninger av polyetersulfonater som Concentrated aqueous solutions of polyethersulfonates which
er fortynnet med kortkjedede alkoholer for nedsettelse av viskositeten er kjente, eksempelvis fra EP-A 156 601 og EP-A is diluted with short-chain alcohols to reduce the viscosity are known, for example from EP-A 156 601 and EP-A
206 678. 206,678.
Disse alkoholisk-vandige tensid-løsninger har, når det dreier seg om tekniske løsninger, ofte den ulempe at de ved fallende temperatur allerede ved 20 til 15°C blir faste på vokslignende måte, ettersom polyetersulfonatene krystalliserer ut. Slike blandinger er i praksis ikke lenger transportable, og kan stoppe til rørledninger og blokkere lagertanker. I tillegg er gjenoppløseligheten av polyetersulfonatene også vanskelig. Denne ulempe er spesielt tungtveiende for anvendelsen av disse tensid-løsninger ved utvinning av jordolje i jordens kaldere klimasoner og kalde hav som eksempelvis Nordsjøen. These alcoholic-aqueous surfactant solutions, when it comes to technical solutions, often have the disadvantage that when the temperature drops, they already become solid in a wax-like manner at 20 to 15°C, as the polyethersulfonates crystallize out. Such mixtures are in practice no longer transportable, and can clog pipelines and block storage tanks. In addition, the resolubility of the polyethersulfonates is also difficult. This disadvantage is particularly significant for the use of these surfactant solutions in the extraction of petroleum in the earth's colder climate zones and cold seas such as the North Sea.
Det var således foreliggende oppfinnelses oppgave å stille til disposisjon kuldestabile polyetersulfonat-løsninger. It was thus the task of the present invention to make cold-stable polyethersulfonate solutions available.
Som en følge av dette, ble den innledningsvis definerte fremgangsmåte oppfunnet. Denne fremgangsmåte er kjennetegnet ved at man etter reaksjonen varmer opp reaksjonsblandingen til 60 til 150°C ved 1 til 5 bar, og skiller fra den overveiende vandige fase som derved danner seg. As a result of this, the initially defined method was invented. This method is characterized by the fact that, after the reaction, the reaction mixture is heated to 60 to 150°C at 1 to 5 bar, and separated from the predominantly aqueous phase which thereby forms.
Ved oppvarming av reaksjonsblandingen til 60 til 150'C ved 1 til 5 bar, fortrinnsvis 90 til 105°C ved normaltrykk, danner det seg en fase som i overveiende grad er vandig og en fase som i overveiende grad er organisk. Den i hovedsak vandige fase inneholder ved siden av vann en del av alkanolen og den største del av de uorganiske salter, i hovedsak halogenider som natriumklorid, som stammer fra reaksjonen av II med sulfitt-løsningen, og som er ansvarlige for kuldestabilitetsforholdet for løs-ningene av I. Den i hovedsak organiske fase inneholder ved siden av alkanol og noe vann, resten av de uorganiske salter og nesten hele mengden av polyetersulfonatet I. When the reaction mixture is heated to 60 to 150°C at 1 to 5 bar, preferably 90 to 105°C at normal pressure, a phase which is predominantly aqueous and a phase which is predominantly organic is formed. The mainly aqueous phase contains next to water a part of the alkanol and the largest part of the inorganic salts, mainly halides such as sodium chloride, which originate from the reaction of II with the sulphite solution, and which are responsible for the cold stability of the solutions of I. The mainly organic phase contains, in addition to alkanol and some water, the rest of the inorganic salts and almost the entire amount of the polyethersulfonate I.
Det er hensiktsmessig at faseskillingen også gjennomføres It is appropriate that the phase separation is also carried out
i varm tilstand i det angitte temperaturområde. Etter fraskil-ling av den i overveiende grad vandige fase kan den i overveiende grad organiske fase stilles inn med vann på et tensid-innhold som vanligvis er 25 til 35 vekt%, og tilføres den videre anvendelse. in a warm state in the specified temperature range. After separation of the predominantly aqueous phase, the predominantly organic phase can be adjusted with water to a surfactant content which is usually 25 to 35% by weight, and added to it for further use.
Resten R i polyetersulfonatene I står spesielt for en alkylgruppe med 8 til 25 C-atomer, fortrinnsvis 10 til 22 C-atomer, eksempelvis n-oktyl, 2-etylheksyl, n-nonyl, iso-nonyl, n-decyl, n-undecyl, n-dedecyl, n-tridecyl, iso-tridecyl, myri-styl, cetyl, stearyl og eicosyl, men også for en alkylengruppe med 8 til 25 C-atomer, fortrinnsvis 10 til 22 C-atomer, eksempelvis oleyl, linolyl og linolenyl, eller for en alkylfenylgruppe med 8 til 18 C-atomer, fortrinnsvis 10 til 16 C-atomer i alkylresten, eksempelvis p-decylfenyl, p-dodecylfenyl, p-myri-stylfenyl, p-cetylfenyl og p-stearylfenyl. The residue R in the polyethersulfonates I stands in particular for an alkyl group with 8 to 25 C atoms, preferably 10 to 22 C atoms, for example n-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl , n-dedecyl, n-tridecyl, iso-tridecyl, myri-styl, cetyl, stearyl and eicosyl, but also for an alkylene group with 8 to 25 C atoms, preferably 10 to 22 C atoms, for example oleyl, linolyl and linolenyl , or for an alkylphenyl group with 8 to 18 C atoms, preferably 10 to 16 C atoms in the alkyl residue, for example p-decylphenyl, p-dodecylphenyl, p-myristylphenyl, p-cetylphenyl and p-stearylphenyl.
Grupperingen A betegner fortrinnsvis en etylengruppe, ved siden av denne imidlertid også en propylen-, 1,2-butylen- eller 2 ,3-butylengruppe. The grouping A preferably denotes an ethylene group, alongside this, however, also a propylene, 1,2-butylene or 2,3-butylene group.
Alkosyleringsgraden n har en verdi på mellom 1 og 15, fortrinnsvis mellom 2 og 6. The degree of alkylation n has a value of between 1 and 15, preferably between 2 and 6.
Kationet M betyr et alkalimetallkation, spesielt natrium eller kalium, eller et ammoniumkation som fortrinnsvis er usubstituert, men som også kan være substituert med G1-C4~ alkylgrupper eller C1-C4-hydroksyalkylgrupper, eksempelvis trimetylammonium, trietylammonium, trietanolammonium eller triisopropanolammonium. The cation M means an alkali metal cation, especially sodium or potassium, or an ammonium cation which is preferably unsubstituted, but which can also be substituted with G1-C4~ alkyl groups or C1-C4 hydroxyalkyl groups, for example trimethylammonium, triethylammonium, triethanolammonium or triisopropanolammonium.
Polyeterhalogenidene II fremstilles vanligvis på kjent måte av de tilsvarende polyeteralkoholer ved reaksjon med et halogeneringsmiddel, fortrinnsvis med et kloreringsmiddel som tionylklorid eller sulfurylklorid. Polyeteralkoholene på sin side er lett tilgjengelige ved alkoksylering av eksempelvis fettalkoholer eller oksoalkoholer. The polyether halides II are usually prepared in a known manner from the corresponding polyether alcohols by reaction with a halogenating agent, preferably with a chlorinating agent such as thionyl chloride or sulfuryl chloride. The polyether alcohols, on the other hand, are easily accessible by carboxylation of, for example, fatty alcohols or oxoalcohols.
Som alkalimetall- eller ammoniumsulfitter egner seg i hovedsak sulfitter, hydrogensulfitter eller disulfitter, som kantioner kommer de kationer i betraktning som er angitt for M. Som eksempler kan nevnes natriumsulfitt, kaliumsulfitt, ammo-niumsulf itt, natriumhydrogensulfitt, kaliumhydrogensulfitt og ammoniumhydrogensulfitt. Alkali metal or ammonium sulphites are mainly suitable sulphites, hydrogen sulphites or disulphites, as cations the cations indicated for M come into consideration. Examples include sodium sulphite, potassium sulphite, ammonium sulphite, sodium hydrogen sulphite, potassium hydrogen sulphite and ammonium hydrogen sulphite.
Reaksjonen av polyeterhalogenidene II til sulfonatene I med den vandige sulfitt-løsning foretas på i og for seg kjent vis. Man arbeider vanligvis med temperaturer fra 130 til 200'C og ved et trykk fra 2 til 5 bar. Man oppnår på denne måte vanligvis høy-viskøse vandige tensid-rløsninger med et høyt innhold av uorganiske salter. Innholdet av I innstilles vanligvis på 25 til 40 vekt%. The reaction of the polyether halides II to the sulfonates I with the aqueous sulfite solution is carried out in a manner known per se. One usually works with temperatures from 130 to 200°C and at a pressure from 2 to 5 bar. In this way, highly viscous aqueous surfactant solutions with a high content of inorganic salts are usually obtained. The content of I is usually set at 25 to 40% by weight.
Som C4-C8-alkanoler egner seg eksempelvis n-butanol, iso-butanol, n-pentanol, iso-pentanol, n-heksanol, n-heptanol og n-oktanol. Spesielt gode resultater oppnår man med en pentanol eller med en blanding av forskjellige pentanolisomerer, fortrinnsvis n-pentanol og iso-pentanol eller med blandinger av disse. Teknisk pentanol utgjør en slik blanding med en sammen-setning av ca. 70 vekt% av n-isomerer og ca. 3 0 vekt% av iso-isomerer. Examples of suitable C4-C8 alkanols are n-butanol, iso-butanol, n-pentanol, iso-pentanol, n-hexanol, n-heptanol and n-octanol. Particularly good results are obtained with a pentanol or with a mixture of different pentanol isomers, preferably n-pentanol and iso-pentanol or with mixtures of these. Technical pentanol constitutes such a mixture with a composition of approx. 70% by weight of n-isomers and approx. 30% by weight of iso-isomers.
Man tilsetter alkanolen til reaksjonsløsningen under eller umiddelbart etter reaksjonen av II med sulfitt. Man kan imidlertid også arbeide slik at man tilsetter alkanolen til den vandige løsning I som allerede er oppvarmet til 60 til 150°C og foretar blandingen med denne først i varm tilstand. Mengden av alkanol velges da slik at den vanligvis utgjør 50 til 250 vekt%, beregnet på mengden av tensider I; de beste resultater oppnår man med 100 til 150 vekt% alkanol. The alkanol is added to the reaction solution during or immediately after the reaction of II with sulfite. However, it is also possible to work in such a way that the alkanol is added to the aqueous solution I which has already been heated to 60 to 150°C and the mixture is carried out with this first in a warm state. The amount of alkanol is then chosen so that it usually amounts to 50 to 250% by weight, calculated on the amount of surfactants I; the best results are obtained with 100 to 150% by weight of alkanol.
Løsningene av polyetersulfonatene I som er fremstilt ved hjelp av fremgangsmåten ifølge oppfinnelsen egner seg på frem-ragende vis som tensid-løsninger ved tertiær jordoljeutvinning, hvor man ved innsprøyting av løsninger av overflateaktive stoffer i de underjordiske jordoljereservoarer setter ned grenseflatespenningen mellom olje og omgivende vann, slik at utbyttet av utvunnet jordolje på denne måte kan forhøyes. The solutions of the polyethersulfonates I which are produced using the method according to the invention are eminently suitable as surfactant solutions in tertiary crude oil extraction, where the interfacial tension between oil and surrounding water is lowered by injecting solutions of surfactants into the underground crude oil reservoirs, so that the yield of extracted petroleum can be increased in this way.
Fremgangsmåten ifølge oppfinnelsen gir tyntflytende, konsentrerte polyetersulfat-løsninger som er kuldestabile til temperaturer på 5 - CC. Den utgjør en enkel og effektiv rense-metode for tekniske løsninger av polyetersulfonatene I, og ved hjelp av denne fremgangsmåte kan man senke løsningenes innhold av uorganiske salter. The method according to the invention produces thin-flowing, concentrated polyether sulphate solutions which are cold-stable to temperatures of 5 - CC. It constitutes a simple and effective cleaning method for technical solutions of the polyethersulfonates I, and with the help of this method the solution's content of inorganic salts can be lowered.
Eksempel I Example I
En 27 vekt% vandig løsning av natrium-p-dodecylfenyloksy-di (etylenoksy) -etansulf onat ble fremstilt ved reaksjon mellom p-dodecylfenoloksy-di(etylenoksy)-etylklorid og vandig natriumsulfitt-løsning ved 160°C og 3 bar. Løsningen inneholdt 6,4 vekt% natriumklorid. A 27% by weight aqueous solution of sodium p-dodecylphenyloxy-di(ethyleneoxy)-ethanesulfonate was prepared by reaction between p-dodecylphenoloxy-di(ethyleneoxy)-ethyl chloride and aqueous sodium sulphite solution at 160°C and 3 bar. The solution contained 6.4% by weight sodium chloride.
Til 500 g av denne løsning ble det ved 95 til 98°C og ved normaltrykk tilsatt 194 g teknisk pentanol under intensiv om-røring. Blandingen dannet deretter hurtig to faser som uten vanskeligheter lot seg skille. Den organiske fase (556 g) inneholdt 2,4 vekt% NaCl, den vandige fase (138 g) inneholdt 13,3 vekt% NaCl. Den organiske fase ble fortynnet med vann til et tensid-innhold på 30 vekt%. Denne løsning var kulde- og lagringsstabil ved 5 - 0°C. To 500 g of this solution, 194 g of technical pentanol were added at 95 to 98°C and at normal pressure with intensive stirring. The mixture then rapidly formed two phases which separated without difficulty. The organic phase (556 g) contained 2.4 wt% NaCl, the aqueous phase (138 g) contained 13.3 wt% NaCl. The organic phase was diluted with water to a surfactant content of 30% by weight. This solution was cold and storage stable at 5 - 0°C.
Eksempel 2 Example 2
En 35 vekt% vandig løsning av natrium-tridecyloksy-tri-(etylenoksy)-etansulfonat ble fremstilt ved reaksjon mellom tridecyloksy-tri(etylenoksy)-etylklorid og vandig natriumsulfitt-løsning ved 160"C og 3 bar. Løsningen inneholdt 5,1 vekt% natriumklorid. A 35% by weight aqueous solution of sodium tridecyloxy-tri-(ethyleneoxy)-ethanesulfonate was prepared by reaction between tridecyloxy-tri(ethyleneoxy)-ethyl chloride and aqueous sodium sulphite solution at 160°C and 3 bar. The solution contained 5.1 weight % sodium chloride.
Til 2000 g av denne løsning ble det ved 100"C og ved normaltrykk tilsatt 700 g teknisk pentanol under intensiv omrøring. Blandingen dannet deretter hurtig to faser som uten vanskeligheter lot seg skille. Den organiske fase (2137 g) inneholdt 1,0 vekt% NaCl, den vandige fase (557 g) inneholdt 14,3 vekt% NaCl. Den organiske fase ble fortynnet med vann til et tensid-innhold på 30 vekt%. Denne løsning var kulde- og lagringsstabil ved 5°C. To 2000 g of this solution, 700 g of technical pentanol was added at 100°C and at normal pressure with intensive stirring. The mixture then rapidly formed two phases which could be separated without difficulty. The organic phase (2137 g) contained 1.0% by weight NaCl, the aqueous phase (557 g) contained 14.3% by weight NaCl. The organic phase was diluted with water to a surfactant content of 30% by weight. This solution was cold and storage stable at 5°C.
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3931840A DE3931840A1 (en) | 1989-09-23 | 1989-09-23 | METHOD FOR PRODUCING REFRIGERABLE ALKANOLIC-AQUEOUS SOLUTIONS OF POLYETHERSULFONATES |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO904131D0 NO904131D0 (en) | 1990-09-21 |
| NO904131L NO904131L (en) | 1991-03-25 |
| NO171062B true NO171062B (en) | 1992-10-12 |
| NO171062C NO171062C (en) | 1993-01-20 |
Family
ID=6390069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO904131A NO171062C (en) | 1989-09-23 | 1990-09-21 | PROCEDURE FOR THE PREPARATION OF COLD-STABLE ALKANOLIC-Aqueous SOLUTIONS OF POLYETER SULPHONATES |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0419954B1 (en) |
| DE (2) | DE3931840A1 (en) |
| NO (1) | NO171062C (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1077700A (en) * | 1976-06-01 | 1980-05-20 | Melvin E. Tuvell | Alkyl glyceryl ether sulfonate salts in oil recovery |
| DE3346676A1 (en) * | 1983-02-17 | 1984-08-23 | Hoechst Ag, 6230 Frankfurt | TRIBUTYLPHENOL ETHERSULFONATES, THE USE THEREOF AND METHOD FOR THE PRODUCTION OF ETHERSULFONATES |
| CA1236482A (en) * | 1984-03-16 | 1988-05-10 | Werner A. Lidy | Preparation of sulphonates |
| GB8515225D0 (en) * | 1985-06-15 | 1985-07-17 | British Nuclear Fuels Plc | Preparation of surfactants |
| DE3622439A1 (en) * | 1986-07-04 | 1988-01-07 | Henkel Kgaa | HAIR TREATMENT |
-
1989
- 1989-09-23 DE DE3931840A patent/DE3931840A1/en not_active Withdrawn
-
1990
- 1990-09-13 DE DE9090117618T patent/DE59000542D1/en not_active Expired - Fee Related
- 1990-09-13 EP EP90117618A patent/EP0419954B1/en not_active Expired - Lifetime
- 1990-09-21 NO NO904131A patent/NO171062C/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3931840A1 (en) | 1991-04-04 |
| NO171062C (en) | 1993-01-20 |
| NO904131L (en) | 1991-03-25 |
| NO904131D0 (en) | 1990-09-21 |
| EP0419954B1 (en) | 1992-12-02 |
| EP0419954A1 (en) | 1991-04-03 |
| DE59000542D1 (en) | 1993-01-14 |
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