NO155810B - OIL-BASED DRILLING AND GASKING FLUID AND USE THEREOF. - Google Patents
OIL-BASED DRILLING AND GASKING FLUID AND USE THEREOF. Download PDFInfo
- Publication number
- NO155810B NO155810B NO813869A NO813869A NO155810B NO 155810 B NO155810 B NO 155810B NO 813869 A NO813869 A NO 813869A NO 813869 A NO813869 A NO 813869A NO 155810 B NO155810 B NO 155810B
- Authority
- NO
- Norway
- Prior art keywords
- group
- clay
- carbon atoms
- organic
- acid
- Prior art date
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- 239000012530 fluid Substances 0.000 title claims description 18
- 238000005553 drilling Methods 0.000 title claims description 12
- 239000004927 clay Substances 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 47
- 125000004432 carbon atom Chemical group C* 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 23
- 150000002892 organic cations Chemical class 0.000 claims description 22
- 150000002891 organic anions Chemical class 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 238000005341 cation exchange Methods 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 8
- 229910021647 smectite Inorganic materials 0.000 claims description 8
- 125000002015 acyclic group Chemical group 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 125000006165 cyclic alkyl group Chemical group 0.000 claims 1
- 125000005313 fatty acid group Chemical group 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- -1 alkyl radical Chemical class 0.000 description 54
- 239000000440 bentonite Substances 0.000 description 28
- 229910000278 bentonite Inorganic materials 0.000 description 28
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 28
- 239000003921 oil Substances 0.000 description 25
- 235000019198 oils Nutrition 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000002253 acid Substances 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 11
- 150000001768 cations Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002283 diesel fuel Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000003760 tallow Substances 0.000 description 8
- 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 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 5
- 239000010428 baryte Substances 0.000 description 5
- 229910052601 baryte Inorganic materials 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 4
- 229960001860 salicylate Drugs 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001449 anionic compounds Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 3
- 229910000271 hectorite Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical class OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid group Chemical group C(C=CC1=CC=CC=C1)(=O)O WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- FRXGWNKDEMTFPL-UHFFFAOYSA-N dioctadecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCCCC FRXGWNKDEMTFPL-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 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 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 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 2
- 230000008719 thickening Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- UKVYVZLTGQVOPX-IHWYPQMZSA-N (z)-3-aminobut-2-enoic acid Chemical compound C\C(N)=C\C(O)=O UKVYVZLTGQVOPX-IHWYPQMZSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- BQOKCDNRAHUORJ-UHFFFAOYSA-N 1,1,1-tribromooctane Chemical compound CCCCCCCC(Br)(Br)Br BQOKCDNRAHUORJ-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- 125000006033 1,1-dimethyl-2-propenyl group Chemical group 0.000 description 1
- 125000006035 1,2-dimethyl-2-propenyl group Chemical group 0.000 description 1
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- CCFAKBRKTKVJPO-UHFFFAOYSA-N 1-anthroic acid Chemical compound C1=CC=C2C=C3C(C(=O)O)=CC=CC3=CC2=C1 CCFAKBRKTKVJPO-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
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- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 150000003330 sebacic acids Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003442 suberic acids Chemical class 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/12—Packers; Plugs
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
-
- 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
Description
Oppfinnelsen angår oljebaserte væsker som inneholder organofile, organiske-leirekomplekser som kan dispergeres i organiske væsker under dannelse av en gel i disse. Slike geler er mer spesielt anvendbare i oljebaserte borevæsker og i oljebaserte pakningsvæsker. The invention relates to oil-based liquids containing organophilic, organic-clay complexes which can be dispersed in organic liquids while forming a gel therein. Such gels are more particularly applicable in oil-based drilling fluids and in oil-based packing fluids.
Det er velkjent at organiske forbindelser som inneholder et kation, vil reagere med leirer som inneholder et negativt laggitter og utbyttbare kationer, under dannelse av organofile organiske-leireprodukter. Reaksjonen for et organisk kation som inneholder minst én alkylgruppe med minst to carbonatomer, med leire fører generelt til organoleirer som er svellbare i visse organiske væsker. It is well known that organic compounds containing a cation will react with clays containing a negative layer lattice and exchangeable cations, forming organophilic organoclay products. The reaction of an organic cation containing at least one alkyl group with at least two carbon atoms with clay generally leads to organoclays which are swellable in certain organic liquids.
Tidligere publikasjoner omfatter US patentskrifter 2531427 og 2966506 og boken "Clay Mineralogy", 2. utgave, 1968, av Ralph E. Grim (McGraw Hill Book Co., Inc.), Previous publications include US Patents 2,531,427 and 2,966,506 and the book "Clay Mineralogy", 2nd edition, 1968, by Ralph E. Grim (McGraw Hill Book Co., Inc.),
spesielt kapittel 10, "Clay-Mineral-Organic Reactions", especially Chapter 10, "Clay-Mineral-Organic Reactions",
s. 356-368 - "Ionic Reactions, Smectite", og s. 392-401 - "Organophilic Clay-Mineral Complexes". pp. 356-368 - "Ionic Reactions, Smectite", and pp. 392-401 - "Organophilic Clay-Mineral Complexes".
En maksimal geldannelsesvirkning (fortykningsvirkning) fra disse organoleirer fås ved tilsetning av et polart, organisk dispergerende materiale med lav molekylvekt til blandingen. Slike materialer er beskrevet i US patentskrifter 2677661, 2704276, 2833720, 2879229 og 3294683. Anvendelsen av slike dispersjonshjelpemidler viste seg unødvendig da spesielle organofile leirer som var avledet fra kvartære ammoniumforbindelser, som beskrevet i US patentskrift 4105578 og 4208218, ble anvendt. A maximum gelling effect (thickening effect) from these organoclays is obtained by adding a polar, low molecular weight organic dispersing material to the mixture. Such materials are described in US patents 2677661, 2704276, 2833720, 2879229 and 3294683. The use of such dispersion aids proved unnecessary when special organophilic clays derived from quaternary ammonium compounds, as described in US patents 4105578 and 4208218, were used.
Kjente organofile leirer har oppvist en begrenset generell anvendbarhet for geldannelse på grunn av varierende dispersjons- og viskositetsegenskaper. Selv om materialene som er beskrevet i US patentskrift 4105578 ikke har oppvist slike mangler, er slike materialer vanskelige og kostbare å produsere. Known organophilic clays have shown limited general applicability for gelation due to varying dispersion and viscosity properties. Although the materials described in US Patent 4105578 have not shown such defects, such materials are difficult and expensive to produce.
Oppsummering av oppfinnelsen Summary of the invention
Oppfinnelsen angår en oljebasert bore- og pakningsvæske bestående av 0-60,. fortrinnsvis 2-50volum% The invention relates to an oil-based drilling and packing fluid consisting of 0-60,. preferably 2-50% by volume
av en dispergert vandig fase og/eller eventuelt 5,7-85,6, of a dispersed aqueous phase and/or optionally 5.7-85.6,
fortrinnsvis 14,3-57,1, g pr. liter av væsken av en vann-i-oljeemulgator, og 2,9-142,6 g pr. liter av væsken av et organofilt leiregelmiddel, resten olje, og den oljebaserte bore- og pakningsvæske er særpreget ved de i krav l's karakteriserende del angitte trekk. preferably 14.3-57.1, g per liter of the liquid of a water-in-oil emulsifier, and 2.9-142.6 g per liters of the liquid of an organophilic clay control agent, the rest oil, and the oil-based drilling and packing fluid is characterized by the features specified in claim 1's characterizing part.
Oppfinnelsen angår også anvendelse av væsken som pakningsvæske i et brønnborehull og spesielt for å isolere for-ingsrør i et brønnborehull. The invention also relates to the use of the liquid as packing fluid in a wellbore and in particular to insulate casing in a wellbore.
Detaljert beskrivelse av oppfinnelsen Detailed description of the invention
Den oljebaserte væske ifølge oppfinnelsen består av en oljefase og fra 2,9 til 142,6 g pr. liter av væske av et organofilt leiregelmiddel. Væsken er fortrinnsvis ikke-vandig. The oil-based liquid according to the invention consists of an oil phase and from 2.9 to 142.6 g per liters of liquid of an organophilic clay regulator. The liquid is preferably non-aqueous.
En egnet oljefase kan ifølge oppfinnelsen utgjøres av rå-olje eller fraksjoner derav, omfattende, men ikke begrenset til, dieselolje, kerosen, brenselolje, lette smøreoljefrak-sjoner og tungnaftha med et kokepunkt mellom 148 og 316°C. Det foretrukne oljefasemateriale er dieselolje. According to the invention, a suitable oil phase can be constituted by crude oil or fractions thereof, including, but not limited to, diesel oil, kerosene, fuel oil, light lubricating oil fractions and heavy naphtha with a boiling point between 148 and 316°C. The preferred oil phase material is diesel oil.
Mengden av organofil leire som anvendes, kan være tilstrekkelig til at den nødvendige geldannelse (fortykning) The amount of organophilic clay used may be sufficient for the necessary gelation (thickening)
av den oljebaserte væske for den beregnede anvendelse opp-nås, dvs. som borevæske eller pakningsvæske. Minimums-konsentrasjonen av organofil leire som er nødvendig for å gelere en spesiell væske,er avhengig av slike faktorer som typen av den anvendte organofile leire, oljefasens karakteristika, den høyeste temperatur som væsken skal opp-varmes til, og typen av eventuelt anvendt emulgeringsmiddel. Maksimumskonsentrasjonen av organofil leire er begrenset til den som vil danne en pumpbar væske. of the oil-based fluid for the intended application is achieved, i.e. as drilling fluid or packing fluid. The minimum concentration of organophilic clay required to gel a particular liquid depends on such factors as the type of organophilic clay used, the characteristics of the oil phase, the highest temperature to which the liquid is to be heated, and the type of any emulsifier used. The maximum concentration of organophilic clay is limited to that which will form a pumpable liquid.
Konsentrasjonen av organofil leire innen området fra The concentration of organophilic clay within the area from
2,9 til 142,6 g pr. liter vil i alminnelighet gi en tilstrekkelig gelert væske for vidstrakt anvendelse. Fortrinnsvis anvendes 2,9 til 29 g pr. liter ved fremstilling av oljebaserte borevæsker, mens en mengde av 17,1-142,6 g pr. liter har vist seg tilstrekkelig for fremstilling av oljebaserte pakningsvæsker. Det har vist seg at når den organofile leire blandes inn i den oljebaserte væske, 2.9 to 142.6 g per liters will generally provide a sufficiently gelled liquid for extensive use. Preferably, 2.9 to 29 g are used per liter when producing oil-based drilling fluids, while an amount of 17.1-142.6 g per liter has proven to be sufficient for the production of oil-based sealing fluids. It has been found that when the organophilic clay is mixed into the oil-based liquid,
fås en i det vesentlige fullstendig geldannelse ved blanding med lav skjærkraft. Den erholdte oljebaserte væske essentially complete gel formation is obtained by mixing with low shear. The obtained oil-based liquid
er en stabil oljebasert væske ved overflate- is a stable oil-based liquid at surface
temperatur under -29°C og temperaturer nede i hullet på opp til 260°C. Dannelsen av temperature below -29°C and temperatures down the hole of up to 260°C. Formation of
den stabile væske finner sted i løpet av noen minutter efter tilsetning og blanding med lav skjærkraft av den organofile leire i den oljebaserte væske. the stable liquid takes place within a few minutes after the addition and low shear mixing of the organophilic clay in the oil-based liquid.
En pakningsvæske ifølge oppfinnelsen fremstilles ved A sealing fluid according to the invention is produced by
til et oljemedium å tilsette den organofile leire. Paknings-væskens sammensetning reguleres som nevnt ovenfor slik at det fås en pumpbar blanding. Eventuelt kan emulgeringsmidler, vektøkende midler og materialer for å regulere tap av flytbarhet tilsettes på et hvilket som helst tidspunkt. Når den er blitt fremstilt, overføres pakningsvæsken,f.eks. ved pumping, til et brønnborehull av hvilket minst en del skal isoleres. to an oil medium to add the organophilic clay. The composition of the packing liquid is regulated as mentioned above so that a pumpable mixture is obtained. Optionally, emulsifiers, bulking agents and materials to control loss of fluidity may be added at any time. Once it has been produced, the packing fluid is transferred, e.g. when pumping, to a well borehole of which at least a part must be isolated.
Den oljebaserte væske kan fremstilles og anvendes enten før boringen begynner eller mens boringen utføres. Til-setningsmetoden av bestanddelen for å fremstille væsken er ikke av kritisk betydning. Blandingen gjøres ved anvendelse av vanlig utstyr som kan gi blanding ved lav skjærkraft. The oil-based fluid can be prepared and used either before drilling begins or while drilling is being carried out. The method of addition of the ingredient to prepare the liquid is not of critical importance. The mixing is done using ordinary equipment that can provide mixing at low shear.
En høyere blandingskraft kan anvendes selv om dette ikke er nødvendig. Når den er blitt fremstilt, overføres emulsjons-borevæsken, f.eks. ved pumping, til et brønnborehull og sirkuleres til borekronen og gjennom borehullet i kontakt med borehullets vegger. A higher mixing power can be used even if this is not necessary. Once it has been produced, the emulsion drilling fluid is transferred, e.g. by pumping, to a wellbore and is circulated to the drill bit and through the borehole in contact with the walls of the borehole.
De organofile leirer som anvendes ifølge oppfinnelsen, kan fremstilles ved å blande leiren, organisk kation, organisk anion og vann med hverandre, fortrinnsvis ved en temperatur av 20-100°C, og mer foretrukket 35-7<70>C, i tilstrekkelig tid til at det organiske kation-og organiske anionkompleks vil trenge seg inn (bli innskutt) blant leirepartiklene. Blandetrinnet følges av filtrering, vasking, tørking og nedmaling. Tilsetningen av det organiske kation og det organiske anion kan gjøres separat eller i form av et kom-pleks. Når de organofile leirer anvendes i form av emul-sjoner, kan tørke- og nedmalingstrinnene sløyfes. Når leiren, det organiske kation, det organiske anion og vannet blandes sammen i slike konsentrasjoner at en oppslemning ikke dannes, kan filtrerings- og vasketrinnene sløvfes. The organophilic clays used according to the invention can be produced by mixing the clay, organic cation, organic anion and water with each other, preferably at a temperature of 20-100°C, and more preferably 35-7<70>C, for a sufficient time so that the organic cation and organic anion complex will penetrate (be inserted) among the clay particles. The mixing step is followed by filtration, washing, drying and grinding down. The addition of the organic cation and the organic anion can be done separately or in the form of a complex. When the organophilic clays are used in the form of emulsions, the drying and grinding steps can be omitted. When the clay, the organic cation, the organic anion and the water are mixed together in such concentrations that a slurry does not form, the filtration and washing steps can be blunted.
De organofile leirer kan også The organophilic clays can too
fremstilles ved å blande det organiske anion med en vandig leireoppslemning, fortrinnsvis ved en temperatur av 20-100 C, is produced by mixing the organic anion with an aqueous clay slurry, preferably at a temperature of 20-100 C,
i tilstrekkelig tid til å fremstille en homogen blanding, fulgt av tilsetning av det organiske kation i tilstrekkelige mengder til å tilfredsstille leirens kationbytteevne og det organiske anions kapasitet overfor kationer. Blandingen omsettes under omrøring ved en temperatur av 20-100°C i tilstrekkelig tid til at et organisk kation- organisk anionkompleks vil dannes som trenger seg inn i leiren, og kation-byttesentraene i leiren erstattes med det organiske kation. Reaksjonstemperaturer under 20 ° C eller over 100 oC er ikke foretrukne på grunn av at dette ville kreve ytterligere behandlingsutstyr. for a sufficient time to produce a homogeneous mixture, followed by the addition of the organic cation in sufficient quantities to satisfy the cation exchange capacity of the clay and the capacity of the organic anion towards cations. The mixture is reacted with stirring at a temperature of 20-100°C for a sufficient time for an organic cation-organic anion complex to form which penetrates into the clay, and the cation-exchange centers in the clay are replaced with the organic cation. Reaction temperatures below 20°C or above 100°C are not preferred due to the fact that this would require additional processing equipment.
De organiske^kationaktive forbindelser som kan anvendes ifølge oppfinnelsen, kan velges fra et bredt spektrum av materialer som er istand til å danne en organofil leire ved bytte av kationer med leiren av smectittypen. Den organiske, kationaktive forbindelse bør ha en positiv ladning på ett enkelt atom eller på en liten gruppe av atomer i forbindelsen. Det organiske kation velges fortrinnsvis fra gruppen kvar-tare ammoniumsalter, fosfoniumsalter, sulfoniumsalter og blandinger derav, hvor det organiske kation inneholder minst én lineær eller forgrenet alkylgruppe med 8-60 carbonatomer. Det organiske kation inneholder mer foretrukket en del fra The organic cation-active compounds which can be used according to the invention can be selected from a wide spectrum of materials which are able to form an organophilic clay by exchanging cations with the clay of the smectite type. The organic cationic compound should have a positive charge on a single atom or on a small group of atoms in the compound. The organic cation is preferably selected from the group of quaternary ammonium salts, phosphonium salts, sulfonium salts and mixtures thereof, where the organic cation contains at least one linear or branched alkyl group with 8-60 carbon atoms. The organic cation more preferably contains a part from
en første gruppe bestående av $,y-umettet alkylgruppe med under 7 alifatiske carbonatomer, en hydroxyalkylgruppe med 2-6 carbonatomer og en aralkylgruppe og blandinger derav, a first group consisting of $,y-unsaturated alkyl group with less than 7 aliphatic carbon atoms, a hydroxyalkyl group with 2-6 carbon atoms and an aralkyl group and mixtures thereof,
og en annen del fra en annen gruppe bestående av en alkylgruppe. De to ytterligere deler av forbindelsen velges mer foretrukket individuelt fra en tredje gruppe bestående av en 3,Y-umettet alkylgruppe med under 7 alifatiske carbonatomer, en hydroxyalkylgruppe med 2-6 carbonatomer, en aralkylgruppe, en alkylgruppe med 1-22 carbonatomer og blandinger derav. and another part from another group consisting of an alkyl group. The two further parts of the compound are more preferably selected individually from a third group consisting of a 3,Y-unsaturated alkyl group of less than 7 aliphatic carbon atoms, a hydroxyalkyl group of 2-6 carbon atoms, an aralkyl group, an alkyl group of 1-22 carbon atoms and mixtures thereof .
Det organiske kation har formelen The organic cation has the formula
hvori X betegner nitrogen eller fosfor, Y betegner svovel, betegner en alkylgruppe med 8-22 carbonatomer, og R^, R^ og R4 er individuelt valgt fra gruppen hydrogen, hydroxy-alky lgrupper med 2-6 carbonatomer, alkylgrupper med 1-22 carbonatomer, arylgrupper, aralkylgrupper med 1-22 carbonatomer på alkylkjeden og blandinger derav. X er fortrinnsvis nitrogen. wherein X represents nitrogen or phosphorus, Y represents sulfur, represents an alkyl group of 8-22 carbon atoms, and R^, R^ and R4 are individually selected from the group of hydrogen, hydroxy-alkyl groups of 2-6 carbon atoms, alkyl groups of 1-22 carbon atoms, aryl groups, aralkyl groups with 1-22 carbon atoms on the alkyl chain and mixtures thereof. X is preferably nitrogen.
Dette alkylradikal kan være forgrenet eller uforgrenet, mettet eller umettet, substituert eller usubstituert og skal ha 8-22 carbonatomer i den rette kjededel av radikalet. R-^ er fortrinnsvis en alkylgruppe med 12-22 carbonatomer. This alkyl radical can be branched or unbranched, saturated or unsaturated, substituted or unsubstituted and must have 8-22 carbon atoms in the correct chain part of the radical. R-^ is preferably an alkyl group with 12-22 carbon atoms.
Alkylradikalene kan skrive seg fra naturlige oljer, omfattende forskjellige vegetabilske oljer, som maisolje, kokosnøttolje, soyabønneolje, bomullsfrøolje eller ricinusolje, og forskjellige animalske oljer og fett, som talgolje. Alkylradikalene kan fås syntetisk fra slike utgangsmaterialer som a-olefiner. The alkyl radicals can be derived from natural oils, including various vegetable oils, such as corn oil, coconut oil, soybean oil, cottonseed oil or castor oil, and various animal oils and fats, such as tallow oil. The alkyl radicals can be obtained synthetically from such starting materials as α-olefins.
Representative eksempler på anvendbare forgrenede, mettede alkylradikaler omfatter 12-methylsteary1 og 12-ethyl-stearyl. Representative eksempler på anvendbare forgrenede, umettede radikaler omfatter 12-methyloleyl og 12-ethyloleyl. Representative eksempler på uforgrenede, mettede radikaler omfatter lauryl, stearyl, tridecyl, myristyl (tetradecyl), pentadecyl, hexadecyl, hydrogenert talg og docosanyl. Representative eksempler på uforgrenede, umettede og usubstituerte langkjedede alkylradikaler omfatter oleyl, linoleyl, linoleriyl / soya og talg. Representative examples of useful branched saturated alkyl radicals include 12-methylstearyl and 12-ethyl-stearyl. Representative examples of useful branched unsaturated radicals include 12-methyloleyl and 12-ethyloleyl. Representative examples of unbranched saturated radicals include lauryl, stearyl, tridecyl, myristyl (tetradecyl), pentadecyl, hexadecyl, hydrogenated tallow and docosanyl. Representative examples of unbranched, unsaturated and unsubstituted long chain alkyl radicals include oleyl, linoleyl, linoleriyl / soy and tallow.
V V R4 V V R4
R2, R^ og R^ velges individuelt fra gruppen hydrogen, R 2 , R 1 and R 2 are individually selected from the group hydrogen,
en hydroxyalkylgruppe med 2- 6 carbonatomer, en alkylgruppe med 1-22 carbonatomer, en arylgruppe, en aralkylgruppe med 1- 22 carbonatomer i aralkylgruppens alkylkjede og blandinger derav. a hydroxyalkyl group with 2-6 carbon atoms, an alkyl group with 1-22 carbon atoms, an aryl group, an aralkyl group with 1-22 carbon atoms in the alkyl chain of the aralkyl group and mixtures thereof.
R^ velges fortrinnsvis fra gruppen en (3,Y-umettet alkylgruppe med under 7 alifatiske carbonatomer, en hydroxyalkylgruppe med 2-6 carbonatomer og en aralkylgruppe som inneholder 1-22 carbonatomer i aralkylgruppens alkylkjede, R^ is preferably selected from the group a (3,Y-unsaturated alkyl group with less than 7 aliphatic carbon atoms, a hydroxyalkyl group with 2-6 carbon atoms and an aralkyl group containing 1-22 carbon atoms in the alkyl chain of the aralkyl group,
og blandinger derav. R 3 , og R 4 er fortrinnsvis individuelt valgt fra gruppen en 3,Y-umettet alkylgruppe, en hydroxyalkylgruppe med 2-6 carbonatomer, en alkylgruppe med 1-22 carbonatomer, en aralkylgruppe som omfatter benzyl- og substituerte benzyldeler som omfatter kondenserte ringdeler med lineære eller forgrenede kjeder med 1-22 carbonatomer i aralkylgruppens alkyldel.og blandinger derav. and mixtures thereof. R 3 , and R 4 are preferably individually selected from the group of a 3,Y-unsaturated alkyl group, a hydroxyalkyl group of 2-6 carbon atoms, an alkyl group of 1-22 carbon atoms, an aralkyl group comprising benzyl and substituted benzyl moieties comprising fused ring moieties with linear or branched chains with 1-22 carbon atoms in the alkyl part of the aralkyl group. and mixtures thereof.
Hydroxyalkylgruppen kan være valgt fra et hydroxyl-substituert alifatisk radikal med 2-6 alifatiske carbonatomer, hvori hydroxylgruppen ikke er substituert på det carbonatom som befinner seg nærmest det positivt ladede atom. Alkylgruppen kan være substituert med en aromatisk ring. Representative eksempler omfatter 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxypentyl, 6-hydroxyhexyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxypentyl, 2- hydroxyhexyl, 2- hydroxycyclohexyl, 3-hydroxyc'yc lohexyl, 4-hydroxycyclohexyl, 2-hydroxycyclopentyl, 3-hydroxycyclopentyl, 2-methyl-2-hydroxypropyl, 3-methyl-2-hydroxybutyl eller 5-hydroxy-2-pentenyl. The hydroxyalkyl group can be selected from a hydroxyl-substituted aliphatic radical with 2-6 aliphatic carbon atoms, in which the hydroxyl group is not substituted on the carbon atom which is closest to the positively charged atom. The alkyl group may be substituted with an aromatic ring. Representative examples include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxypentyl, 6-hydroxyhexyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxypentyl, 2-hydroxyhexyl, 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, 4-hydroxycyclohexyl, 2-hydroxycyclopentyl, 3-hydroxycyclopentyl, 2-methyl-2-hydroxypropyl, 3-methyl-2-hydroxybutyl or 5-hydroxy-2-pentenyl.
Alkylgruppen som inneholder 1-22 carbonatomer, kan The alkyl group containing 1-22 carbon atoms can
være lineær eller forgrenet, syklisk eller asyklisk, substituert eller usubstituert. Representative eksempler på anvendbare alkylgrupper omfatter methyl, ethyl, propyl, 2-propyl, isobutyl, cyclopentyl eller cyclohexyl. be linear or branched, cyclic or acyclic, substituted or unsubstituted. Representative examples of useful alkyl groups include methyl, ethyl, propyl, 2-propyl, isobutyl, cyclopentyl or cyclohexyl.
Alkylradikalene kan vær» oppnådd fra råmaterialer The alkyl radicals can be obtained from raw materials
lignende dem for det ovennevnte alkylradikal R^. similar to those for the above-mentioned alkyl radical R^.
Den foretrukne [3, Y-umettede alkylgruppe kan være cyklisk eller acyklisk, usubstituert eller substituert. The preferred [3, Y-unsaturated alkyl group may be cyclic or acyclic, unsubstituted or substituted.
(3, Y-umettede alkylradialer inneholder fortrinnsvis under 7 alifatiske carbonatomer. Alifatiske radikaler som er substituert på den 0,y-umettede gruppe, inneholder fortrinnsvis under 4 carbonatomer . Det |3, y-umettede alkylradikal kan være substituert med en aromatisk ring som er konjugert med umettetheten for 3,Y~delen. &,Y-radikalet kan også være substituert både med alifatiske radikaler og aromatiske ringer. (3,Y-unsaturated alkyl radicals preferably contain less than 7 aliphatic carbon atoms. Aliphatic radicals which are substituted on the 0,y-unsaturated group preferably contain less than 4 carbon atoms. The |3,y-unsaturated alkyl radical may be substituted with an aromatic ring which is conjugated with the unsaturation for the 3,Y~ part.The &,Y radical can also be substituted both with aliphatic radicals and aromatic rings.
Representative eksempler på cykliske Y-umettede alkylgrupper omfatter 2-cyclohexeny1 og 2-cyclopentenyl. Representative eksempler på acykliske 0,Y-umettede alkylgrupper inneholdende 6 carbonatomer eller færre omfatter propargyl, 2-propenyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 3-methyl-2-butenyl, 3-methyl-2-pentenyl, 2,3-dimethyl-2-butenyl, 1,l-dimethyl-2-propenyl, 1,2-dimethyl-2-propeny1, 2,4-penta-dienyl eller 2,4-hexadienyl. Representative eksempler på aoykliske, aromatisk substituerte forbindelser omfatter 3-fenyl-2-propenyl, 2-fenyl-2-propenyl, eller 3-(4-methoxy-fenyl)-2-propenyl. Representative eksempler på aromatisk og alifatisk substituerte materialer omfatter 3-feny1-2-cyclo-hexenyl eller 3-fenyl-2-cyclopentenyl. Alkylgruppen kan være substituert med en aromatisk ring. Representative examples of cyclic Y-unsaturated alkyl groups include 2-cyclohexenyl and 2-cyclopentenyl. Representative examples of acyclic 0,Y-unsaturated alkyl groups containing 6 carbon atoms or fewer include propargyl, 2-propenyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 3-methyl-2-butenyl, 3-methyl-2-pentenyl, 2,3-dimethyl-2-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 2,4-pentadienyl or 2,4-hexadienyl. Representative examples of acyclic aromatic substituted compounds include 3-phenyl-2-propenyl, 2-phenyl-2-propenyl, or 3-(4-methoxy-phenyl)-2-propenyl. Representative examples of aromatically and aliphatically substituted materials include 3-phenyl-2-cyclohexenyl or 3-phenyl-2-cyclopentenyl. The alkyl group may be substituted with an aromatic ring.
Eksempler på arylgrupper vil inneholde fenyl, som Examples of aryl groups would include phenyl, which
i N-alkyl- eller N,N-dialkylaniliner, hvori alkylgruppene inneholder mellom 1 og 22 carbonatomer, o-, m- eller p-nitrofenyl, o-, m- eller p-alkylfeny1, hvori alkylgruppene inneholder mellom 1 og 22 carbonatomer, 2-, 3- eller 4-halogen-fenyl, hvori halogengruppen er klor, brom eller jod, eller 2-, 3- eller 4-carboxyfenyl eller estere derav, hvor alkoholen for esteren skriver seg fra en alkylalkohol hvori alkylgruppen inneholder mellom 1 og 2 2 carbonatomer, aryl, som fenol, eller aralkyl, som benzylalkoholer, kondenserte ring-aryldeler, som nafthalen, anthracen eller fenanthren. in N-alkyl- or N,N-dialkylanilines, in which the alkyl groups contain between 1 and 22 carbon atoms, o-, m- or p-nitrophenyl, o-, m- or p-alkylphenyl1, in which the alkyl groups contain between 1 and 22 carbon atoms, 2-, 3- or 4-halo-phenyl, in which the halogen group is chlorine, bromine or iodine, or 2-, 3- or 4-carboxyphenyl or esters thereof, where the alcohol for the ester is written from an alkyl alcohol in which the alkyl group contains between 1 and 2 2 carbon atoms, aryl, such as phenol, or aralkyl, such as benzyl alcohols, fused ring aryl moieties, such as naphthalene, anthracene or phenanthrene.
Representative eksempler på en aralkylgruppe omfatter benzyl og slike materialer som er avledet fra forbindelser, som benzylhalogenider, benzhydrylhalogenider, tritylhalo-genider, 1-halogen-l-fenylalkaner hvori alkylkjeden har fra 1 til 22 carbonatomer,som 1-halogen-l-fenylethan, 1-haloaen-l-f enylethan, 1-halogen-l-f enyl propan eller 1-halogen-l-f eny loe ta-decan, substituerte benzyldeler slike som vil være avledet fra o-, m- eller p-klorbenzylhalogenider, p-methoxybenzyl-halogenider, o-, m- eller p-nitrilbenzylhalogenider eller o-, m- eller p-alkylbenzylhalogenider hvori alkylkjeden inneholder 1-22 carbonatomer, og kondenserte ringdeler av benzyltypen som slike som vil være avledet fra 2-halomethvl-nafthaien, 9-halogenmethylanthracen eller 9-halogenmethylfenanthren, hvori halogengruppen utgjøres av klor, brom eller jod, eller en hvilken som helst annen slik gruppe som vil virke som en forlatende gruppe ved det nukleofile angrep av delen av benzyltypen, slik at den nukleofile del vil erstatte den forlatende gruppe på benzyltypedelen. Representative examples of an aralkyl group include benzyl and such materials derived from compounds such as benzyl halides, benzhydryl halides, trityl halides, 1-halo-l-phenylalkanes in which the alkyl chain has from 1 to 22 carbon atoms, such as 1-halo-l-phenylethane, 1-halo-1-phenylethane, 1-halogen-1-phenyl propane or 1-halogen-1-phenyl decadecane, substituted benzyl moieties such as will be derived from o-, m- or p-chlorobenzyl halides, p-methoxybenzyl halides, o-, m- or p-nitrile benzyl halides or o-, m- or p-alkylbenzyl halides in which the alkyl chain contains 1-22 carbon atoms, and fused ring moieties of the benzyl type such as would be derived from 2-halomethylnaphthalene, 9-halomethylanthracene or 9 -halomethylphenanthrene, in which the halogen group is chlorine, bromine or iodine, or any other such group which will act as a leaving group in the nucleophilic attack of the benzyl-type moiety, so that the nucleophilic moiety vi l replace the leaving group on the benzyl type moiety.
En forbindelse dannes av det ovenfor beskrevne organiske kation og et anionaktivt radikal fra gruppen klorid, bromid, jodid, nitritt, hydroxyd, acetat, methyl-sulfat og blandinger derav. Anionet velges fortrinnsvis fra gruppen klorid og bromid og blandinger derav og er mer foretrukket klorid selv om andre anioner, som jodid, acetat, hydroxyd eller nitritt etc, kan være tilstede i den organiske, kationaktive forbindelse for å nøytralisere kationet. A compound is formed by the organic cation described above and an anionic radical from the group of chloride, bromide, iodide, nitrite, hydroxide, acetate, methyl sulfate and mixtures thereof. The anion is preferably selected from the group of chloride and bromide and mixtures thereof and is more preferably chloride although other anions, such as iodide, acetate, hydroxide or nitrite etc, may be present in the organic, cation-active compound to neutralize the cation.
Organiske, kationaktive salter kan fremstilles ved slike metoder som er beskrevet i US patentskrifter 2355356, 2775617 og 3136819. Organic, cationically active salts can be prepared by such methods as are described in US patents 2355356, 2775617 and 3136819.
De organiske anioner som kan anvendes ifølge oppfinnelsen, skal være istand til å reagere med et organisk kation og danne inntrengninger i en leire av smectittypen i form av et organisk kation - organisk anionkompleks. Molekylvekten (grammolekylvekten) for det organiske anion The organic anions that can be used according to the invention must be able to react with an organic cation and form penetrations in a clay of the smectite type in the form of an organic cation - organic anion complex. The molecular weight (gram molecular weight) of the organic anion
er fortrinnsvis 3000 eller derunder, helst 1000 eller derunder, og molekylet inneholder minst én sur del pr. molekyl som her beskrevet. Det organiske anion er fortrinnsvis avledet fra en organisk syre med en pK ri under 11,0. Som an- is preferably 3000 or less, preferably 1000 or less, and the molecule contains at least one acidic part per molecule as described here. The organic anion is preferably derived from an organic acid with a pK ri below 11.0. As an-
tydet må utgangssyren inneholde minst ett ioniserbart hydro-genatom med den foretrukne pKA for å muliggjøre dannelsen a<y >det organiske kation-organiske anionkompleks og den påfølg-ende inntrengningsreaksjon. therefore, the starting acid must contain at least one ionizable hydrogen atom with the preferred pKA to enable the formation of the organic cation-organic anion complex and the subsequent penetration reaction.
Dessuten kan en hvilken som helst forbindelse anvendes som vil gi det ønskede organiske anion eller hydrolyse. Representative forbindelser omfatter: 1) syreanhydrider, omfattende eddiksyreanhydrid, malein-syreanhydrid, ravsyreanhydrid eller fthalsyreanhydrid, 2) syrehalogenider, omfattende acetylklorid, octanoyl-klorid, lauroylklorid, lauroylbromid eller benzoyl-bromid, 3) 1,1,1-trihalogenider, omfattende 1,1,1-triklorethan eller 1,1,1-tribromoctan, eller 4) orthoestere, omfattende ethylorthoformat eller ethyl-orthostearat. Also, any compound can be used which will give the desired organic anion or hydrolysis. Representative compounds include: 1) acid anhydrides, including acetic anhydride, maleic anhydride, succinic anhydride, or phthalic anhydride, 2) acid halides, including acetyl chloride, octanoyl chloride, lauroyl chloride, lauroyl bromide, or benzoyl bromide, 3) 1,1,1-trihalides, including 1 ,1,1-trichloroethane or 1,1,1-tribromooctane, or 4) orthoesters, including ethyl orthoformate or ethyl orthostearate.
De organiske anioner kan foreligge i form av en syre eller et salt. , Salter kan velges fra alkalimetallsalter, jordalkalimetallsalter, ammoniakk eller organiske aminer. Representative salter omfatter hydrogen-, lithium-, natrium-, kalium-, magnesium-, kalsium-, barium- eller ammoniumsalter eller organiske aminer, som ethanolamin, diethanolamin, triethanolamin, methyldiethanolamin, butyldiethanolamin, diethylamin, dimethylamin, triethylamin, dibutylamin eller blandinger derav. Det foretrukne alkalimetallsalt er natriumsaltet. The organic anions can be in the form of an acid or a salt. , Salts may be selected from alkali metal salts, alkaline earth metal salts, ammonia or organic amines. Representative salts include hydrogen, lithium, sodium, potassium, magnesium, calcium, barium or ammonium salts or organic amines, such as ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, butyldiethanolamine, diethylamine, dimethylamine, triethylamine, dibutylamine or mixtures thereof . The preferred alkali metal salt is the sodium salt.
Egnede sure, funksjonelle, organiske forbindelser omfatter: Suitable acidic functional organic compounds include:
1) Carboxylsyrer omfattende: 1) Carboxylic acids including:
(a) benzencarboxylsyrer, som benzosyre, o-, m- eller p-fthalsyre, 1,2,3-benzentricarboxylsyre, 1,2,4-benzentricarboxylsyre, 1,3,5-benzentricarboxylsyre, 1,2,4,5-benzentetracarboxylsyre eller 1,2,3,4,5,6-benzenhexa-carboxylsyre (mellittsyre), (b) alkylcarboxylsyrer med formelen H-(CH^)n~COOH, hvori n er et tall fra 0 til 20, og slike forbindelser omfatter eddiksyre, propionsyre, butansyre, pentansyre, hexan-syre, heptansyre, octansyre, nonansyre, decansyre, undecan-syre, laurinsyre, tridecansyre, tetradecansyre, pentadecan-syre, hexadecansyre, heptadecansyre, octadecansyre (stearin-syre), nonadecansyre eller eicosansyre, (c) alkyldicarboxylsyrer med formelen HOOC-(CH2)n~COOH, hvori n varierer fra 0 til 8, som oxalsyre, malonsyre, ravsyre, glutarsyre, adipinsyre, pimelinsyre, suberinsyre, azelain-syre eller sebacinsyre, (d) hydroxyalkylcarboxylsyrer som sitronsyre, vin-syrer, eplesyre, mandel syre eller 12-hydroxystearinsyre, (e) umettede alkylcarboxylsyrer som maleinsyre, fumar-syre eller kanelsyre, (a) benzenecarboxylic acids, such as benzoic acid, o-, m- or p-phthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5- benzenetetracarboxylic acid or 1,2,3,4,5,6-benzenehexacarboxylic acid (mellitic acid), (b) alkylcarboxylic acids of the formula H-(CH^)n~COOH, where n is a number from 0 to 20, and such compounds includes acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid or eicosanoic acid, (c) alkyldicarboxylic acids of the formula HOOC-(CH2)n~COOH, where n varies from 0 to 8, such as oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic or sebacic acids, (d) hydroxyalkylcarboxylic acids such as citric acid , tartaric acids, malic acid, mandelic acid or 12-hydroxystearic acid, (e) unsaturated alkylcarboxylic acids such as maleic acid, fumaric acid or is cinnamic acid,
(f) aromatiske carboxylsyrer med kondensert ring, (f) fused ring aromatic carboxylic acids,
som nafthalensyre eller anthracencarboxylsyre, such as naphthalene acid or anthracenecarboxylic acid,
(g) cycloalifatiske syrer, som cyclohexancarboxyl-syre, cyclopentancarboxylsyre eller furancarboxylsyrer. (2) organiske svovelsyrer omfattende (a) sulfonsyrer som omfatter (1) benzensulfonsyrer som benzensulfonsyre, fenolsulfonsyre, dodecylbenzensulfonsyre, benzendisulfonsyre, benzentrisulfonsyrer eller p-toluensulfonsyre, eller (2) alkylsulfonsyrer, som methansulfonsyre, ethan-sulfonsyre, butansulfonsyre eller butandisulfonsyre, sulfo-succinatalkylestere, som dioctylsuccinylsulfonsyre, eller alkylpolyethanoxysuccinylsulfonsyre, eller (b) alkylsulfater, som laurylhalvesteren av svovelsyre eller octadecylhalvesteren av svovelsyre. (g) cycloaliphatic acids, such as cyclohexanecarboxylic acid, cyclopentanecarboxylic acid or furancarboxylic acids. (2) organic sulfuric acids comprising (a) sulfonic acids comprising (1) benzenesulfonic acids such as benzenesulfonic acid, phenolsulfonic acid, dodecylbenzenesulfonic acid, benzenedisulfonic acid, benzenetrisulfonic acids or p-toluenesulfonic acid, or (2) alkylsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid or butanedisulfonic acid, sulfo- succinate alkyl esters, such as dioctylsuccinyl sulfonic acid, or alkylpolyethanoxysuccinyl sulfonic acid, or (b) alkyl sulfates, such as the lauryl half-ester of sulfuric acid or the octadecyl half-ester of sulfuric acid.
(3) organofosforsyrer, omfattende (3) organophosphoric acids, comprehensive
(a) fosfonsyrer med formelen (a) phosphonic acids of the formula
hvori R betegner en arylgruppe eller alkylgruppe med 1-2 2 carbonatomer, in which R denotes an aryl group or alkyl group with 1-2 2 carbon atoms,
(b) fosfinsyrer med formelen (b) phosphinic acids of the formula
hvori R betegner er arylgruppe eller en alkylgruppe med 1-22 carbonatomer, som dicyclohexylfosfinsyre, dibutylfos-finsyre eller dilaurylfosfinsyre, in which R represents aryl group or an alkyl group with 1-22 carbon atoms, such as dicyclohexylphosphinic acid, dibutylphosphinic acid or dilaurylphosphinic acid,
(c) thiofosfinsyrer med formelen (c) thiophosphinic acids of the formula
hvori R betegner en arylgruppe eller alkylgruppe med 1 -22 carbonatomer, som diisobutyldithiofosfinsyre, dibutyldi-thiofosfinsyre eller dioctadecyldithiofosfinsyre, (d) fosfitter, dvs. diestere av fosforsyrling, med formelen: HO-P(OR)2, hvori R betegner en alkylgruppe med 1-22 carbonatomer, som dioctadecylfosfitt, (e) fosfater, dvs. diestere av fosforsyre, med formelen hvori R betegner en alkylgruppe med 1-22 carbonatomer, som dioctadecylfosfat. (4) Eenoler, som fenol, hydrokinon, t-butylcatechol, p-methoxyfenol eller naftholer.. in which R denotes an aryl group or alkyl group with 1-22 carbon atoms, such as diisobutyldithiophosphinic acid, dibutyldithiophosphinic acid or dioctadecyldithiophosphinic acid, (d) phosphites, i.e. diesters of phosphoric acid, with the formula: HO-P(OR)2, in which R denotes an alkyl group with 1-22 carbon atoms, such as dioctadecyl phosphite, (e) phosphates, i.e. diesters of phosphoric acid, of the formula in which R denotes an alkyl group with 1-22 carbon atoms, such as dioctadecyl phosphate. (4) Enols, such as phenol, hydroquinone, t-butylcatechol, p-methoxyphenol or naphthols..
(5) Thiosyrer med formelene: (5) Thioacids with the formulas:
hvori R betegner en arylgruppe eller alkylgruppe med 1-22 carbonatomer, som thiosalicylsyre, thiobenzosyre, thio-eddiksyre, thiolaurinsyre eller thiostearinsyre. (6) Aminosyrer, som de naturlige aminosyrer eller derivater derav, som 6-aminohexansyre, 12-aminododecansyre, N-fenylglycin eller 3-aminocrotonsyre. (7) Polymere syrer fremstilt fra sure monomerer hvor syrefunksjonen holder seg i polymerkjeden, som acrylsyre-polymerer med lav molekylvekt eller copolymerer derav eller styren-maleinsyreanhydridcopolymerer. (8) Forskjellige syrer og syresalter, som ferro-cyanid, ferricyanid, natriumtetrafenylborat, fosforwolfram* syre, fosforsiliciumsyre eller et hvilket som helst annet slikt anion som vil danne et tett ionepar med et organisk kation, dvs. et hvilket som helst slikt anion som vil danne et vannuoppløselig bunnfall sammen med et organisk kation. wherein R denotes an aryl group or alkyl group with 1-22 carbon atoms, such as thiosalicylic acid, thiobenzoic acid, thioacetic acid, thiolauric acid or thiostearic acid. (6) Amino acids, such as the natural amino acids or derivatives thereof, such as 6-aminohexanoic acid, 12-aminododecanoic acid, N-phenylglycine or 3-aminocrotonic acid. (7) Polymeric acids prepared from acidic monomers where the acid function remains in the polymer chain, such as low molecular weight acrylic acid polymers or copolymers thereof or styrene-maleic anhydride copolymers. (8) Various acids and acid salts, such as ferrocyanide, ferricyanide, sodium tetraphenylborate, phosphortungstic* acid, phosphorsilicic acid or any other such anion which will form a close ion pair with an organic cation, i.e. any such anion which will form a water-insoluble precipitate together with an organic cation.
For enkelhets skyld ved håndteringen foretrekkes det at det samlede innhold av organisk materiale i de organofile leirereaksjonsprodukter ifølge oppfinnelsen skal ut-gjøre under ca. 50 vekt% av organoleiren. Selv om høyere mengder er anvendbare, vil reaksjonsproduktet da være van-skelig å filtrere, tørke og nedmale. For ease of handling, it is preferred that the total content of organic material in the organophilic clay reaction products according to the invention should amount to less than approx. 50% by weight of the organoclay. Although higher amounts are usable, the reaction product will then be difficult to filter, dry and grind down.
En tilstrekkelig mengde med organisk kation anvendes A sufficient amount of organic cation is used
for å tilfredsstille leirens kationbytteevne og det organiske anions kationaktivitet. Ytterligere mengder kation utover summen av leirens bytteevne dg anionet er valgfrie. For eksempel krever leirer av smectittypen minst 90 milliekvivalenter organisk kation for å tilfredsstille i det minste en del av det samlede organiske kationbehov. En anvendelse av mengder fra 80-200 milliekvialenter (me), fortrinnsvis 100-160 me, to satisfy the cation exchange capacity of the clay and the cation activity of the organic anion. Additional amounts of cation beyond the sum of the exchange capacity of the clay and the anion are optional. For example, smectite-type clays require at least 90 milliequivalents of organic cation to satisfy at least part of the total organic cation requirement. An application of amounts from 80-200 milliequivalents (me), preferably 100-160 me,
er aksepterbar. Ved lavere milliekvivalentforhold vil en ufullstendig reaksjon finne sted som vil føre til et ueffek-tivt gelmiddel. is acceptable. At lower milliequivalent ratios, an incomplete reaction will take place which will lead to an ineffective gelling agent.
Mengden av organisk anion som tilsettes til leiren, skal være tilstrekkelig til at den organofile leire får den ønskede forbedrede dispergeringsegenskap. Denne mengde er definert som det milliekvivalentforhold som representeres av antallet av milliekvivalenter (me) av det organiske anion i organoleiren pr. 100 g av leiren, basert på 100% aktiv leire. Anionmilliekvivalentforholdet bør fortrinnsvis ligge innen området 5-100, fortrinnsvis 10-50. The amount of organic anion added to the clay must be sufficient for the organophilic clay to obtain the desired improved dispersion property. This amount is defined as the milliequivalent ratio represented by the number of milliequivalents (me) of the organic anion in the organoclay per 100 g of the clay, based on 100% active clay. The anion milliequivalent ratio should preferably lie within the range 5-100, preferably 10-50.
Det organiske anion tilsettes fortrinnsvis til reaktantene i det ønskede milliekvivalentforhold i form av et fast materiale eller en oppløsning i vann og under omrør-ing for å oppnå en makroskopisk homogen blanding. The organic anion is preferably added to the reactants in the desired milliequivalent ratio in the form of a solid material or a solution in water and with stirring to obtain a macroscopically homogeneous mixture.
Leirer av smectittypen forekommer i naturen eller fremstilles syntetisk. Egnede leirer omfatter montmorillo-nitt, bentonitt, beidelitt, hectoritt, saponitt eller steven-sitt. Nærmere bestemt skal leirer av smectittypen ha en kationbytteevne av minst 75 milliekvivalenter pr. 100 g leire. Spesielt ønskede leiretyper er de naturlig fore-kommende Wyoming-kvaliteter av bentonitt eller hectoritt, Clays of the smectite type occur in nature or are produced synthetically. Suitable clays include montmorillonite, bentonite, beidelite, hectorite, saponite or stevensite. More specifically, clays of the smectite type must have a cation exchange capacity of at least 75 milliequivalents per 100 g of clay. Particularly desirable types of clay are the naturally occurring Wyoming grades of bentonite or hectorite,
en svellende magnesium-lithiumsilikatleire. Egnede syn-tetiske leirer kan fremstilles syntetisk på vanlig måte, omfattende pneumatolyttiske eller hydrotermiske metoder. a swelling magnesium-lithium silicate clay. Suitable synthetic clays can be produced synthetically in the usual way, including pneumatolytic or hydrothermal methods.
Leirene, spesielt leirene av bentonittypen, omvandles fortrinnsvis til natriumformen dersom de ikke allerede fore-ligger i denne form. Dette kan enkelt gjøres ved å fremstille en vandig leireoppslemning og ved å føre oppslemningen gjennom et skikt av kationbytteharpiks i natriumform. Leiren kan alternativt blandes med vann og en egnet natriumforbind-else, som natriumcarbonat eller natriumhydroxyd, hvorefter blandingen utsettes for skjærkrefter i en eltemølle eller ekstruder. The clays, especially clays of the bentonite type, are preferably converted to the sodium form if they are not already present in this form. This can be easily done by preparing an aqueous clay slurry and by passing the slurry through a layer of cation exchange resin in sodium form. Alternatively, the clay can be mixed with water and a suitable sodium compound, such as sodium carbonate or sodium hydroxide, after which the mixture is subjected to shearing forces in a kneading mill or extruder.
Kationbytteevnen for leirene av smectittypen kan be-stemmes ved hjelp av ammoniumacetatmetoden. The cation exchange capacity of the clays of the smectite type can be determined using the ammonium acetate method.
Leiren blir fortrinnsvis dispergert i vann i en konsentrasjon av 1-80%, fortrinnsvis 2-20%, og mer foretrukket 2-7%. Oppslemningen blir omrørt før reaksjonen. The clay is preferably dispersed in water in a concentration of 1-80%, preferably 2-20%, and more preferably 2-7%. The slurry is stirred before the reaction.
De organiske, kationaktive forbindelser som anvendes ifølge oppfinnelsen, ble fremstilt ved hjelp av standard kjente metoder ut fra et amin med det ønskede antall langkjedede alkylgrupper bundet til nitrogenatomet. Dette langkjedede alkylamin ble derefter omsatt ved reduserende alkylering med et aldehyd og/eller ved nukleofil fortreng-ning av et alkylhalogenid under dannelse av den ønskede kvartære ammoniumforbindelse. The organic, cationic compounds used according to the invention were prepared using standard known methods from an amine with the desired number of long-chain alkyl groups bound to the nitrogen atom. This long-chain alkylamine was then reacted by reductive alkylation with an aldehyde and/or by nucleophilic displacement of an alkyl halide to form the desired quaternary ammonium compound.
Væsken ifølge oppfinnelsen kan inneholde en dispergert vandig fase, omfattende vandige oppløsninger av uorganiske salter, som natriumklorid eller kalsiumklorid. Selv om tilsetningen av disse salter er valgfrie, vil slike salter øke det osmotiske trykk for vannfasen i formasjonene som inneholder hydratiserbare leirer. The liquid according to the invention can contain a dispersed aqueous phase, comprising aqueous solutions of inorganic salts, such as sodium chloride or calcium chloride. Although the addition of these salts is optional, such salts will increase the osmotic pressure of the water phase in the formations containing hydratable clays.
Konsentrasjonen av vann i væsken er bestemt av The concentration of water in the liquid is determined by
slike variable som væskevektbehov, ønskede flyteegenskaper, temperaturer ved hullets bunn og arbeidskrav hva gjelder boring, kjerneboring eller komplettering. Det foretrekkes i alminnelighet å anvende vann i en mengde av 2-50 volum%. Dette område gjør den oljebaserte væske brannsikker når den utsettes for temperaturer som ellers ville ha antent oljen. Dessuten oppviser væsken en utmerket toleranse overfor vannforurensning, og væskens flytbarhetsegenskaper kan reguleres til verdier som er sammenlignbare med de til-svarende verdier for vannbaserte væsker. such variables as liquid weight requirements, desired flow properties, temperatures at the bottom of the hole and work requirements in terms of drilling, core drilling or completion. It is generally preferred to use water in an amount of 2-50% by volume. This area makes the oil-based fluid fireproof when exposed to temperatures that would otherwise have ignited the oil. In addition, the liquid exhibits an excellent tolerance towards water contamination, and the fluidity properties of the liquid can be regulated to values which are comparable to the corresponding values for water-based liquids.
Vanlige emulgeringsmidler bør anvendes for vann-i-oljefasen og kan anvendes for den ikke-vandige væske. Den anvendte mengde emulgeringsmiddel er først og fremst avhengig av den tilstedeværende vannmengde og av den ønskede emulgeringsgrad. I alminnelighet har 5,7-85,6, fortrinnsvis 14,3-57,1 g pr. liter vist seg tilfredsstillende for å oppnå de nødvendige gelstyrker og kontroll med filtreringen. Common emulsifiers should be used for the water-in-oil phase and can be used for the non-aqueous liquid. The amount of emulsifier used is primarily dependent on the amount of water present and the desired degree of emulsification. In general, 5.7-85.6, preferably 14.3-57.1 g per liter proved satisfactory for achieving the required gel strengths and control of the filtration.
Blandingene kan eventuelt inneholde vanlige vekt-bidragende midler, som barytt, for å regulere væskens densitet til mellom 0,9 og 2,6 kg/liter, og dessuten midler for å kontrollere tap av flytbarhet. The mixtures may optionally contain common weight-contributing agents, such as baryte, to regulate the liquid's density to between 0.9 and 2.6 kg/litre, and also agents to control loss of fluidity.
Leirene av smectittypen anvendt i eksemplene var hectoritt og Wyoming-bentonitt. Leiren ble oppslemmet i vann og sentrifugert for å fjerne i det vesentlige alle forurensninger som ikke var av leiretypen og som kan oppgå til 10-50% av utgangsleireblandingen. Oppslemningen med Wyoming-bentonittleire ble ledet gjennom et skikt med kationbytteharpiks for å omdanne leiren til natriumformen. The smectite-type clays used in the examples were hectorite and Wyoming bentonite. The clay was slurried in water and centrifuged to remove essentially all impurities that were not of the clay type and which can amount to 10-50% of the starting clay mixture. The Wyoming bentonite clay slurry was passed through a bed of cation exchange resin to convert the clay to the sodium form.
Eksemplene 1-4 viser fremstilling av forskjellige organiske, kationaktive forbindelser som kan anvendes som reaktanter sammen med en organoleire for fremstilling av de organofile leirereaksjonsprodukter som anvendes i væskene ifølge oppfinnelsen. Examples 1-4 show the preparation of various organic, cationically active compounds which can be used as reactants together with an organoclay for the preparation of the organophilic clay reaction products which are used in the liquids according to the invention.
De i eksemplene beskrevne organiske, kationaktive forbindelser er representative for kationene for de forbindelser som anvendes iføl<q>e oppfinnelsen, The organic cation-active compounds described in the examples are representative of the cations for the compounds used according to the invention,
I de nedenstående eksempler er alle prosenter basert på vekt dersom intet annet er angitt. Plastisk viskositet, flytegrense og ti sekunders geler ble målt ved hjelp av den metode som er beskrevet i API RP13B, American Petroleum Institutes Standard Procedure for Testing Fluids, 6. utgave, april 1976. In the examples below, all percentages are based on weight if nothing else is stated. Plastic viscosity, yield strength and ten second gels were measured using the method described in API RP13B, American Petroleum Institute's Standard Procedure for Testing Fluids, 6th Edition, April 1976.
Eksempel 1 Example 1
Allylmethyl-di(hydrogenert-talg)-ammoniumklorid (AM2HT). Allylmethyl-di(hydrogenated-tallow)-ammonium chloride (AM2HT).
824,7 g methyl-di(hydrogenert-talg)-amin, 350 ml isopropylalkohol, 250 g NaHC03, 191,3 g allylklorid og 10 g allylbromid (som katalysator) ble blandet i en 4 liters reaksjonsbeholder forsynt med en kondensator. Blandingen ble oppvarmet og tilbakeløpsdestillert. En prøve ble fjernet, filtrert og titrert med HCl og NaOH. Reaksjonen ble be-traktet som avsluttet når 0,0% amin-HCl og 1,8% amin var tilstede. Sluttanalysen for dette AM2HT ga en effektiv grammolekylvekt av 831,17. 824.7 g of methyl-di(hydrogenated-tallow)amine, 350 ml of isopropyl alcohol, 250 g of NaHCO 3 , 191.3 g of allyl chloride and 10 g of allyl bromide (as catalyst) were mixed in a 4 liter reaction vessel fitted with a condenser. The mixture was heated and refluxed. A sample was removed, filtered and titrated with HCl and NaOH. The reaction was considered complete when 0.0% amine-HCl and 1.8% amine were present. The final analysis for this AM2HT gave an effective gram molecular weight of 831.17.
Eksempel 2 Example 2
En 3%-ig leireoppslemning (natriumform av Wyoming-bentonitt) ble oppvarmet til 60°C under omrøring. 4,8637 g (milliekvivalentforhold=22,5) av en organisk, anionaktiv forbindel.se, natriumbenzoat (molekylvekt 144,11), ble opp-løst i vann. Den organiske anionoppløsning ble tilsatt til leireoppslemningen og omsatt i 10 minutter ved 60°C. 136,89 g (me-forhold=122,5) ethanolmethyl-di(hydrogenert-talg) -ammoniumklorid (EM2HT) (mv 745) (fra Armak Co., avdeling av Akzona Corp.) ble oppløst i 50%-ig vandig 2-propanoloppløsning. Kationoppløsningen ble tilsatt og omrørt ved 60°C i 45 minutter. Organoleiren (EM2HT/benzoat/ bentonitt) ble oppsamlet på et vakuumfilter. Filterkaken ble vasket med varmt vann og tørket ved 6 0°C. Den tørkede organoleire ble malt i en hammermølle for å redusere par-tikkelstørrelsen og derefter siktet gjennom en 74^um sikt. A 3% clay slurry (sodium form of Wyoming bentonite) was heated to 60°C with stirring. 4.8637 g (milliequivalent ratio=22.5) of an organic, anionic compound, sodium benzoate (molecular weight 144.11), was dissolved in water. The organic anion solution was added to the clay slurry and reacted for 10 minutes at 60°C. 136.89 g (me ratio=122.5) ethanolmethyl-di(hydrogenated-tallow)-ammonium chloride (EM2HT) (mv 745) (from Armak Co., division of Akzona Corp.) was dissolved in 50% aqueous 2-propanol solution. The cation solution was added and stirred at 60°C for 45 minutes. The organoclay (EM2HT/benzoate/bentonite) was collected on a vacuum filter. The filter cake was washed with hot water and dried at 60°C. The dried organoclay was milled in a hammer mill to reduce particle size and then sieved through a 74 µm sieve.
Eksempel 3 Example 3
En 3%-ig leireoppslemning (natriumform av Wyoming-bentonitt) ble oppvarmet til 60°C under omrøring. 7,83 g (m.e.forhold=22,5) av en organisk, anionaktiv forbindelse, natriumsaltet av p-fenolsulfonsyre (m.v. 232,19), ble opp-løst i vann. Den organiske anionoppløsning ble tilsatt til leireoppslemningen og omsatt i 10 minutter ved 60°C. 134,42 g (m.e. forhold=122,5) benzylmethyl-di(hydrogenert-talgV-ammoniumklorid, BM2HT, ble oppløst i en 50%-ig vandig 2-propanoloppløsning. Kationoppløsningen ble tilsatt og omrørt i 45 minutter ved 60°C. Organoleiren (BM2HT/p-fenolsulfonat/bentonitt) ble oppsamlet på et vakuumfilter. Filterkaken ble vasket med varmt vann og tørket ved 60°C. Den tørkede organoleire ble malt i en hammermølle for å redusere partikkelstørrelsen og derefter siktet gjennom en 74^um sikt. A 3% clay slurry (sodium form of Wyoming bentonite) was heated to 60°C with stirring. 7.83 g (m.e. ratio=22.5) of an organic, anionic compound, the sodium salt of p-phenolsulfonic acid (m.v. 232.19), was dissolved in water. The organic anion solution was added to the clay slurry and reacted for 10 minutes at 60°C. 134.42 g (m.e. ratio=122.5) benzylmethyl-di(hydrogenated-tallowV-ammonium chloride, BM2HT) was dissolved in a 50% aqueous 2-propanol solution. The cation solution was added and stirred for 45 minutes at 60°C. The organoclay (BM2HT/p-phenolsulfonate/bentonite) was collected on a vacuum filter. The filter cake was washed with hot water and dried at 60° C. The dried organoclay was ground in a hammer mill to reduce particle size and then sieved through a 74 µm sieve .
Eksempel 4 Example 4
En 3%-ig leireoppslemning (natriumform av Wyoming-bentonitt) ble oppvarmet til 60°C under omrøring. 5,40 g (m.e. forhold= 22,5) av en organisk, anionaktiv forbindelse, natriumsaltet av salicylsyre (m.v. 160,11), ble oppløst i vann. Den organiske anionoppløsning ble tilsatt til leireoppslemningen og omsatt i 10 minutter ved 60°C. 134,72 g (m.e. forhold = 122,5) av AM2HT fremstilt som beskrevet i eksempel 1, ble oppløst i en 50%-ig vandig 2-propanoloppløsning. Kation-oppløsningen ble tilsatt og omrørt i 45 minutter ved 60°C. Organoleiren (AM2HT/salicylat/bentonitt) ble oppsamlet på A 3% clay slurry (sodium form of Wyoming bentonite) was heated to 60°C with stirring. 5.40 g (m.e. ratio = 22.5) of an organic, anionic compound, the sodium salt of salicylic acid (m.v. 160.11), was dissolved in water. The organic anion solution was added to the clay slurry and reacted for 10 minutes at 60°C. 134.72 g (m.e. ratio = 122.5) of AM2HT prepared as described in example 1 was dissolved in a 50% aqueous 2-propanol solution. The cation solution was added and stirred for 45 minutes at 60°C. The organoclay (AM2HT/salicylate/bentonite) was collected on
et vakuumfilter. Filterkaken ble vasket med varmt vann og tørket ved 60°C. Den tørkede organoleire ble malt i en hammermølle for å redusere partikkelstørrelsen og ble derefter siktet gjennom en 74^um sikt. a vacuum filter. The filter cake was washed with hot water and dried at 60°C. The dried organoclay was milled in a hammer mill to reduce the particle size and then sieved through a 74 µm sieve.
Eksempler 5- 9 Examples 5-9
100 liter dieselolje, 3,6 kg emulgeringsmiddel (selges under betegnelsen"Invermul" ), 3,6 kg filtrerings-reguleringsmiddel, dvs. aminlignitt (selges under beteg-nelsen"Duratone"HT), 1,8 kg kalk og 17,5 liter vann ble om-rørt i 20 minutter. 100 liters of diesel oil, 3.6 kg of emulsifier (sold under the name "Invermul"), 3.6 kg of filtration-regulating agent, i.e. amine lignite (sold under the name "Duratone" HT), 1.8 kg of lime and 17.5 liter of water was stirred for 20 minutes.
10,0 kg kalsiumklorid, 147,4 kg barytt (som selges under betegnelsen"Baroid") og 2,3 kg av de tre bentonitt-leirefortykningsmidler fremstilt ifølge eksemplene 2-4 foruten kommersielle produkter dimethyl-di(hydrogenert-talg)-ammoniumklorid (2M2HT)/bentonitt og benzylmethyl-di (hydro-genert-talg)-ammoniumklorid (BM2HT)/bentonitt ble tilsatt. 10.0 kg of calcium chloride, 147.4 kg of barite (which is sold under the name "Baroid") and 2.3 kg of the three bentonite clay thickeners prepared according to examples 2-4 in addition to commercial products dimethyl-di(hydrogenated-tallow)-ammonium chloride (2M2HT)/bentonite and benzylmethyl-di(hydrogenated-tallow)-ammonium chloride (BM2HT)/bentonite were added.
Den blandede væske ble undersøkt ved 35 C for å fastslå standard rheologiske data, og resultatene er gjen-g-itt i tabell 2. Ingen av væskene ifølge eksemplene viste bunnavsetning efter omrøring: The mixed liquid was examined at 35°C to determine standard rheological data, and the results are given in Table 2. None of the liquids according to the examples showed sedimentation after stirring:
De uomrørte satser ifølge eksemplene 5-9 ble valset ved 66°C i 16 timer, og ingen bunnavsetning kunne noteres for noen av satsene. Væsken ble omrørt i 25 minutter og undersøkt ved 31°C for å fastslå standard rheologiske data som i eksempel 5. Resultatene er gjengitt i den nedenstående tabell 3. Ingen av satsene i disse eksempler viste avsetning efter omrøring. The unstirred batches according to Examples 5-9 were rolled at 66°C for 16 hours, and no bottom deposit could be noted for any of the batches. The liquid was stirred for 25 minutes and examined at 31°C to determine standard rheological data as in Example 5. The results are shown in Table 3 below. None of the batches in these examples showed sedimentation after stirring.
Eksempler 10- 14 Examples 10-14
350 ml satser av væske bestående av 95,4 liter dieselolje, 3,6 kg emulgeringsmiddel Clnvermul" ) , 3,6 kg aminlignittfiltreringskontrollmiddel ('Duratone ") , 2,3 kg kalk, 31,8 liter kalsiumklorid i en konsentrasjon av 2,9 deler pr. liter og 145,1 kg bar ytt (Baroid ") ble blandet, omrørt i 15 minutter i et blandeapparat av typen Hamilton Beach og avkjølt til -2,2°C i et isbad.. En konsentrasjon av 1,74 kg/100 liter av gelmidler EM2HT/benzoat/bentonitt, BM2HT/p-fenolsulfonat/bentonitt og AM2HT/salicylat/bentonitt fremstilt som beskrevet i eksemplene 2-4 ble innblandet i 5 minutter ved lav skjærkraft med et blandeapparat av typen 350 ml batches of liquid consisting of 95.4 liters of diesel oil, 3.6 kg of emulsifier Clnvermul" ), 3.6 kg of amine lignite filtration control agent ('Duratone") , 2.3 kg of lime, 31.8 liters of calcium chloride in a concentration of 2, 9 parts per liters and 145.1 kg bar ytt (Baroid ") were mixed, stirred for 15 minutes in a Hamilton Beach type mixer and cooled to -2.2°C in an ice bath.. A concentration of 1.74 kg/100 liters of gelling agents EM2HT/benzoate/bentonite, BM2HT/p-phenolsulfonate/bentonite and AM2HT/salicylate/bentonite prepared as described in examples 2-4 were mixed for 5 minutes at low shear with a mixer of the type
Lightnin. Kaldprøvene i en viskosimeterskål ble anbragt på et viskosimeter av typen Fann 35 og omrørt ved 600 rpm mens temperaturen steg til 21°C. Satsene ble derefter anbragt i en på forhånd oppvarmet skål med varmekapper innstilt på en temperatur av 52°C og ble oppvarmet til 43°C. Den plastiske viskositet, flytegrensen og 10-s gel ble målt for hvert intervall av 2,78°C mellom -1,1°C og 21°C og ved hvert intervall av 5,56°C mellom 26°C og 43°C. Resultatene av målingene er gjengitt på Fig. 1. Lightning. The cold samples in a viscometer dish were placed on a Fann 35 viscometer and stirred at 600 rpm while the temperature rose to 21°C. The batches were then placed in a preheated dish with heating mantles set at a temperature of 52°C and were heated to 43°C. The plastic viscosity, yield strength and 10-s gel were measured for each 2.78°C interval between -1.1°C and 21°C and at each 5.56°C interval between 26°C and 43°C . The results of the measurements are shown in Fig. 1.
Satsene ifølge eksemplene 10-14 og ved en temperatur av 46°C ble omrørt i 15 minutter i et blandeapparat av typen Hamilton Beach og avkjølt til 27°C og undersøkt som i eksempel 5. Resultatene er gjengitt i den nedenstående tabell 4. The batches according to examples 10-14 and at a temperature of 46°C were stirred for 15 minutes in a mixer of the Hamilton Beach type and cooled to 27°C and examined as in example 5. The results are reproduced in table 4 below.
Eksempler 15- 19 Examples 15-19
Satser av væsker bestående av 65,2 liter dieselolje og 5,4 kg gelmiddelleirer fremstilt ifølge eksemplene 2, 3, 4 og 5 foruten 2M2HT/bentonitt og BM2HT/bentonitt som ble fremstilt uten anionaktive reaktanter, ble blandet og om-rørt i 5 minutter i et blandeapparat av typen Hamilton Beach ved lav hastighet. 65,2 liter dieselolje, 8,2 kg asfalt ( "Baroid Asphalti' ) og 0,12 kg barytt ("Baroid") ble blandet med de ovenfor fremstilte satser og omrørt i 15 minutter i et blandeapparat av typen Hamilton Beach. Batches of liquids consisting of 65.2 liters of diesel oil and 5.4 kg of gelling clays prepared according to Examples 2, 3, 4 and 5 except 2M 2 HT/bentonite and BM 2 HT/bentonite prepared without anionic reactants were mixed and stirred for 5 minutes. in a Hamilton Beach type mixer at low speed. 65.2 liters of diesel oil, 8.2 kg of asphalt ("Baroid Asphalti'") and 0.12 kg of barite ("Baroid") were mixed with the above prepared batches and stirred for 15 minutes in a Hamilton Beach type mixer.
350 ml prøver av satsene ifølge eksemplene 15-19 ble undersøkt for å fastslå de rheologiske egenskaper ved 34°C, på samme måte som i eksempel 5. Resultatene er gjengitt i den nedenstående tabell 5. 350 ml samples of the batches according to Examples 15-19 were examined to determine the rheological properties at 34°C, in the same way as in Example 5. The results are reproduced in Table 5 below.
350 ml prøver ifølge eksemplene 15-19 ble varmvalset i 16 timer ved 66°C. Efter at satsene var blitt avkjølt til 27°C, ble en eventuell avsetning av faste stoffer kontrollert før de rheologiske egenskaper ble målt som i eksempel 5 ved 34°C. Resultatene er gjengitt i den nedenstående tabell 6. 350 ml samples according to examples 15-19 were hot rolled for 16 hours at 66°C. After the batches had been cooled to 27°C, any deposition of solids was checked before the rheological properties were measured as in example 5 at 34°C. The results are reproduced in table 6 below.
Slamkake og filtrater ble rørt tilbake inn i de-respektive prøver, og gatsene ble aldret i 16 timer ved 177°C. Sludge cake and filtrates were stirred back into the respective samples, and the holes were aged for 16 hours at 177°C.
Hver sats ble avkjølt til 27°C og kontrollert for å notere eventuell avsetning av faste stoffer. Satsene ble omrørt i 5 minutter og undersøkt på samme måte som i eksempel 5. Resultatene er gjengitt i den nedenstående tabell 7. Each batch was cooled to 27°C and checked to note any settling of solids. The batches were stirred for 5 minutes and examined in the same way as in example 5. The results are reproduced in table 7 below.
Eksempler 20- 24 Examples 20-24
350 ml satser av væsker bestående av 109,7 liter dieselolje, 2,7 kg emulgeringsmiddel ("EZ mul"), 19,1 liter vann, 350 ml batches of liquids consisting of 109.7 liters of diesel oil, 2.7 kg of emulsifier ("EZ mul"), 19.1 liters of water,
102 kg barytt ("Baroid"), 10,9 kg kalsiumklorid og 2,7 kg gelmiddelleirer EM2HT/benzoat/bentonitt, BM2HT/p-fenolsul-fonat/bentonitt og AM2HT/salicylat/bentonitt fremstilt ifølge hhv. eksemplene 2-4 foruten 2M2HT/bentonitt og BM2HT/bentonitt beskrevet i eksempel 5 ble blandet og omrørt i 20 minutter i et blandeapparat av typen Hamilton Beach. 102 kg of barite ("Baroid"), 10.9 kg of calcium chloride and 2.7 kg of gelling clays EM2HT/benzoate/bentonite, BM2HT/p-phenolsulfonate/bentonite and AM2HT/salicylate/bentonite prepared according to respectively examples 2-4 in addition to 2M2HT/bentonite and BM2HT/bentonite described in example 5 were mixed and stirred for 20 minutes in a Hamilton Beach type mixer.
350 ml satser ifølge eksemplene 20-24 ble undersøkt 350 ml batches according to Examples 20-24 were examined
ved 31°C for å fastslå deres rheologiske egenskaper, på at 31°C to determine their rheological properties, at
samme måte som i eksempel 5. Resultatene er gjengitt i den nedenstående tabell 8. 350 ml prøver ifølge eksemplene 20-24 ble varmvalset i 16 timer ved 66°C. Efter avkjøling av satsene til 27°C ble eventuell avsetning av faste stoffer kontrollert før de rheologiske egenskaper ble målt som i eksempel 5 ved 29°C. Resultatene er gjengitt i den nedenstående tabell 9. the same way as in example 5. The results are reproduced in table 8 below. 350 ml samples according to examples 20-24 were hot-rolled for 16 hours at 66°C. After cooling the batches to 27°C, any deposition of solids was checked before the rheological properties were measured as in example 5 at 29°C. The results are reproduced in table 9 below.
Slamkake og filtrat ble rørt tilbake i de respektive prøver, og satsene ble aldret i 16 timer ved 177°C. Hver sats ble avkjølt til 27°c og kontrollert for eventuell avsetning av faste stoffer. Satsene ble omrørt i 5 minutter og undersøkt som i eksempel 5. HT-HP-filtrater ble utført for hver sats ved 177°C. Resultatene er gjengitt i den nedenstående tabell 10. Sludge cake and filtrate were stirred back into the respective samples, and the batches were aged for 16 hours at 177°C. Each batch was cooled to 27°c and checked for possible deposition of solids. Batches were stirred for 5 minutes and examined as in Example 5. HT-HP filtrates were run for each batch at 177°C. The results are reproduced in table 10 below.
Eksempler 25- 29 Examples 25-29
350 ml satser av en væske bestående av 100,2 liter dieselolje, 3,6 kg emulgeringsmiddel ("Invermul"), 17,5 liter vann, 147,4 kg barytt ("Baroid"), 3,6 kg filtreringshjelpe-middel ( "Duratone "),10 kg kalsiumklorid, 1,8 kg kalk og 4,1 kg gelmiddelleirer, EM2HT/benzoat/bentonitt, BM2HT/ p-fenolsulfonat/bentonitt og AM2HT/salicylat/bentonitt fremstilt ifølge hhv. eksemplene 2-4, kommersielle leirer 2M2HT/bentonitt, BM2HT/foentonittbeskrevet i eksempel 5 ovenfor og en ytterligere kommersiell leire. 350 ml batches of a liquid consisting of 100.2 liters of diesel oil, 3.6 kg of emulsifier ("Invermul"), 17.5 liters of water, 147.4 kg of barite ("Baroid"), 3.6 kg of filter aid ( "Duratone"), 10 kg of calcium chloride, 1.8 kg of lime and 4.1 kg of gelling clays, EM2HT/benzoate/bentonite, BM2HT/p-phenolsulfonate/bentonite and AM2HT/salicylate/bentonite prepared according to respectively examples 2-4, commercial clays 2M2HT/bentonite, BM2HT/foentonite described in example 5 above and a further commercial clay.
350 ml prøver ifølge eksemplene 25-29 ble undersøkt 350 ml samples according to examples 25-29 were examined
ved 33°C for å fastslå de rheologiske egenskaper, på samme måte som i eksempel 5. Resultatene er gjengitt i den nedenstående tabell 11. at 33°C to determine the rheological properties, in the same way as in example 5. The results are reproduced in the table 11 below.
Satsene ble aldret i 16 timer ved 149°C, avkjølt til 27°C og kontrollert for eventuell avsetning av faste stoffer. Satsene ble omrørt i 10 minutter og undersøkt som i eksempel 5 ved 32°C. Resultatene er gjengitt i den nedenstående tabell 12. The batches were aged for 16 hours at 149°C, cooled to 27°C and checked for any solids deposition. The batches were stirred for 10 minutes and examined as in example 5 at 32°C. The results are reproduced in table 12 below.
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US3929849A (en) * | 1973-10-01 | 1975-12-30 | Exxon Research Engineering Co | Tetraalkyl phosphonium aluminosilicates |
CA1105348A (en) * | 1977-11-01 | 1981-07-21 | Claude M. Finlayson | Oil base fluids with organophilic clays having enhanced dispersibility |
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1981
- 1981-11-16 CA CA000390181A patent/CA1160033A/en not_active Expired
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1982
- 1982-07-02 IN IN498/DEL/82A patent/IN158427B/en unknown
Also Published As
Publication number | Publication date |
---|---|
AU558370B2 (en) | 1987-01-29 |
IT1194110B (en) | 1988-09-14 |
FR2514662B1 (en) | 1987-01-16 |
FR2514662A1 (en) | 1983-04-22 |
EG15459A (en) | 1986-03-31 |
BR8107426A (en) | 1983-05-24 |
SE8106796L (en) | 1983-04-20 |
JPS5876484A (en) | 1983-05-09 |
IN158427B (en) | 1986-11-15 |
CA1160033A (en) | 1984-01-10 |
IT8125111A0 (en) | 1981-11-16 |
AU7751981A (en) | 1983-04-28 |
NO813869L (en) | 1983-04-20 |
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