WO2016025137A1 - High density aqueous well fluids - Google Patents
High density aqueous well fluids Download PDFInfo
- Publication number
- WO2016025137A1 WO2016025137A1 PCT/US2015/041662 US2015041662W WO2016025137A1 WO 2016025137 A1 WO2016025137 A1 WO 2016025137A1 US 2015041662 W US2015041662 W US 2015041662W WO 2016025137 A1 WO2016025137 A1 WO 2016025137A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bromide
- inorganic
- salt
- manganese
- water
- Prior art date
Links
- 239000012530 fluid Substances 0.000 title description 25
- 229910001503 inorganic bromide Inorganic materials 0.000 claims abstract description 173
- 150000003842 bromide salts Chemical class 0.000 claims abstract description 169
- 239000000203 mixture Substances 0.000 claims abstract description 154
- 229910001622 calcium bromide Inorganic materials 0.000 claims abstract description 151
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims abstract description 149
- 150000003839 salts Chemical class 0.000 claims abstract description 101
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims abstract description 91
- 239000012267 brine Substances 0.000 claims abstract description 69
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 65
- 229910021568 Manganese(II) bromide Inorganic materials 0.000 claims abstract description 64
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000002425 crystallisation Methods 0.000 claims abstract description 43
- 230000008025 crystallization Effects 0.000 claims abstract description 43
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 claims abstract description 40
- JKNHZOAONLKYQL-UHFFFAOYSA-K tribromoindigane Chemical compound Br[In](Br)Br JKNHZOAONLKYQL-UHFFFAOYSA-K 0.000 claims description 78
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 72
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 claims description 58
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 56
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 claims description 51
- JBVOSZYUSFDYIN-UHFFFAOYSA-N dimethyl cyclopropane-1,2-dicarboxylate Chemical compound COC(=O)C1CC1C(=O)OC JBVOSZYUSFDYIN-UHFFFAOYSA-N 0.000 claims description 45
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 42
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 33
- 150000004679 hydroxides Chemical class 0.000 claims description 32
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 30
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 24
- 229910052783 alkali metal Inorganic materials 0.000 claims description 23
- 150000001340 alkali metals Chemical class 0.000 claims description 23
- 229910001853 inorganic hydroxide Inorganic materials 0.000 claims description 23
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 16
- 235000019253 formic acid Nutrition 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical compound [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- RJMMFJHMVBOLGY-UHFFFAOYSA-N indium(3+) Chemical compound [In+3] RJMMFJHMVBOLGY-UHFFFAOYSA-N 0.000 claims description 6
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical group [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- JDIBGQFKXXXXPN-UHFFFAOYSA-N bismuth(3+) Chemical compound [Bi+3] JDIBGQFKXXXXPN-UHFFFAOYSA-N 0.000 claims description 5
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 4
- MSBGPEACXKBQSX-UHFFFAOYSA-N (4-fluorophenyl) carbonochloridate Chemical compound FC1=CC=C(OC(Cl)=O)C=C1 MSBGPEACXKBQSX-UHFFFAOYSA-N 0.000 claims description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 3
- 229910021509 tin(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 description 77
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000000306 component Substances 0.000 description 19
- 239000002244 precipitate Substances 0.000 description 19
- 238000002156 mixing Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 11
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- -1 bromide anions Chemical class 0.000 description 3
- 150000001768 cations Chemical class 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
- 239000013078 crystal Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001509 metal bromide Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001620 barium bromide Inorganic materials 0.000 description 1
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical group 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910001625 strontium bromide Inorganic materials 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/05—Aqueous well-drilling compositions containing inorganic compounds only, e.g. mixtures of clay and salt
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
Definitions
- This invention relates to high density aqueous brines suitable for use as well fluids.
- aqueous brine fluids like calcium bromide, which can have densities up to about 14.2 pounds per gallon (1.70 kg/L), are widely used in oilfield production as clear completion fluids, drilling fluids, packer fluids, and so forth.
- downhole pressures can reach 30,000 psi (2.1xl0 8 Pa).
- Such high pressures occur downhole at least in the Gulf of Mexico, and temperatures at the mud line in the Gulf of Mexico can reach 40°F (4.4°C).
- each 10,000 pounds per square inch (6.9xl0 7 Pa) increase in pressure can increase the crystallization temperature of an aqueous brine by about ten Fahrenheit degrees (about 5.6 Celsius degrees).
- Typical aqueous brine fluids include calcium bromide having densities up to about 14.2 ppg (1.70 kg/L).
- a calcium bromide aqueous brine of about 14.2 ppg (1.70 kg/L) density has a true crystallization temperature of 10°F (-12.2°C).
- Calcium bromide aqueous brines having densities as high as 15 ppg (1.8 kg/L) can be made; however, these solutions have a true crystallization temperature of about 61°F (16.1°C).
- Zinc-containing calcium bromide aqueous brines of high density e.g., about 14.5 pounds per gallon (1.74 kg/L) or greater, are easily obtained by blending enough zinc bromide into the calcium bromide aqueous brine to reach the desired density value.
- Zinc- containing calcium bromide aqueous brines have true crystallization temperatures that are usually about 20°F (-6.7°C) or lower, making these zinc-containing brines more suitable for downhole use.
- inclusion of zinc necessitates increased reporting to government agencies for environmental reasons, resulting in more costly environmental mitigation measures.
- zinc is regulated as a Priority Pollutant by the United States Environmental Protection Agency (EPA).
- EPA United States Environmental Protection Agency
- This invention provides aqueous brines of high density and low crystallization temperature that are zinc-free. It has been discovered, for example, that a high density, zinc-free aqueous brine can be prepared from a combination of water and one or more inorganic bromide salts such as calcium bromide, manganese bromide (MnBr 2 ) tin bromide (SnBr 2 or SnBr 4 ), bismuth bromide, and/or indium bromide; calcium bromide is used in combination with one or more other water-soluble inorganic salts, preferably selected from an inorganic bromide salt, manganese(II) nitrate, and a water-soluble polytungstate salt; lithium bromide is used in combination with an alkali metal polytungstate salt; bismuth(III) bromide is used in combination with one or more other water-soluble inorganic salts, preferably selected from an inorganic bromide salt; when lithium bromide is present,
- Such brines can exhibit densities of about 15.0 ppg (1.78 kg/L) or greater, and have crystallization temperatures of about 20°F (-6.7°C) or less, often about 10°F (-12.2°C) or less.
- These brines are suitable for use as wellbore fluids, such as completion fluids, especially clear completion fluids, drilling fluids, packer fluids, workover fluids, and other fluids that employ aqueous brines, particularly aqueous brines of high density.
- the aqueous brines of this invention are well suited for offshore completion activities involving high pressure reservoirs, such as oil and gas fields located in the Gulf of Mexico.
- An embodiment of this invention is a zinc-free aqueous brine composition.
- the composition has a density of about 14.3 pounds per gallon (1.71 kg/L) or more, and a true crystallization temperature of about 20°F (-6.7°C) or less, preferably about 10°F (-12.2°C) or less, and comprises water and one or more inorganic bromide salts, with the proviso that when calcium bromide is present, one or more other water-soluble inorganic salts is also present, preferably selected from an inorganic bromide salt, manganese(II) nitrate, and a water-soluble polytungstate salt; with the proviso that when bismuth(III) bromide is present, one or more other water-soluble inorganic salts is also present, preferably selected from an inorganic bromide salt, with the proviso that when lithium bromide is present, calcium bromide is absent, and with the proviso that for true crystallization temperatures of about 10°F or less
- zinc-free means that except for adventitious impurities, neither zinc nor zinc compounds are present in, or introduced into, the compositions or processes of this invention. Generally, there is about 25 ppm or less of zinc present in the aqueous brines of this invention.
- ppm means parts per million (wt/wt), as used throughout this document, unless specifically stated otherwise herein. Throughout this document, both "ppg” and “lb/gal” are abbreviations for pounds per gallon.
- TCT true crystallization temperature (or true crystallization point) as used throughout this document.
- True crystallization temperature is the temperature at which precipitate begins to form in the absence of supercooling. A method for determining true crystallization temperature is described hereinbelow.
- Solutions comprising one or more inorganic bromide salts and manganese(II) nitrate or a water-soluble polytungstate are aqueous brines of the present invention.
- compositions of the invention can be used as clear completion fluids, precipitates and/or cloudiness in the aqueous brines of the invention are undesirable.
- the aqueous brines of the invention have little or no precipitate formation over time (e.g. , about one week) at ambient temperature and pressure (e.g. , 17 to 25°C and 14 to 15 psi) or at elevated temperature (e.g. , about 60°C) and ambient pressure.
- compositions of the invention are aqueous brine solutions comprising one or more inorganic bromide salts other than zinc bromide.
- inorganic bromide salts other than zinc bromide.
- the species in the compositions may be complexed with water, or in some other form.
- the other water-soluble inorganic salts which are comprised in the aqueous brine solutions of the invention that are referred to as salts or their respective cations and/or anions may be complexed with water, or in some other form.
- the inorganic bromide salts are selected from calcium bromide, manganese(II) bromide, tin(II) bromide, tin(IV) bromide, bismuth(III) bromide, indium(III) bromide, and mixtures of any two or more of these; when calcium bromide is used, one or more other water-soluble inorganic salts is also used, and preferably is selected from an inorganic bromide salt, manganese(II) nitrate, and a water- soluble polytungstate salt; when bismuth(III) bromide is used, one or more other water- soluble inorganic salts is also used, and preferably is selected from an inorganic bromide salt.
- Manganese(II) bromide is preferably used in combination with one or more other water-soluble inorganic salts, especially when a brine with a true crystallization temperature of about 10°F (-12.2°C) or less is needed; in preferred embodiments, the other inorganic salt is preferably selected from an inorganic bromide salt, manganese(II) nitrate, and a water-soluble polytungstate salt, more preferably an inorganic bromide, which inorganic bromide is preferably calcium bromide or a combination of calcium bromide and one or more other inorganic bromide salts. In some embodiments, the inorganic bromide salt is lithium bromide in combination with an alkali metal polytungstate salt.
- Preferred inorganic bromide salts when only one bromide salt is present include tin(IV) bromide and indium(III) bromide, especially tin(IV) bromide.
- tin(IV) bromide and indium(III) bromide especially tin(IV) bromide.
- two bromide salts are used, they are preferably a combination of calcium bromide and manganese(II) bromide; when three bromide salts are used, they are preferably a combination of calcium bromide, manganese(II) bromide and tin(IV) bromide, or a combination of calcium bromide, manganese(II) bromide, and bismuth(III) bromide.
- the inorganic bromide salt is manganese(II) bromide, tin(II) bromide, tin(IV) bromide, indium(III) bromide, or a mixture of any two or more of these.
- the inorganic bromide salt is a combination of calcium bromide and one or more inorganic bromide salts selected from manganese(II) bromide, tin(II) bromide, tin(IV) bromide, bismuth(III) bromide, indium(III) bromide, or a mixture of any two or more of these.
- the inorganic bromide salt is a combination of bismuth(III) bromide and one or more inorganic bromide salts selected from manganese(II) bromide, tin(II) bromide, tin(IV) bromide, indium(III) bromide, or a mixture of any two or more of these.
- one inorganic bromide salt is present, and the inorganic bromide salt is tin(IV) bromide or indium(III) bromide.
- the other water-soluble inorganic salt is a water-soluble polytungstate salt
- it can be an alkali metal polytungstate, an alkaline earth metal polytungstate, manganese polytungstate, and the like.
- Alkali metal polytungstates include lithium polytungstate, lithium metatungstate, sodium polytungstate, sodium metatungstate, potassium polytungstate, potassium metatungstate, and the like; preferred alkali metal polytungstates include sodium metatungstate and potassium metatungstate.
- Alkaline earth metal polytungstates include calcium polytungstate, magnesium polytungstate, and strontium polytungstate; preferred alkaline earth polytungstates include calcium polytungstate.
- metalatungstate often refers to a hydrated form of a polytungstate salt.
- the alkali metal polytungstate salts include lithium polytungstate, lithium metatungstate, sodium polytungstate, sodium metatungstate, potassium polytungstate, potassium metatungstate, and the like; preferred alkali metal polytungstates include lithium metatungstate and sodium metatungstate.
- the total amount of inorganic bromide salt(s) in the aqueous brine is typically in the range of about 40 wt to about 75 wt , relative to the total weight of the composition.
- Preferred total amounts of inorganic bromide salt(s) are from about 45 wt to about 75 wt , relative to the total weight of the composition.
- the total amount of inorganic bromide salt(s) in the aqueous brine is preferably in the range of about 45 wt to about 65 wt , more preferably about 55 wt to about 65 wt , relative to the total weight of the composition, especially when calcium bromide and one other inorganic bromide salt are used, and the other inorganic bromide salt is selected from tin(II) bromide, tin(IV) bromide, bismuth(III) bromide, and indium(III) bromide.
- the total amount of inorganic bromide salt(s) in the aqueous brine is preferably in the range of about 55 to about 70 wt , relative to the total weight of the composition, especially when the inorganic bromide salts are calcium bromide and two other inorganic bromide salts, which other inorganic bromide salts are a combination of manganese(II) bromide and one other metal bromide selected from tin(II) bromide, tin(IV) bromide, bismuth(III) bromide, and indium(III) bromide.
- the total amount of inorganic bromide salt(s) in the aqueous brine is typically in the range of about 15 wt to about 60 wt , preferably about 20 wt to about 55 wt , more preferably about 25 wt to about 55 wt , relative to the total weight of the composition.
- the total amount of the other water-soluble inorganic salt(s) varies, depending on the identity of the inorganic salt.
- the total amount in the aqueous brine is usually in the range of about 5 wt to about 75 wt , sometimes preferably about 35 wt to about 70 wt , sometimes preferably about 10 wt to about 50 wt , relative to the total weight of the composition; for water-soluble polytungstate salts, the total amount in the aqueous brine is typically in the range of about 5 wt to about 40 wt , preferably about 10 wt to about 35 wt , relative to the total weight of the composition.
- the total amount of inorganic salts in an aqueous brine comprised of one or more inorganic bromide salts and one or more other water-soluble inorganic salts is in the range of about 60 wt to about 85 wt , sometimes preferably in the range of about 65 wt to about 85 wt , relative to the total weight of the composition when the other water-soluble inorganic salt is manganese(II) nitrate.
- the total amount of inorganic salts in an aqueous brine comprised of one or more inorganic bromide salts and one or more other water-soluble inorganic salts is in the range of about 50 wt to about 75 wt , preferably in the range of about 55 wt to about 70 wt , relative to the total weight of the composition.
- compositions of the invention have densities of about 14.3 pounds per gallon (1.71 kg/L) or more.
- the compositions Preferably, the compositions have densities of about 14.6 ppg (1.75 kg/L) or more.
- the compositions preferably have densities of about 14.8 ppg (1.77 kg/L) or more, or preferably about 15.0 ppg (1.80 kg/L) or more, or more preferably about 15.1 ppg (1.81 kg/L) or more.
- the compositions preferably have densities of about 16.0 ppg (1.92 kg/L) or more.
- Density ranges for the compositions of this invention are preferably about 14.3 ppg (1.71 kg/L) to about 19.0 ppg (2.28 kg/L), more preferably about 14.6 ppg (1.75 kg/L) to about 18.0 ppg (2.16 kg/L).
- preferred densities are about 14.8 ppg (1.77 kg/L) to about 16.0 ppg (1.92 kg/L),more preferably about 15.0 ppg (1.80 kg/L) to about 16.0 ppg (1.92 kg/L), and still more preferably about 15.1 ppg (1.81 kg/L) to about 15.6 ppg (1.87 kg/L).
- preferred densities are about 14.6 ppg (1.75 kg/L) to about 15.0 ppg (1.80 kg/L), more preferably about 14.6 to about 14.8 ppg (1.77 kg/L). In still other embodiments, preferred densities are about 15.0 ppg (1.80 kg/L) to about 18.0 ppg (2.16 kg/L), more preferably about 15.5 ppg (1.86 kg/L) to about 17.75 ppg (2.13 kg/L).
- preferred densities are about 16.0 ppg (1.92 kg/L) to about 17.5 ppg (2.10 kg/L), more preferably about 16.2 ppg (1.94 kg/L) to about 17.2 ppg (2.06 kg/L).
- preferred densities are about 14.5 ppg (1.74 kg/L) to about 16.0 ppg (1.92 kg/L).
- preferred densities are about 14.5 ppg (1.74 kg/L) to about 17.5 ppg (2.10 kg/L), more preferably about 14.5 ppg (1.74 kg/L) to about 16.5 ppg (1.98 kg/L), especially when the inorganic bromide salt is calcium bromide or manganese(II) bromide and the other water-soluble inorganic salt is a water-soluble polytungstate salt, or when the inorganic bromide salt is lithium bromide in combination with an alkali metal polytungstate salt.
- the true crystallization temperatures are generally about 20°F (-6.7°C) or less, preferably about 10°F (-12.2°C) or less, more preferably about 8°F (-13.3°C) or less, and still more preferably about 7.5°F (-13.6°C) or less.
- Aqueous brine compositions of the invention normally have pH values of about -2 or more, and can range from about -2 to about 8.
- Preferred pH values are in the range of about 0 to about 7; more preferred are pH values in the range of about 1 to about 6; still more preferred are pH values in the range of about 1.5 to about 5, especially about 2.5 to about 5. Even more preferred are pH values in the range of about 3 to about 4.
- Optional additives can include, for example, corrosion inhibitors, lubricants, pH control additives, surfactants, and/or solvents. Glycerol and formic acid are preferred optional additives.
- Glycerol and formic acid are preferred optional additives.
- inorganic bromide salts In some preferred zinc-free aqueous brine compositions of the invention, only water, inorganic bromide salts, one or more other water-soluble inorganic salts, and species derived from these components are present in the composition; in some of these preferred embodiments, one of the inorganic bromide salts is calcium bromide.
- the other water-soluble inorganic salts are selected from manganese(II) nitrate, and a water-soluble polytungstate salt, and more preferably, one of the inorganic bromide salts is calcium bromide.
- compositions of this invention include zinc-free aqueous brines which comprise water; calcium bromide; and one or more other inorganic bromide salts, preferably selected from manganese(II) bromide, tin(II) bromide, tin(IV) bromide, bismuth(III) bromide, indium(III) bromide, and mixtures of any two or more of these; wherein the composition has a density of about 14.3 ppg (1.71 kg/L) or more, preferably about 14.6 ppg (1.75 kg/L) or more, more preferably about 15.0 ppg (1.80 kg/L) or more; and a true crystallization temperature of about 20°F (-6.7°C) or less, preferably about 10°F (-12.2°C) or less, more preferably about 8°F (-13.3°C) or less.
- the inorganic bromide salt(s) other than calcium bromide is preferably in an amount of about 3.0 wt to about 40 wt , relative to the total weight of the composition; preferably, these calcium bromide-containing compositions have a pH in the range of about 0 to about 8, more preferably about 1 to 7.
- compositions of this invention include zinc-free aqueous brines which comprise water and one inorganic bromide salt selected from tin(IV) bromide and indium(III) bromide; more preferably tin(IV) bromide; wherein the composition has a density of about 15.0 ppg (1.80 kg/L) or more, preferably about 16.0 ppg (1.92 kg/L) or more, more preferably about 18.0 ppg (2.16 kg/L) or more.
- the inorganic bromide salts are calcium bromide and manganese(II) bromide
- the composition has a density of about 14.6 ppg (1.75 kg/L) or more and a true crystallization temperature at atmospheric pressure of about 20°F (-6.7°C) or less, preferably about 10°F (-12.2°C) or less.
- Particularly preferred are compositions containing calcium bromide and manganese(II) bromide which have densities of about 15 lb/gal (1.8 kg/L) or more, and true crystallization temperatures at atmospheric pressure of about 8°F (-13.3°C) or less.
- these compositions containing calcium bromide and manganese(II) bromide have pH values in the range of about 2.5 to 5, more preferably about 3 to 4.
- the inorganic bromide salts are calcium bromide and manganese(II) bromide in combination with another inorganic bromide salt selected from tin(IV) bromide, tin(II) bromide, bismuth(III) bromide, and indium(III) bromide.
- the inorganic bromide salts are calcium bromide, manganese(II) bromide, and tin(IV) bromide, and the composition has a density of about 15.0 ppg (1.80 kg/L) or more.
- Particularly preferred compositions containing calcium bromide, manganese(II) bromide, and tin(IV) bromide as the inorganic bromide salts have densities of about 16.0 ppg (1.92 kg/L) or more, more preferably densities of about 16.5 ppg (1.98 kg/L) or more.
- the inorganic bromide salts are calcium bromide, manganese(II) bromide, and bismuth(III) bromide, and the composition has a density of about 16.0 ppg (1.92 kg/L) or more.
- Particularly preferred compositions containing calcium bromide, manganese(II) bromide, and bismuth(III) bromide as the inorganic bromide salts have densities of about 16.3 ppg (1.95 kg/L) or more.
- the inorganic bromide salt is calcium bromide, and manganese(II) nitrate is present; preferably, the composition has a density of about 14.5 ppg (1.74 kg/L) or more, more preferably about 14.8 ppg (1.77 kg/L) or more.
- the inorganic bromide salt is calcium bromide or manganese(II) bromide, and a water-soluble polytungstate, preferably an alkali metal polytungstate, more preferably sodium metatungstate, is present; more preferably, the composition has a density of about 14.5 ppg (1.74 kg/L) or more, more preferably about 14.8 ppg (1.77 kg/L) or more.
- the inorganic bromide salt is lithium bromide in combination with an alkali metal polytungstate salt; more preferably the alkali metal polytungstate salt is lithium metatungstate or sodium metatungstate; more preferably, the composition has a density of about 14.5 ppg (1.74 kg/L) or more, more preferably about 14.8 ppg (1.77 kg/L) or more.
- Zinc-free aqueous brines having a density of about 14.3 pounds per gallon (1.71 kg/L) or more and a true crystallization temperature of about 20°F (-6.7°C) or less are formed by processes which comprise combining, in any order, components comprising water and one or more inorganic bromide salts, with the proviso that when calcium bromide is present, one or more other water-soluble inorganic salts is also present, and preferably is selected from an inorganic bromide salt, manganese(II) nitrate, and a water- soluble polytungstate salt; with the proviso that when lithium bromide is present, calcium bromide is absent; with the proviso that when bismuth(III) bromide is present, one or more other water-soluble inorganic salts are also present; and with the proviso that, for a true crystallization temperature of about 10°F or less, when manganese(II) bromide is present, one or more other water
- the inorganic bromide salt(s) include calcium bromide, manganese(II) bromide, tin(II) bromide, tin(IV) bromide, bismuth(III) bromide, indium(III) bromide, and mixtures of any two or more of these.
- calcium bromide one or more other water- soluble inorganic salts, preferably selected from an inorganic bromide salt, manganese(II) nitrate, and a water-soluble polytungstate salt
- bismuth(III) bromide one or more other water-soluble inorganic salts, preferably selected from an inorganic bromide salt, is also used.
- an alkali metal polytungstate salt is also used.
- Manganese(II) bromide is preferably used in combination with one or more other water-soluble inorganic salts, especially when a brine with a true crystallization temperature of about 10°F (-12.2°C) or less is needed; in preferred embodiments, the other inorganic salt is an inorganic bromide, manganese(II) nitrate, or a water-soluble polytungstate salt; the inorganic bromide is preferably calcium bromide or a combination of calcium bromide and one or more other inorganic bromide salts.
- one inorganic bromide salt is preferably tin(IV) bromide or indium(III) bromide, more preferably, tin(IV) bromide.
- Manganese(II) bromide is preferred as an inorganic bromide salt to use with calcium bromide, especially when calcium bromide and one other bromide salt are present; when two bromide salts are used with calcium bromide, they are preferably a combination of manganese(II) bromide and tin(IV) bromide, or a combination of manganese(II) bromide and bismuth(III) bromide.
- the combining of the water and inorganic bromide salt(s), and, when used, other water-soluble inorganic salts can be conducted in any manner used to mix inorganic salts and water. Normally and preferably, concentrated solutions of the inorganic salts can be mixed with addition or removal of water to provide the composition desired. Alternatively, the inorganic bromide salt(s) are added to the water. When there are two or more inorganic bromide salts, the inorganic bromide salts can be mixed with a portion of water before being combined with each other and, if needed, more water.
- each feed may be entirely coextensive in time, and each feed may be interrupted at one or more points during the cofeeding.
- Another preferred way of operating when there are two or more inorganic bromide salts is to introduce one or more of the inorganic bromide salt(s) as a solid into a preformed aqueous solution of the other inorganic bromide salts(s). A combination of methods can be used as desired.
- One or more of the inorganic bromide salts can be formed during the process. Formation of an inorganic bromide salt during the process can be used to form a portion of, or all of, the inorganic bromide salt. When an inorganic bromide salt is formed during the process, it can be formed in water before some or all of any other inorganic bromide(s) are introduced, or, preferably, in an aqueous solution of the other inorganic bromide(s).
- an inorganic bromide salt can be formed during the process in various ways.
- an inorganic bromide salt can be formed from the metal in elemental form and elemental bromine (Br 2 ), especially where the metal is calcium, manganese, tin, bismuth, and/or indium.
- manganese metal and elemental bromine can be used to form manganese(II) bromide.
- an inorganic bromide salt can be formed from an inorganic oxide and/or hydroxide and a bromide source which is hydrogen bromide and/or elemental bromine.
- the inorganic bromide salt is formed from (i) an inorganic oxide and/or hydroxide and (ii) hydrogen bromide and/or bromine.
- Inorganic oxides and/or hydroxides that can be used to form an inorganic bromide salt during the process include one or more of calcium oxide and/or hydroxide, manganese oxides and/or hydroxides, tin(II) oxide and/or hydroxide, tin(IV) oxide and/or hydroxide, bismuth(III) oxide and/or hydroxide, indium(III) oxide and/or hydroxide, or mixtures of any two or more of the foregoing.
- Preferred inorganic oxides and hydroxides include one or more manganese oxides and/or hydroxides, tin(IV) oxide and/or hydroxide, and bismuth(III) oxide and/or hydroxide.
- the bromide source for forming an inorganic bromide during the process is hydrogen bromide, bromine, or a mixture thereof.
- the bromide source is hydrogen bromide or a mixture of hydrogen bromide and bromine; more preferred is a mixture of hydrogen bromide and bromine.
- the hydrogen bromide and bromine can be in any desired proportions from 100% hydrogen bromide to 100% Br 2 , or at any relative proportion therebetween.
- bromine (elemental bromine, Br 2 )
- a reducing agent is also present, and is typically methanol, ethanol, formic acid, hydrazine, and the like.
- the lithium bromide can be made by any of the methods described above, including from lithium metal and elemental bromine, and from lithium oxide and/or hydroxide and a bromide source (typically hydrogen bromide or elemental bromine).
- the inorganic bromide salt is manganese(II) bromide, tin(II) bromide, tin(IV) bromide, indium(III) bromide, or a mixture of any two or more of these.
- the inorganic bromide salt is a combination of calcium bromide and manganese(II) bromide, tin(II) bromide, tin(IV) bromide, bismuth(III) bromide, indium(III) bromide, or a mixture of any two or more of these.
- a combination of bismuth(III) bromide and manganese(II) bromide, tin(II) bromide, tin(IV) bromide, indium(III) bromide, or a mixture of any two or more of these is used.
- only one inorganic bromide salt is used, and the inorganic bromide salt is tin(IV) bromide or indium(III) bromide.
- the inorganic bromide is typically in an amount in the range of about 40 wt% to about 75 wt%, preferably about 45 wt% to about 75 wt%, relative to the total weight of the aqueous brine composition being formed.
- this range refers to the combined weight of all of the inorganic bromide salts.
- preferred amounts of inorganic bromide salts other than the calcium bromide in the aqueous brine are from about 5 wt% to about 35 wt%; more preferably about 6 wt% to about 30 wt%, relative to the total weight of the composition.
- the inorganic bromide is typically about 15 wt to about 60 wt , preferably about 20 wt to about 55 wt , more preferably about 25 wt to about 55 wt , relative to the total weight of the composition.
- the manganese(II) nitrate is generally in the range of about 5 wt to about 75 wt , sometimes preferably about 35 wt to about 70 wt , sometimes preferably about 10 wt to about 50 wt , relative to the total weight of the composition.
- the other water-soluble inorganic salt is a water-soluble polytungstate salt
- the polytungstate salt is usually in the range of about 5 wt to about 40 wt , preferably about 10 wt to about 35 wt , relative to the total weight of the composition.
- the amount of that inorganic bromide salt is calculated as if the inorganic bromide salt had been added. Amounts of inorganic bromide salt will vary, depending to some extent on the amount(s) of other inorganic bromide(s), because less inorganic bromide salt is needed to reach a particular density value as the amount of other inorganic bromide salt(s) increases.
- the amount of inorganic bromide salt in the aqueous brine is preferably in the range of about 45 wt to about 65 wt , more preferably about 55 wt to about 65 wt , relative to the total weight of the composition, especially when calcium bromide and one other inorganic bromide salt are used, and the other inorganic bromide salt is selected from tin(II) bromide, tin(IV) bromide, bismuth(III) bromide, and indium(III) bromide.
- the amount of inorganic bromide salt in the aqueous brine is preferably in the range of about 55 to about 70 wt , relative to the total weight of the composition, especially when the inorganic bromide salts are calcium bromide and two other inorganic bromide salts, which are a combination of manganese(II) bromide and another metal bromide selected from tin(II) bromide, tin(IV) bromide, bismuth(III) bromide, and indium(III) bromide.
- the amount of water and/or the inorganic bromide salt(s) and/or other water- soluble inorganic salt(s) used to form the aqueous brines of the invention can be adjusted to reach the desired density. Removal of water, for example by heating and/or applying a vacuum, can be employed to reach the desired density for the zinc-free aqueous brine composition.
- the zinc-free aqueous brine can be heated during combination of the components and/or after the components are combined, to ensure dissolution of the components.
- the mixture being formed during the process and/or the aqueous brine formed by the process is heated at a temperature of about 40°C or above to form a heated solution.
- Elevated temperatures can increase the rate of dissolution of the inorganic bromide salt(s).
- Such elevated temperatures for heating the aqueous brine are typically in the range of about 40°C up to the boiling point of the mixture, preferably about 45°C to about 100°C, more preferably about 50°C to about 95°C, and still more preferably about 60°C to about 95°C.
- increased pressure typically about 20 psi to about 40 psi (1.4xl0 5 to 2.77xl0 5 Pa)
- ambient temperatures typically about 15°C to about 25°C, often about 17°C to about 23°C
- the inorganic bromide salt(s) usually remain dissolved.
- the pH of the zinc-free aqueous brine can be adjusted by adding an acid or a base as needed.
- Suitable acids include mineral acids and water-soluble organic acids; suitable bases are usually inorganic oxides and/or hydroxides.
- a precipitate may form; after filtration, a clear aqueous brine is obtained.
- suitable inorganic oxides and hydroxides which include oxides and hydroxides of manganese(II), tin(II), tin(IV), bismuth(III), indium(III), alkali metals including lithium, sodium, and potassium, alkaline earth metals including calcium and magnesium, and mixtures of any of these oxides and/or hydroxides, may be used.
- Preferred inorganic oxides and hydroxides include those of manganese, tin, calcium, and sodium.
- the inorganic oxide(s) and/or hydroxide(s) has one or more of the same cations already present in the aqueous brine.
- a small amount of precipitate forms when an inorganic oxide and/or hydroxide is used to increase the pH. Once the precipitate has been removed, e.g. , by filtration, additional precipitate formation usually does not occur.
- Acids suitable for pH adjustment include mineral acids and organic acids that are water-soluble.
- Suitable mineral acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, sulfuric acid, phosphoric acid, and the like.
- Suitable organic acids include formic acid, tartaric acid, citric acid, gluconic acid, lactic acid, malic acid, maleic acid, malonic acid, oxalic acid, and the like. Mixtures of any two or more acids can be employed if desired.
- Hydrogen bromide is a preferred acid, and can be used in gaseous form, or, preferably, as an aqueous solution.
- Any optional additives that are included in the aqueous brines can be introduced in any of the ways that the inorganic bromide salt(s) are introduced, or in any other convenient manner.
- aqueous brines having a density of about 15.0 ppg (1.80 kg/L) or greater often form a precipitate.
- Stabilization of these dense aqueous brines can be achieved by adjusting the pH of the aqueous brine. Adjustment of the pH value is accomplished by adding an inorganic hydroxide and/or oxide and/or by adding an acid, preferably hydrogen bromide, usually to a value in the range of about 1 to about 7, more preferably about 1 to about 6; still more preferably about 2.5 to about 5.
- aqueous brine compositions of the invention which have a pH of about 3.5 or higher, and in which the inorganic bromide salts are calcium bromide and manganese(II) bromide.
- the pH can be adjusted as described above.
- the presence of glycerol and/or formic acid in the composition is preferred.
- Glycerol can be introduced at any point during the process of the invention by any convenient method for combining the glycerol and/or formic acid with the components of the process.
- a preferred method for inclusion of glycerol and/or formic acid is by adding glycerol and/or formic acid to the aqueous brine.
- the amount of glycerol is preferably about 3 wt to about 15 wt , more preferably about 5 wt to about 10 wt , relative to the total weight of the composition.
- the amount of formic acid, when present, is typically about 500 ppm to about 5000 ppm, preferably about 750 ppm to about 3000 ppm, more preferably about 1000 ppm to about 2500 ppm, relative to the total weight of the composition. It has been observed that the presence of glycerol in manganese-containing aqueous brines of the invention may prevent or minimize precipitation in the aqueous brines, especially at pH values of about 3.5 or above.
- only water, one or more inorganic bromide salts, and one or more other water-soluble inorganic salts are combined to form the zinc-free aqueous brines of this invention.
- the other water-soluble inorganic salts are selected from manganese(II) nitrate and a water-soluble polytungstate salt.
- Preferred processes of this invention comprise combining, in any order, components comprising water and one or more inorganic bromide salts preferably selected from the group consisting of calcium bromide, manganese(II) bromide, tin(II) bromide, tin(IV) bromide, bismuth(III) bromide, indium(III) bromide, and mixtures of any two or more of these; when calcium bromide is present, one or more other water-soluble inorganic salts, preferably selected from an inorganic bromide salt, manganese(II) nitrate, and a water-soluble polytungstate salt, is also present.
- inorganic bromide salts preferably selected from the group consisting of calcium bromide, manganese(II) bromide, tin(II) bromide, tin(IV) bromide, bismuth(III) bromide, indium(III) bromide, and mixtures of any two or more of these; when
- one or more other water-soluble inorganic salts preferably selected from an inorganic bromide salt
- Lithium bromide is used in combination with one or more alkali metal polytungstate salts.
- Manganese(II) bromide is preferably used in combination with one or more other water-soluble inorganic salts preferably selected from an inorganic bromide salt, manganese(II) nitrate, and a water-soluble polytungstate salt; in preferred embodiments, the other inorganic salt is a bromide, and is calcium bromide or a combination of calcium bromide and one or more other inorganic bromide salts.
- preferred inorganic bromide salts include tin(IV) bromide and indium(III) bromide, especially tin(IV) bromide.
- two bromide salts are used, they are preferably a combination of calcium bromide and manganese(II) bromide; when three bromide salts are used, they are preferably a combination of calcium bromide, manganese(II) bromide and tin(IV) bromide, or a combination of calcium bromide, manganese(II) bromide, and bismuth(III) bromide.
- the composition formed has a density of about 14.3 ppg (1.71 kg/L) or more, preferably of about 14.6 ppg (1.75 kg/L) or more; and a true crystallization temperature of about 20°F (-6.7°C) or less, preferably about 10°F (-12.2°C) or less.
- An aqueous brine in which the only salt is manganese(II) bromide at a density of 15.0 ppg (1.80 kg/L) has a true crystallization temperature of about -10.3°C.
- the compositions formed preferably have densities of about 14.8 ppg (1.77 kg/L) or more, or preferably about 15.0 ppg (1.80 kg/L) or more, or more preferably about 15.1 ppg (1.81 kg/L) or more.
- the inorganic bromide salts are calcium bromide and another inorganic bromide selected from tin(IV) bromide, bismuth(III) bromide, or indium(III) bromide
- the compositions preferably have densities of about 16.0 ppg (1.92 kg/L) or more.
- the other inorganic bromide salt When in combination with calcium bromide, the other inorganic bromide salt is usually in an amount of about 3.0 wt to about 45 wt , preferably about 5 wt to about 40 wt ; more preferably about 6 wt to about 35 wt , relative to the total weight of the composition formed.
- the manganese(II) nitrate When calcium bromide is used in combination with manganese(II) nitrate, the manganese(II) nitrate is usually in the range of about 30 wt to about 75 wt , sometimes preferably about 35 wt to about 70 wt , sometimes preferably about 10 wt to about 50 wt , relative to the total weight of the composition formed.
- the water-soluble polytungstate salt is typically in the range of about 5 wt to about 40 wt , preferably about 10 wt to about 35 wt , relative to the total weight of the composition formed.
- the alkali metal polytungstate salt is generally in the range of about 5 wt to about 40 wt , preferably about 10 wt to about 35 wt , relative to the total weight of the composition formed.
- the water, inorganic bromide salt(s) and, when used, one or more other water-soluble inorganic salts are combined to form an aqueous solution.
- one or more inorganic bromide salts are formed during the process from hydrogen bromide and/or bromine and an inorganic oxide and/or hydroxide.
- the inorganic oxide and/or hydroxide is preferably selected from oxides and/or hydroxides of calcium, manganese(II), tin(II), tin(IV), bismuth(III), indium(III), and mixtures of any two or more of the foregoing.
- one or more other water-soluble inorganic salts preferably selected from an inorganic bromide salt, manganese(II) nitrate, and a water-soluble polytungstate salt
- oxides and/or hydroxides of manganese they are preferably used in combination with one or more other water-soluble inorganic salts preferably selected from an inorganic bromide salt, manganese(II) nitrate, and a water-soluble polytungstate salt.
- lithium bromide in combination with a water-soluble polytungstate salt lithium bromide can be formed from lithium oxide and/or hydroxide with hydrogen bromide and/or bromine.
- Preferred combinations of inorganic oxides and/or hydroxides are oxides and/or hydroxides of manganese(II), tin(II), tin(IV), indium(III), and/or bismuth(III), in combination with calcium bromide or oxides and/or hydroxides of calcium.
- inorganic oxides and/or hydroxides are combinations of calcium bromide or oxides and/or hydroxides of calcium with oxides and/or hydroxides of manganese(II); and/or tin(IV); combinations of calcium bromide or oxides and/or hydroxides of calcium with oxides and/or hydroxides of manganese(II) and oxides and/or hydroxides of tin(IV), or a combination of calcium bromide with oxides and/or hydroxides of manganese(II) bromide and oxides and/or hydroxides bismuth(III) bromide.
- preferred inorganic oxides and/or hydroxides are oxides and/or hydroxides of tin(IV), and oxides and/or hydroxides of indium(III), especially oxides and/or hydroxides of tin(IV).
- the processes further comprise heating the aqueous brine during and/or after combining the components; temperatures and preferences therefor are as described above.
- These preferred processes can further comprise adjusting the pH to a value in the range of about 1 to about 7 by adding an acid and/or an inorganic oxide and/or hydroxide to the aqueous brine composition; preferably, the inorganic oxide and/or hydroxide is an oxide and/or hydroxide of calcium, manganese(II), or tin(II), tin(IV), bismuth(III), indium(III), or mixtures of any two or more of these.
- Preferred pH ranges are as described above.
- Manganese nodules are formed in oceans throughout the world, and the most abundant metals in these nodules are manganese and iron.
- TCT true crystallization temperature
- a series of samples was prepared starting from 50.0 g of an aqueous CaBr 2 solution having a density of 14.2 ppg (1.70 kg/L).
- the salts LiBr (4.18 g), SrBr 2 »6H 2 0 (7.01 g), and BaBr 2 (2.21 g) were added to separate CaBr 2 solutions. Testing of the strontium-containing and barium-containing samples was discontinued due to solubility and density issues.
- a sample was prepared starting from 50.0 g of an aqueous CaBr 2 solution having a density of 14.2 ppg (1.70 kg/L). MnBr 2 (3.27 g) was added to the CaBr 2 solution. Results are summarized in Table 2 below.
- a sample was prepared starting from 40.0 g of an aqueous CaBr 2 solution having a density of 12.8 ppg (1.53 kg/L). MnBr 2 (10.18 g) was added to the CaBr 2 solution. Results are summarized in Table 2 below.
- EXAMPLE 5 [0085] Into a 3 L jacketed round-bottom flask equipped with a mechanical stirrer, a thermocouple, and an addition funnel was charged aqueous CaBr 2 (14.2 ppg; 673.68 g), deionized water (126.32 g), and MnO powder (99 wt , 67.92 g). While mixing, this slurry was heated at 67°C, and aqueous HBr (48 wt ; 320.96 g) was added over 1 hour via the addition funnel.
- aqueous CaBr 2 (14.2 ppg; 673.68 g
- deionized water 126.32 g
- MnO powder 99 wt , 67.92 g
- aqueous NaOH 50 wt
- aqueous HBr 48 wt
- the total amount of HBr and/or NaOH solution added was less than 10 g.
- the mixture was filtered under vacuum, more aqueous HBr (48 wt%) was added to adjust the pH to 3.0 to 3.5.
- a total of 2.04 g of NaOH solution was added; less than 5 g of aqueous HBr were added.
- Water (159 g) was removed under weak vacuum at 54°C to give a clear pink solution (1004 g) with a density of 1.78 g/mL (14.8 ppg) and a pH of 3.4. Results are summarized in Table 2 below.
- aqueous CaBr 2 (14.2 ppg; 673.68 g), deionized water (126.32 g), and MnO powder (99 wt , 67.92 g). While mixing, this slurry was heated at 67°C and aqueous HBr (48 wt ; 320.96 g) was added over 1 hour via the addition funnel. After holding at 67 °C for 35 minutes, aqueous HBr (48 wt ; 0.12 g) was added to titrate the pH to 3.18; some solid formation was observed.
- Example 8 was repeated, except that the samples were allowed to sit at ambient temperature rather than oven-aging. Results are summarized in Table 3 below.
- a sample was prepared starting from 100.0 g of an aqueous CaBr 2 /MnBr 2 (1.75: 1 (wt:wt) CaBr 2 :MnBr 2 ) clear brine fluid having a density of 15.0 ppg (1.80 kg/L).
- SnBr 2 (7.00 g) was mixed with the CaBr 2 /MnBr 2 clear brine fluid at 48°C. After the solids had dissolved, the mixture was cooled to room temperature and then vacuum filtered through a 2 micron glass filter, to give a clear liquid having a density of 15.8 ppg (1.89 kg/L).
- Examples 12, 13, 14, 15 and 16 the densities were measured with calibrated graduated cylinders.
- a 50 mL graduated cylinder was calibrated using 30.000 g of deionized water.
- the volume (29.7 mL) was recorded to calibrate the scale on the graduated cylinder.
- a 10 mL graduated cylinder was calibrated and used in the same manner to determine the densities.
- a sample was prepared by mixing SnBr 4 (10.17 g) and deionized water (4.11 g) containing HBr (0.02 g; 48%). The mixture was heated at 35°C to dissolve the solids. After the solids had dissolved, the mixture was cooled to room temperature, yielding a clear liquid having a density of 18.8 ppg (2.25 kg/L). A sample from the solution was placed in a freezer at -16°C, and another sample from the solution was placed in an oven at 60°C. The samples in both the oven and the freezer remained clear after 72 hours. Results are summarized in Table 6 below.
- a sample was prepared by mixing InBr 3 and deionized water in amounts to form a clear solution having a density of 16.0 ppg (1.92 kg/L), a sample of which was placed in a freezer at -16°C. Results are summarized in Table 6 below.
- each mixture was cooled to room temperature. The cooled solutions were clear. After cooling to room temperature, each sample was filtered through a 1 micron syringe filter and analyzed to determine its density. A portion of each sample was placed in a freezer at -16°C. All of the samples in the freezer remained crystal-free for at least one week. Results are summarized in Table 7 below.
- a sample was prepared by adding ⁇ ( ⁇ 0 3 ) 2 ⁇ 2 0 (3.00 g) to an aqueous CaBr 2 solution (57.6 wt , 25.05 g). The mixture was heated to 50°C and then cooled to room temperature to give a clear, light pink solution with a density of 15.3 ppg (1.83 kg/L). After filtration through a 1 -micron syringe filter, a portion of the sample was placed in a freezer at -16°C, and another portion of the sample was placed in an oven at 60°C. Both samples remain clear after 24 hours. Results are summarized in Table 7 below.
- each mixture was cooled to room temperature. After cooling to room temperature, each sample was filtered through a 1 micron syringe filter, and clear, colorless solutions were obtained. Each sample was then analyzed to determine its density. A portion of each sample was placed in a freezer at -16°C. All of the samples in the freezer remained clear at least overnight. Results are summarized in Table 8 below.
- LiBr (8.00g) was dissolved in deionized water (12.04 g). Into this solution was added sodium metatungstate hydrate (8.33 g), to give a colorless solution with a density of 15.0 ppg (1.80 kg/L); and
- the invention may comprise, consist, or consist essentially of the materials and/or procedures recited herein.
- the term "about" modifying the quantity of an ingredient in the compositions of the invention or employed in the methods of the invention refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like.
- the term about also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term "about”, the claims include equivalents to the quantities.
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