LU103163B1 - High-density, sub-zero stable clear liquid composition and the method for producing thereof - Google Patents
High-density, sub-zero stable clear liquid composition and the method for producing thereof Download PDFInfo
- Publication number
- LU103163B1 LU103163B1 LU103163A LU103163A LU103163B1 LU 103163 B1 LU103163 B1 LU 103163B1 LU 103163 A LU103163 A LU 103163A LU 103163 A LU103163 A LU 103163A LU 103163 B1 LU103163 B1 LU 103163B1
- Authority
- LU
- Luxembourg
- Prior art keywords
- composition
- liquid composition
- composition according
- alkali
- tppg
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 199
- 239000007788 liquid Substances 0.000 title claims abstract description 138
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 238000005553 drilling Methods 0.000 claims abstract description 85
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 238000005065 mining Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 104
- 239000002253 acid Substances 0.000 claims description 67
- 239000003513 alkali Substances 0.000 claims description 56
- 239000007787 solid Substances 0.000 claims description 56
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 47
- 150000007513 acids Chemical class 0.000 claims description 40
- 230000007797 corrosion Effects 0.000 claims description 37
- 238000005260 corrosion Methods 0.000 claims description 37
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- -1 alkali metal salts Chemical class 0.000 claims description 29
- 229910019142 PO4 Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 235000000346 sugar Nutrition 0.000 claims description 25
- 239000010452 phosphate Substances 0.000 claims description 23
- 238000012546 transfer Methods 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 19
- 235000011007 phosphoric acid Nutrition 0.000 claims description 19
- 239000008398 formation water Substances 0.000 claims description 18
- 239000004927 clay Substances 0.000 claims description 16
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 15
- 230000005764 inhibitory process Effects 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- 150000001447 alkali salts Chemical class 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 9
- 150000001735 carboxylic acids Chemical group 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 235000013305 food Nutrition 0.000 claims description 8
- 239000000174 gluconic acid Substances 0.000 claims description 8
- 235000012208 gluconic acid Nutrition 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 150000001261 hydroxy acids Chemical class 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000002734 clay mineral Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 6
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003139 biocide Substances 0.000 claims description 4
- 239000002537 cosmetic Substances 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 150000003016 phosphoric acids Chemical class 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 239000008247 solid mixture Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 claims 1
- 229910052722 tritium Inorganic materials 0.000 claims 1
- 239000012530 fluid Substances 0.000 abstract description 99
- 230000015572 biosynthetic process Effects 0.000 abstract description 53
- 238000005755 formation reaction Methods 0.000 abstract description 51
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 14
- 239000013529 heat transfer fluid Substances 0.000 abstract description 7
- 229910000318 alkali metal phosphate Inorganic materials 0.000 abstract description 5
- 231100000053 low toxicity Toxicity 0.000 abstract description 5
- 239000004615 ingredient Substances 0.000 abstract description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- 101100207327 Arabidopsis thaliana TPPG gene Proteins 0.000 description 93
- 235000021317 phosphate Nutrition 0.000 description 26
- 239000012267 brine Substances 0.000 description 24
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 23
- 150000003839 salts Chemical class 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 230000008901 benefit Effects 0.000 description 15
- 230000007613 environmental effect Effects 0.000 description 15
- 235000012209 glucono delta-lactone Nutrition 0.000 description 15
- 230000006378 damage Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 238000005259 measurement Methods 0.000 description 13
- 150000004820 halides Chemical class 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- 230000002378 acidificating effect Effects 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000010257 thawing Methods 0.000 description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 9
- 239000001110 calcium chloride Substances 0.000 description 9
- 229910001628 calcium chloride Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
- 231100000584 environmental toxicity Toxicity 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910000160 potassium phosphate Inorganic materials 0.000 description 7
- 235000011009 potassium phosphates Nutrition 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229960003975 potassium Drugs 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 229910052792 caesium Inorganic materials 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000001739 density measurement Methods 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 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 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 238000001139 pH measurement Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 150000008163 sugars Chemical class 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 239000004135 Bone phosphate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- MNQZXJOMYWMBOU-UHFFFAOYSA-N glyceraldehyde Chemical compound OCC(O)C=O MNQZXJOMYWMBOU-UHFFFAOYSA-N 0.000 description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 3
- 229940048102 triphosphoric acid Drugs 0.000 description 3
- 238000004260 weight control Methods 0.000 description 3
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 241000607620 Aliivibrio fischeri Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 208000007976 Ketosis Diseases 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 2
- 229920001273 Polyhydroxy acid Polymers 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
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- IAJILQKETJEXLJ-RSJOWCBRSA-N aldehydo-D-galacturonic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-RSJOWCBRSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000010428 baryte Substances 0.000 description 2
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 230000029918 bioluminescence Effects 0.000 description 2
- 238000005415 bioluminescence Methods 0.000 description 2
- ATZQZZAXOPPAAQ-UHFFFAOYSA-M caesium formate Chemical compound [Cs+].[O-]C=O ATZQZZAXOPPAAQ-UHFFFAOYSA-M 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001622 calcium bromide Inorganic materials 0.000 description 2
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
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- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
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- 231100000956 nontoxicity Toxicity 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
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- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
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- CPWJKGIJFGMVPL-UHFFFAOYSA-K tricesium;phosphate Chemical class [Cs+].[Cs+].[Cs+].[O-]P([O-])([O-])=O CPWJKGIJFGMVPL-UHFFFAOYSA-K 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- VHUJINUACVEASK-UHFFFAOYSA-J aluminum;cesium;disulfate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Cs+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VHUJINUACVEASK-UHFFFAOYSA-J 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001664 caesium compounds Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- DSLZVSRJTYRBFB-DUHBMQHGSA-N galactaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O DSLZVSRJTYRBFB-DUHBMQHGSA-N 0.000 description 1
- 150000001281 gamma hydroxy acids Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229940097043 glucuronic acid Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000008863 intramolecular interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 230000004140 ketosis Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- KBAHJOGZLVQNBH-UHFFFAOYSA-K rubidium(1+);phosphate Chemical class [Rb+].[Rb+].[Rb+].[O-]P([O-])([O-])=O KBAHJOGZLVQNBH-UHFFFAOYSA-K 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 230000004580 weight loss Effects 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
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
- C09K3/185—Thawing materials
-
- 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
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
-
- 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
- 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
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Lubricants (AREA)
Abstract
The invention relates to a liquid composition which is essentially clear and comprises at least one alkali metal phosphate salt in a liquid, further comprising at least one additional ingredient, preferably a carboxylic acid, and discloses the production method thereof. The liquid composition is adapted for the use as a well drilling, completion, and workover fluid, mining fluid, deicing agent and heat transfer fluid and furthermore features a range of desirable properties, including high and low temperature tolerance, low toxicity, low corrosiveness, and high compatibility with formations.
Description
HIGH-DENSITY, SUB-ZERO STABLE CLEAR LIQUID COMPOSITION AND THE METHOD LU103163
FOR PRODUCING THEREOF
TECHNICAL AREA
The present invention pertains to a novel and economical liquid composition according to claim 1. The liquid composition relates to a high-density, sub-zero stable liquid devoid of solids used as a well drilling, completion, and workover fluid, mining fluid, deicing agent and heat transfer fluid featuring a range of desirable properties, including high and low temperature tolerance, low toxicity, low corrosiveness, and high compatibility with formations and discloses the production method thereof.
STATE OF THE ART
In the drilling, completion, and workover of oil and gas wells as well as in mining operations, fluids known as drilling fluids are utilized to achieve various functions, including: Lubrication to reduce friction between the drill bit and the formation, increasing drilling efficiency and reducing wear and tear on drilling equipment; cooling to dissipate heat generated by friction and prevent overheating of drilling equipment; suspension to transport solids from the formation to the surface and prevent solid buildups in the wellbore; weight control to provide adequate downward pressure on the drill bit to prevent wellbore collapse; formation stability to preserve the integrity of the wellbore by preventing collapse or formation sloughing during drilling; and corrosion protection to prevent corrosion of drilling equipment and preserve the wellbore.
Drilling, completion, and workover fluids, also known as well-servicing fluids, can be broadly classified into two categories: traditional and solid-free. Traditional well-servicing fluids include solid weighting agents, such as barite, bentonite, and hematite, to increase fluid density and counteract high formation pressures. On the other hand, solid-free well-servicing fluids with a
NTU less than 40 are clear or nearly clear liquids without any solid components and are generally gentler on the formation, reducing the risk of damage compared to traditional fluids.
Alkali and alkaline earth metal and some transition metal salt solutions, alone or in combination, are commonly utilized in oil and gas well drilling, completion, workover, packer, and perforation. The introduction of solid-free, so called clear-brine fluids has significantly enhanced completion and workover operations by reducing formation plugging and solids settling issues that were previously encountered with traditional water-based or oil-based drilling fluids. Solid-free, clear brine fluids are an advantageous choice for oil and gas well servicing and completion due to the following unique properties: the elimination of solid white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023 particles eliminates formation plugging and solids settling issues associated with water-based LU103163 or oil-based drilling fluids; the inhibition of clay swelling and dispersion in porous media; the preservation of subterranean formation wettability; the reduced corrosiveness to drilling equipment; and the relatively high density and chemical compatibility with the formation.
The formula of a solid-free well-servicing fluid typically includes various components such as the solvent water, soluble weighting materials, corrosion inhibitors, viscosity-enhancing agents, surfactants, pH stabilizers, biocides, and clay inhibitors. Weighting materials, which contribute to the density of the fluid, are particularly significant as they can make up a substantial amount of the fluid's mass, thus greatly affecting the performance of the solid-free well-servicing fluid. When completing a well in a reservoir with a normal pressure system, a low-density brine can be used. However, in reservoirs with abnormally high pressure, a high- density brine is necessary. Despite the need for a high-density fluid, it can be difficult to attain densities above 1.80 g/cm? with a solid-free completion fluid, as there are no solid weighting particles in the liquid. Besides the challenge of maintaining the correct fluid density, many conventional clear brine drilling fluids including halide, phosphate and formate brines encounter technical, environmental, or economic constraints that make them unsuitable for specific well conditions.
Clear brine fluids have garnered significant attention due to their distinctive properties that make them useful in a variety of applications beyond their use in the oil, gas, and mining industry, resulting in the replication or adaptation of these products for other sectors. In particular, their high density and low freezing points make them highly effective as deicing agents for industries such as construction, aviation, and transportation, where cold temperatures and snowfall can hinder or halt operations and lead to safety concerns. These fluids can quickly melt existing ice and prevent the formation of new ice, making them ideal for use on airports, highways, and walkways in cold environments. Clear brine fluids also have exceptional heat transfer properties, making them a valuable tool in various industrial processes, including power generation, chemical processing, and food manufacturing. Their high thermal conductivity and specific heat capacity enable them to quickly transfer heat and regulate temperature effectively. This property and the fact that these clear brine fluids have no global warming and ozone depletion potential make them highly valuable in heat exchangers and cooling systems, where they are used to manage the temperature of fluids in various industrial processes. Yet, the employment of traditional clear brines as heat transfer fluids or deicing agents that are similar to those used in well servicing and mining can bring about comparable technical, environmental, and economic challenges. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
Halide brines, especially chloride brines (NaCl, KCI, CaClz, MgCle) and bromide brines (NaBr, LU103163
KBr, CaBrz, ZnBrz), have been used for several decades as solid-free brines in the oil, gas and mining industry as well as deicing agents and heat transfer fluids. These brines are known for their high density and low cost and are therefore often used as weighting agents to increase the density of drilling fluids. One of the earliest documented uses of halide brines in drilling operations can be found in a paper by C.L. Wendorff (1974). This scientific paper discusses the use of a mixture of calcium chloride and calcium bromide as a solid-free completion and workover fluid and highlights its benefits, including its high density of up to 1.81 g/cm?, low corrosiveness, and low toxicity. Since the issuance of this paper, numerous other scientific literature and patents have been published that describe the use of halide brines as drilling fluids.
For example, patent publication WO1986001253A1 (1984) describes a composition consisting essentially of an admixture of water, calcium bromide and methanol wherein the admixture has a density of between 1.80 and 2.00 g/cm®. The oil and gas industry has further advanced by developing new halide brine materials, such as ZnBr./CaBr: fluids, which can reach high densities of around 2.30 g/cm®. Nevertheless, halide brines pose several problems, as they often are corrosive to drilling equipment and can cause environmental damage, especially to aquatic life and plants, if they are not properly disposed of. The high salt content in halide brines can lead to the formation of scaling in the wellbore, reducing the efficiency of the drilling process and increasing the risk of wellbore instability. Besides in oil drilling, halide brines, especially those based on sodium, magnesium, and calcium chloride, are commonly used as deicing agents and heat transfer fluids due to their affordability and effectiveness.
Nevertheless, these brines can cause corrosion to metals over time, leading to damage to infrastructure. Additionally, they can be harmful to the environment as they have the potential to contaminate both ground and surface water, harm vegetation, and cause harm to wildlife.
Patent publications US6616739B1 (2002) or US6149834A (1999) proposes to mitigate the corrosive properties of chloride solutions used as deicing agents by incorporating corrosion inhibitors into the solution, up to a maximum of 50% w/w. However, this method increases the cost of the final product, which makes the use of halides as deicing agents impractical since they are typically chosen for their cost-effectiveness.
Formate brines are gaining popularity in the drilling industry as a replacement for traditional inorganic salt-based fluids such as calcium chloride, magnesium chloride, and potassium chloride. The use of formate brines is attractive due to their low toxicity and biodegradability, which results in a reduced environmental impact compared to traditional drilling fluids. Of the white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023 formate brine family, potassium formate with a density of around 1.57 g/cm* has become the LU103163 most widely adopted.
Patent no. EP0922079B1 (1996) discloses the addition of potassium citrate to potassium formate solution, resulting in a moderate increase in density to 1.60 g/cm?®. However, this does not provide a low crystallization temperature, making it inadequate for use in the field. Despite claims of achieving densities in excess of 2.00 g/cm*, such formulations are not stable at moderate low temperatures (e.g., 10°C) and require heating for use in the field.
European patent specification EP3178901A1 (2015) offers a solution to the low temperature issue by incorporating lithium or a mixture of lithium and sodium citrate into potassium formate solutions. This results in densities ranging from 1.60 to 1.64 g/cm* and crystallization temperatures below 5°C, however, the use of lithium in the formulation makes it an uneconomical option.
Another instance of using clear brines consisting of organic salts for oil and gas exploration is shown in Patent specification WO99/23188 (1998). This patent highlights the reduced corrosiveness of salts derived from organic acids compared to halides but does not address the challenges of obtaining very high densities or low crystallization temperatures. A significant technological advancement in drilling fluids has been made with caesium formate, which offers very high density and low toxicity with biodegradability.
The US Patent specification US6015535A (1997) discloses the process for producing a purified cesium compound from cesium alum for use as a drilling fluid or heavy medium separation fluid characterized by a density between 1.20 to 2.50 g/cm?. However, the practical application is limited by the material’s scarcity and high cost.
Mixing caesium formate with short-chain organic acid salts like formates, acetates, or propionates, as disclosed in the European patent specification EP0572113A1 (1992), provides higher density and stable solutions but is hindered by the prohibitive cost of caesium compounds. Besides their use as well-servicing fluids, formate brines and other short-chain carboxylic acid-based brines, including acetate brines, are used in various applications, including as deicing agents and heat transfer fluids. However, it is important to note that when compared to chloride solutions, they are generally less effective for these purposes. While formate and acetate brines may be more biocompatible and less corrosive than halide brines, they may still cause infrastructure damage due to their corrosive nature towards certain types white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023 of metals. As a result, proper precautions and corrosion inhibitors must be utilized when using LU103163 these fluids to prevent damage to the equipment or infrastructure.
To alleviate this issue European Patent specification EP0375214A1 (1988) proposes the addition of phosphate and nitrate salts to a deicing composition containing formate salts to reduce its corrosivity.
Similarly, Patent specification US5104562A (1990) suggests the use of additional corrosion inhibitors in a heat transfer fluid composition containing potassium formate. Despite its potential to slightly reduce corrosiveness, adding these components may significantly increase the cost and decrease the effectiveness of the product.
Despite showing great potential, phosphate brines have not been widely adopted in drilling operations in the past, with scientific advancements in this field only made in recent years.
However, the effectiveness of phosphate brines has been proven through successful field testing, as demonstrated by the use of a blend of monopotassium phosphate and dipotassium phosphate brines as completion and workover fluids in China and Indonesia. The highest density that can be achieved with this brine is estimated to be around 1.80 g/cm?, although lower density brine solutions have been known to crystallize under normal conditions.
Tripotassium phosphate brines may have limited usability due to their solubility limit of only 48% w/w and maximum density of below 1.65 g/cm*. Advantages of phosphate brines include their solid-free nature, low cost, low corrosiveness, and environmentally friendly nature.
The Patent specification US9090807B2 (2013) discloses a drill-in and completion fluid comprising water and a potassium phosphate-based brine reaching densities of around 1.80 g/cm®, making the fluid unviable for HT/HP environments requiring densities greater than 1.80 g/cm°. Additionally, the true crystallization temperature (TCT) of this fluid is reported to be 2°C, rendering it unsuitable for storage and use in colder environments.
Another example is a well completion fluid composition for use in well completion or servicing operations comprising a mixture of cesium phosphate and other alkali metal phosphate salts, as described in US20100305010A1. Although the use of cesium allows for higher densities of above 2.40 g/cm, its scarcity and high cost limit its practical application. Compared to halide and carboxylate brines, phosphate brines have not been widely utilized as deicing agents and heat transfer fluids, yet studies have shown that a mixture of mono and dibasic salts of orthophosphoric acid or tetrapotassium pyrophosphate may offer promising deicing results.
However, the cost to benefit advantage of these brines compared to chloride salts is not given. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
OBJECT OF THE INVENTION LU103163
The oil, gas and mining industry urgently need a solution to address the beforementioned limitations of current drilling, completion, and workover fluids, especially addressing the deficits of high environmental impact while maintaining thermal stability, a high density and stability against low temperature precipitations. Finding solutions to address the issues that may arise from the use of these fluids in other applications, including deicing and heat transfer, is equally important.
Thus, it is an objective of the present invention to provide a liquid composition that showcases high density, is free of solids, non-toxic, tolerates low and high temperatures, is economical, is non-corrosive, and is compatible with the environment.
In addition, a simple and cost-efficient manufacturing process is required that uses readily available materials and does not require additives or catalysts for economical large-scale synthesis. Furthermore, it must be possible to transport the liquid economically.
The present invention solves these problems by providing a liquid composition according to claim 1.
Furthermore, it provides a method for preparing the liquid composition according to claim 15, a method for converting the liquid composition according to the invention into a solid form according to claim 20 and converting it back to a liquid composition according to claim 21.
Further advantageous embodiments can be found in the subclaims, the description and the embodiment examples. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
GENERAL ADVANTAGES LU103163
The present invention offers a number of advantages. Drilling fluids are used in oil and gas well drilling, completion and processing, and mining operations for lubrication, cooling, suspension, weight control, formation stability and corrosion protection. Drilling fluids are classified as conventional (with solid weighting agents) or solid-free (clear fluids). Alkali, alkaline earth, and transition metal salt solutions are commonly used.
Ideally, a drilling fluid should provide a clear brine fluid that improves completion and processing operations by reducing clogging and deposition problems. It reduces or prevents formation plugging, prevents clay swelling, maintains formation wettability, and should have low corrosivity while having high density and chemical compatibility. Finally, environmental, and economic factors must also be accounted for.
The present invention discloses a liquid composition that meets and exceeds the above challenges by providing a substantially clear, solids-free, sub-freezing stable, high density alkali phosphate salt solution with an additional component that dramatically improves density while maintaining thermal stability (standing up to high and low temperatures) and liquid integrity. Finally, the inventors provide a method for cost-effectively providing such a liquid composition and a solid form having a preferred water content of less than 10% by weight of the composition, which may allow convenient, cost-effective and safer transportation of the composition.
Advantageously, the inventors describe such a composition without the use of heavy and costly alkali phosphates found in the prior art, such as rubidium or cesium phosphates, or the use of weighting agents that would affect the mechanical properties of the composition. The composition according to the present invention has negligible to low environmental impact and toxicity. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
DETAILED DESCRIPTION LU103163
The invention provides a liquid composition, wherein the composition is essentially clear and comprises at least one alkali metal phosphate salt in a liquid, the liquid preferably being aqueous, further comprising at least one additional ingredient, preferably a solubilizing agent, which dramatically increases the solubility of the alkali metal phosphate salt.
A solution is a homogeneous mixture composed of two or more substances that are evenly distributed. It is formed when one substance, called the solute, is dissolved in another substance, known as the solvent. In the context of the current invention, the solution is aqueous, therefore comprising of water with a dissolved solute, for example a phosphoric acid and/or its alkali metal salts. In the context of this invention, the liquid composition is regarded as a solution.
A liquid is a form of matter that has a definite volume but takes the shape of its container. In other words, liquids flow and can be poured or contained within a vessel, it can be described by a number of physical properties, such as density, viscosity, thermal and electrical conductivity, salinity, thermal stability, boiling and freezing point, etc. The word liquid and fluid are used interchangeably. A liquid in the context is preferably an aqueous system.
An essentially clear liquid refers to a liquid that is transparent or translucent, allowing light to pass through without significant scattering or absorption, which shows the absence of visible suspended particles or solids. In the context of the present invention, the essentially clear liquids refer to in particular salt solutions, also called brine solutions, which are aqueous liquids containing dissolved salts and/or other solids, such as carboxylic acids, the content of undissolved solids being preferably below 5% w/w of dissolved solids, more preferably below 2% w/w, most preferably below 1% w/w at room temperature. In an alternative embodiment of the invention, the solution is clear under working conditions, preferably between -20—170 °C.
Alkali phosphate salts are compounds consisting of alkali metal cations, such as sodium, lithium and preferably potassium, and/or hydrogen cations, and a phosphate anion. The phosphate anion is composed of phosphorus and oxygen atoms, typically arranged in a tetrahedral structure, and is derived from phosphoric acids. Moreover, there are trialkali phosphate salts (also referred to as tribasic), dialkali monohydrogen phosphate salts (also referred to as dibasic) and monoalkali dihydrogen phosphate salts (also referred to as monobasic). For the purpose of the present invention, all alkali and/or alkali hydrogen phosphates are referred to as alkali phosphates and may be used interchangeably. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
In a preferred embodiment of the current invention, a tribasic phosphate salt is used, which LU103163 leads to a high density and basicity which is beneficial for some applications such as use as a drilling fluid, the high basicity can reduce corrosion effects.
In some other aspects of the current invention, mono or dihydrogen phosphate salts may be used, which can reduce the basicity and density of the fluid, allowing for other materials being used. Furthermore, by selecting different alkali metals and adjusting the ratio of alkali hydrogen phosphate to alkali phosphate, it is possible to fine-tune the pH level of a solution. This has the technical effect of tailoring the liquid compositions physical properties according to the task.
In a preferred aspect of the current invention, a potassium phosphate salt is provided, which is advantageous in the context of economic and ecological aspects. Other alkali metal salts, such as sodium or lithium phosphate salts have generally a lower density than potassium phosphate salts, while cesium or rubidium phosphate salts have a generally higher density but are also associated with far greater costs. From a cost-benefit point of view, potassium phosphate salts are therefore the best option, while still being ecologically sound. Preferably, the alkali metal salts provided by the present invention are sodium, potassium, and lithium, with potassium being particularly preferred because this element generally allows for high density of its acid salt derivatives while being much cheaper than the much rarer elements cesium and rubidium.
Further preferably, a mixture of different potassium phosphate salts can be used, for example by using phosphoric acids as precursors and adding a certain stoichiometric amount of basic alkali salts, such as alkali hydroxides, to produce a mixture of mono- and/or di- and/or trialkali phosphates. This mixture can offer significant advantages, such as higher densities or tailored pH values. Additionally, a mixture of different alkali salts may be used in this way, creating mixed alkali metal mixed basicity phosphates.
The basicity of alkali salts refers to the stoichiometric number of replaceable hydrogen ions (H*) present in the salt molecule. It determines the acidity or basicity of the salt when dissolved in water. Alkali acid salts are formed by the partial neutralization of an acid with an alkali (base).
The resulting salt contains both a cation, which comes from the alkali, and an anion, which comes from the acid. The basicity of the salt depends on the number of acidic hydrogen ions present in the acidic part of the salt. For example, if we consider the acid HX and the alkali
MOH, we get the alkaline salt MX. The basicity of MX would be equal to the number of acidic hydrogen ions in HX. If HX contains one acidic hydrogen ion, MX would be monobasic. If HX contains two acidic hydrogen ions, MX would be dibasic, etc. The basicity of alkali salts affects white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023 their behavior when dissolved in water. The higher the basicity, the greater the potential for the LU103163 salt to release hydrogen ions and exhibit acidic properties when dissolved in water.
Conversely, salts with lower basicity tend to exhibit more basic (alkaline) properties when dissolved in water.
Furthermore, the invention provides at least one additional component which is a solubilizing agent that dramatically improves the solubility of the alkali phosphate salt. In an aspect of the current invention a solubilizing agent, when used as an additive in the liquid composition containing at least one alkali phosphate salt, plays a crucial role in enhancing the solubility of the salt, for example in high-density solutions intended for use as drilling agents. This allows several technical advantages to be achieved. The solubilizing agent reduces the surface tension of the solution, aiding in the dispersal and dissolution of the phosphate salt particles.
This increased solubility ensures a more homogeneous, dense, and stable solution, preventing the formation of undesired precipitates or blockages, which results in a highly concentrated and dense liquid composition, ideal for drilling applications that require efficient transport and circulation of the solution within the wellbore. Advantageously, precipitation induced by cooling may also be suppressed, thus allowing for a greater temperature range in which the liquid composition can be stored and used.
The additional component is a carboxylic acid RCO:Y, preferably a hydroxy acid, wherein the acid is provided in its free form and/or its derivatives such as its alkali salts and/or its cyclic esters and/or its anhydrides.
In a preferred embodiment, the additional component may be a hydroxy acid, such as an alpha, beta, and/or gamma hydroxy acid, and/or a di-, tri-, tetra- or polyhydroxy acid. In a preferred embodiment the carboxylic acid may be a di- or tri-carboxylic acid. A hydroxy acid may be derived from sugars, also referred to as sugar acid. The hydroxy acid may be derived from naturally occurring substances. The hydroxy acid may be a fruit acid.
A carboxylic acid in the spirit of the current invention is any substance containing a carboxyl functional group (-COOH). white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
The carboxylic acid and/or its derivatives according to the formula RCO.Y, may be represented LU103163 by the following structure formulas:
Re i
A, AX Ar AS Ar È ! X OH ©
X X Z E
Ag ANR A © oH i
RCO2Y= |; Ö OH © CHa OH 0 à} 0 = i ! 75) dis AO A
ES : n n È
Y=Li,Na,K,H, © \ J Ë
R,-C(OJOR ! n=1+4 t
Q L
"Ro OH L : X=H, OH, COOH,R OH i Z=C4—Cg Alkyl, Aryl, COOH, H A
Lee
The carboxylic acid and/or their derivatives described in the formulas are examples and each a unique aspect of the current invention. All stereoisomers of the presented acids are also disclosed, especially in the case of poly hydroxy acids, which are preferably derived from sugars, the stereo-formations are therefore correlated with the pre-existing stereocenters of the parent compound.
Preferably, the carboxylic acid may be provided in its free form (Y = H) and/or its alkali metal form (Y = Li, Na, K), and/or in its cyclic ester form (Y = -R) and/or its anhydride (Y = -C(O)OR).
The derivates of the acid influence the chemical properties, using a alkali salt may increase the pH value of the liquid composition, while adding a free acid as additional component decreases the pH value of the liquid composition. Advantageously, adding a cyclic lactone may lower the pH value of the liquid composition, allowing for reduced corrosion effects for some applications. À cyclic lactone or anhydride of the carboxylic acid can chemically bind up to one equivalent of water, further increasing the concentration of the liquid composition.
Advantageously, in a preferred embodiment related to hydroxy acids, the acids may be derived from easily accessible natural compounds, such as fruit acids or sugar acids. The use of naturally occurring acids and their derivatives enables high environmental compatibility due to the biodegradability of these compounds. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
In one embodiment of the current invention, Z is chosen from optionally substituted where R? LU103163 may comprise an optionally substituted C+-Cz-alkyl group, or an optionally substituted aryl group, preferably Z is chosen from an optionally substituted C+-Ce-alkyl group, or an optionally substituted aryl group, more preferably R is selected from an optionally hydroxy substituted
C+-C5-alkyl group, or an optionally hydroxy substituted aryl group. The preference for hydroxy substituted alkyl chains is due to their increased hydrophilic character, which allows favorable interactions with the liquid composition and is an aspect of the solubilizer's mode of action.
These aspects are highly relevant for said carboxylic acids in their application in ecological benign applications such a drilling, completing, or workover liquid in oil, gas, and mining applications and/or heat transfer liquid in industrial, pharmaceutical, food, feed, and cosmetic applications.
In one embodiment, the additional component is provided in its free acid form. In another embodiment, the additional component is provided as a derivative, such as its alkali metal salts, its cyclic esters (also referred to as lactone), or anhydrides.
In an especially preferred embodiment, the carboxylic acid is derived from abundant natural products associated with low costs, such as acids derived from sugars (sugar acids) or fruit acids. This enables a cost-effective and at the same time ecologically compatible mixture, as these acids are naturally degradable.
In a further preferred embodiment, the additional component in accordance with the current invention is a sugar acid and/or its derivates, preferably a glucose derived acid, more preferably gluconic acid and/or its derivatives such as its alkali salts and/or its cyclic esters and/or its anhydrides.
Sugar acids are acids derived from sugars by oxidation of one or more alcohol or aldehyde groups. They can be classified into different groups, such as the aldonic acids, in which the aldehyde group of an aldose is oxidized, ulosonic acids, in which the alcohol group at the initial end of a 2-ketosis is oxidized, resulting in an a-keto acid, uronic acids, in which the -alcohol group at the end of an aldose or ketosis is oxidized, and the aldaric acids belonging to the dicarboxylic acids, in which both ends (aldehyde and alcohol group) of an aldose are oxidized.
Preferably, the carbonic acid according to the invention is a sugar acid or one of its derivatives.
Sugar acids can form cyclic esters since they possess both carboxy and hydroxy functional groups, ulosonic acids can form cyclic acetals and aldaric acids may form anhydrides.
Furthermore, all sugar acids can be converted to their respective alkali salts or into an anhydride form. Preferably, the additional component is a sugar acid, such as an aldaric, white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023 aldonic, ulosonic, or uronic acid. More preferably the sugar acid is a aldonic acid. Preferred LU103163 carboxylic acids according to the invention are selected from glyceric acid, xylonic acid, gluconic acid, aldonic acid, glucuronic acid, galacturonic acid, tartaric acid, mucic acid, saccharic acid (glucaric acid). These acids are solids at room temperature. More preferred carboxylic acids according to the invention are selected from the 16 isomers of the 2,3,4,5,6- pentahydroxyhexanoic acid, most preferably gluconic acid. Sugar acids have chiral centers, so there are a variety of stereoisomers. According to the present invention, all stereoisomers of a specific sugar acid are included and can be used interchangeably.
In an alternative embodiment of the current invention, polysaccharides which contain sugar acids can also be used as additional component. This includes pectin, which contains galacturonic acid. This has the technical advantage of using readily available starting materials which are known to have a low environmental impact.
In a preferred embodiment, the use of sugar acids as additional component as solubilizing agents has a number of advantages. It is an outstanding achievement of the inventors to have discovered, that the addition of a small percentage of these acids can dramatically increase the solubility of a alkali potassium phosphate solution. This may be attributed to increased polarity of the solution, favorable intramolecular interactions between the phosphate anions, the sugar acids and the solvent, chemical bonding (such as esterification of the hydroxyl groups of sugar acid with phosphates, mixed phosphoric anhydrides) and colloidal effects. *C-
NMR (nuclear magnetic resonance, 500 MHz, Bruker Avance Ill HDX) studies show, for example, that the chemical shift of the carbonyl carbon of the glucono delta-lactone in the liquid composition according to the invention is shifted compared to the reference in pure deuterated water. This indicates a strong interaction and/or bonding with the phosphate anions in solution.
Furthermore, in an aspect of the invention related to sugar acids, the liquid composition is environmentally benign, cost effective, stable at sub-zero temperatures while being also heat resistant. While the use of alcohols is known to decrease the melting point of a solution, the use of sugar acids as solubilizing agents which also decrease the melting point of a solution is novel.
In one embodiment, at least one alkali phosphate salt comprises a potassium counter cation, preferably dipotassium phosphate and/or, tripotassium phosphate and/or potassium pyrophosphate. Potassium allows for high density of its acid salt derivatives while being much cheaper than the much fewer common elements cesium and rubidium. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
In a more preferred embodiment, the alkali phosphate salt comprises a potassium counter LU103163 cation chosen according to the desired pH value suitable for the application. Too high pH values can lead to corrosion effects, so that the phosphate salts may be matched to the metal alloys used, from which, for example, pipes or drilling means are made.
In an aspect of the present invention relating to drilling fluids, the liquid composition preferably provides a tripotassium phosphate as this allows for the highest density and is advantageous for this application.
The total solids in solution are preferably between 10% to 90%, more preferably 20% to 82% by weight of the formulation. A high solids content is advantageous because it enables higher densities. It is an outstanding achievement of the inventors to have discovered an additional component in the form of a carboxylic acid according to the present invention, which enables this high concentration of dissolved solids. Furthermore, in addition to the high content of dissolved solids, the liquid composition is preferably essentially clear, which is an improvement in regard to the prior art, which is unable to accomplish such high densities, especially of alkali phosphate solutions.
In a preferred embodiment of the current invention, more than 50 % of the solids in solution are alkali phosphate salts and the total solids in solution are at least 70 %, most preferably above 75 %. The total solids in solution in the liquid composition therefore advantageously may exceed the solubility limit of pure alkali phosphate solution. This has the advantage of higher possible densities and allowing alkali phosphate salts to be used in industrial applications such as drilling, completing, or workover liquid in oil, gas and mining applications, which were previously not feasible because of the limitations of obtainable density.
In a preferred embodiment, the additional component is added in a fraction of the alkali phosphate salt, preferably between 1% to 30%, more preferably between 2% and 25%, most preferably between 5% and 20%. The additional component usually involves a higher cost per mass than simple alkali phosphate salts, such as potassium phosphate and/or potassium hydrogen phosphate and/or potassium dihydrogen phosphate, so it is economically advantageous to require only a fraction to obtain the desired properties of the liquid composition.
In a more preferred embodiment, the ratio between phosphate salt and additional component is 80:20, also referred to as in a most preferred embodiment, the ratio is 90:10. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
In an aspect related to a liquid composition in accordance with the current invention wherein LU103163 the additional component a gluconic acid derivate, such as GDL, more preferred embodiment, the ratio between phosphate salt and additional component is 80:20, also referred to as in a most preferred embodiment, the ratio is 90:10.
The density of the liquid composition is between 1.20 g/cm? and 2.40 g/cm°, more preferably between 1.40 g/cm? and 2.30 g/cm?3, most preferably between 1.50 g/cm? and 2.20 g/cm? as a solution at 20°C. The high density is achieved through the solubility enhancing properties of the additional component, which allows for higher density than previously achievedwith alkali phosphate solutions, especially with potassium phosphate solutions. This is a dramatic improvement, since the properties of a alkali phosphate containing liquid composition in relation to environmental and ecological and economic factors are highly desirable, but the low density, especially of potassium phosphate-based liquids was too low for certain industrial applications such as drilling fluids. It is therefore an outstanding achievement of the inventors to have found compositions containing at least one alkali phosphate salt with high densities.
This density is needed in practice to allow suspension to transport solids from the formation to the surface, to prevent deposition of solids in the wellbore, for weight control to apply adequate downward pressure on the drill bit to prevent collapse of the wellbore, and formation stability to maintain the integrity of the wellbore by preventing collapse or fracturing of the formation during drilling.
In an especially preferable embodiment, the density of a liquid composition in accordance with the current invention is above 1.80 g/cm?, a common threshold for drilling fluid applications which counteracts high formation pressures. It achieves these densities without adding solid weighting agents, such as barite, bentonite, and hematite, to increase fluid density. Solid additives increase the load on industrial equipment, so essentially solids-free compositions are desirable to limit damage to high-value equipment.
In one embodiment, the composition has a pH in the range of preferably 7.0 to 13.0, more preferably 8.0 to 12.5. The pH value can be modulated by choosing the alkali phosphate salt, a mixture of alkali phosphate salts and by a least one additional component.
In a preferred embodiment, the additional component is a carboxylic acid, thereby lowering the pH, which can be compensated by the addition of tribasic phosphate salts when high pH values are desired, for example for corrosion protection. In another preferred embodiment, where a relatively low pH is desired, monobasic or dibasic phosphate salts may be provided in addition to a larger amount of additional components, such as a hydroxycarboxylic acid. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
One aspect of the invention provides a clear composition in which the working temperature of the liquid is between -20 to 180 °C, preferably between -10 to 170 °C, and more preferably between 4 to 150 °C. In some aspects of the present invention relating to drilling and cooling applications, the liquid composition is required to cool and dissipate heat generated by friction to prevent overheating of the drilling equipment. The composition must therefore be stable at a range of elevated temperatures to allow efficient heat transfer over an extended period of time to reduce the risk of thermal decomposition and damage to the equipment.
In a preferred embodiment of the current invention, the liquid composition does not form precipitates when stored at a temperature of at preferably at least -5 °C, more preferably at least 0 °C, most preferably at least 4 °C. Many industrial applications are done under aggravated conditions, for example under climatic conditions where temperatures at or below the freezing point are common. It is a common problem in the state of the art, that high density salt solutions are prone to precipitation at low temperatures, which requires heating during the entire transport and storage chain, which add a substantial amount of costs with adding the risk of a single cooling event irreversibly destroying the composition by precipitation.
Precipitation, also known as precipitation reactions or crystallization, occurs when a solid substance forms and separates from a liquid solution. This process usually occurs when the concentration of the solute exceeds its solubility limit, resulting in the formation of solid particles. The solubility limit refers to certain chemical substances and depends on various mechanisms, such as cooling, evaporation, chemical reactions, or changes in pH. The solubility limit typically decreases with temperature; therefore, it is an outstanding achievement of the inventors to have found liquid compositions according to the present invention that exhibit resistance to precipitation even at low temperatures and/or during storage.
Storage in accordance with the present invention is the storage of the composition prior to use.
It includes the systematic storage and preservation of the composition to maintain its quality, integrity, and accessibility over time. Storage of the liquid composition can be over extended periods of time, preferably at least 1 year at room temperature, more preferably at least 6 months at room temperature. Preferably the liquid composition may be stored at reduced temperatures, such as -5 to 4 °C, for extended periods, such as at least one month, more preferably at least 20 days. This allows for transportation to drilling sites under unfavorable climatic conditions.
In a preferred embodiment of the present invention, the liquid composition can be dried by evaporating the solvent (water). Advantageously, this allows for easier and safer transportation white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023 as no liquid handling or storage is required. In addition, this allows storage at low and high LU103163 temperatures without the risk of precipitation or other chemical decomposition processes, and the composition can be readily reliquefied by adding water at the point of use.
A composition according to claims 1 to 10, where the liquid composition is a clear liquid with an NTU less than 40.
The clearness of the solution in relation to undissolved solids is further characterized by the turbidity. The Nephelometric Turbidity Unit (NTU) method can be used to measure the turbidity solution. The process involves shining a light source onto the sample and measuring the amount of light that is scattered by suspended particles in the solution. This measurement was taken by a photodetector at a 90-degree angle from the light source. The greater the amount of scattered light, the higher the turbidity of the sample. In a preferred embodiment of the current invention, the turbidity of the solution is less than 35 NTU, in a more preferred embodiment less than 30, in a most preferred embodiment less than 25. This allows for an essentially solid free solution, as the amount of undissolved solids is relatively low, as implicated by the NTU values.
Additionally, in a preferred embodiment the liquid composition comprises at least one further component, such as corrosion inhibitors, viscosity-enhancing agents, surfactants, pH stabilizers, biocides, and clay inhibitors. Industrial application for high density brine solutions often requires special adjustments, and in order to satisfy these circumstances additional components may be added in small amounts, preferably in less than 5% w/w, more preferably, below 2% w/w.
Clay minerals such as smectite, illite, and kaolinite are commonly found in subsurface formations encountered during drilling operations. These clay minerals have a natural affinity for water, and when they come into contact with water-based drilling fluids, they tend to absorb water, swell, and disperse. This can lead to several problems during drilling, including wellbore instability, stuck tubulars, increased fluid loss, drilling solution precipitation, reduced drilling performance, and formation damage.
Drilling fluid formulations can include inhibition additives to control the interaction between clay minerals and the drilling fluid. The main objective is to prevent or reduce clay swelling and dispersion to maintain wellbore stability and protect the formation. In a preferred embodiment of the present invention, other additives may be added to the composition to provide efficient function under such drilling conditions. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
Advantageously, the liquid composition can be pH adjusted with the selection of alkali phosphate salts and the additional component, but in some cases where extreme pH levels are required, additional components may be necessary. In some applications, biocides may be required to reduce microbial contamination, which is unlikely anyway due to the high salt concentrations of the liquid composition.
Preferably, the composition exhibits minimal impact to its environment, preferably including minimal environmental toxicity, specifically preferably inhibiting a low ECso value between 50 and 250 g/L, more preferably between 80 and 200 g/L, most preferably between 90 and 150 g/L.
The impact on the environment, especially in drilling and other industrial applications, is increasingly regulated, and moreover, it is a moral imperative in the development of new inventions. It is therefore an important concern of the inventors to have found a composition that uses phosphate salts - generally known for relatively low environmental impact and used as fertilizers - in addition with an environmentally friendly additive component, such as carboxylic acids from natural sources or naturally occurring carboxylic acids.
A variety of methods can be used to assess acute environmental toxicity. One method is a bioluminescence test according to regulatory standards such as DIN EN ISO 11348-3, which measures the inhibition of light emission from the marine bioluminescent bacterium Vibrio fischeri. The degree of toxicity can be expressed by the half-maximum effective concentration (EC50). In general, the biotoxicity of industrial chemicals can be classified into five levels based on ECs values: extremely toxic (ECso < 1 mg/L), very toxic (1 mg/L < ECso < 100 mg/L), moderately toxic (100 mg/L < ECso < 1000 mg/L), slightly toxic (1000 mg/L < ECso < 30000 mg/L), and non-toxic (ECso > 30000 mg/L).
In one embodiment, the toxicity (ECso in g/L) according to DIN EN ISO 11348-3 of a liquid composition according to the present invention is between 50 and 250 g/L, more preferably between 80 and 200 g/L, most preferably between 90 and 150 g/L. This ensures that the liquid composition has low to no toxicity to aquatic life and is suitable for use in industrial onshore and offshore operations.
In some preferred aspects of the current invention, the liquid composition exhibits specialized drilling features, such as low corrosiveness to drilling equipment and periphery infrastructure, good inhibition performance with clay minerals, and high compatibility with formation water. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
In the context of the present invention, particularly for use as a drilling fluid and/or other industrial applications such as a heat exchanger, corrosion refers to the deterioration or degradation of metal surfaces that come into contact with the fluid composition. It results from chemical reactions between the liquid composition and the metal components and leads to material loss, weakening of structures and possible operational and safety problems.
Corrosion can be quantified by measuring the mass loss of a sample. The corrosion may be determined using the mass loss according to
R= Mioss * 8.76 * 10%
Pre * A xt where CR is the calculated corrosion rate (mm/yr), miss is the mass loss of the sample (measured in grams), pre is the density of iron (equal to 7.85 g/cm°), A is the surface area (in cm?), and t is the exposure time (in hours).
A corrosion rate of less than 0.1 mm/yr is generally considered not severe, while a corrosion rate between 0.1 and 1.0 mm/yr is considered moderate. A corrosion rate exceeding 1.0 mm/yr is usually considered severe. Preferably, the corrosion rate is determined at elevated temperatures, such as 180 °C, in an autoclave to simulate the conditions during a high intensity application. In an preferred embodiment of the current invention, the corrosion rate of a steel used in industrial and mining operations, such as AISI 316L or a comparable austenitic steel, is less than 0.01 mm/yr, more preferably below 0.03 mm/yr, most preferably below 0.05 mm/yr.
Based on the results, it can be concluded that the liquid composition has low corrosiveness towards industrial equipment and infrastructure, making it a suitable choice as an oil servicing fluid. Therefore, the composition can be considered a viable option for use in oil drilling, deicing and heat transfer operations.
Formation water compatibility of drilling fluids refers to the ability of drilling fluids to coexist and interact with the water naturally present in the drilled formation. Formation water is the water that naturally occurs in the subsurface formations penetrated by the borehole.
The compatibility of drilling fluids with formation water is critical because it can affect drilling operations and the overall performance of the well. Incompatibilities can lead to a variety of problems, including damage to the formation, impaired wellbore stability, reduced drilling performance, and potentially harmful interactions between the drilling fluid and formation minerals or fluids. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
To ensure compatibility with formation water, drilling fluid formulations must be carefully developed and evaluated based on the specific characteristics of the formation being drilled.
The presence of certain ions in formation water can lead to undesirable reactions with drilling fluid components. For example, high levels of calcium or magnesium can lead to the formation of precipitates or gelation of certain drilling fluid additives. Furthermore, infiltration of drilling fluid filtrate into the formation can affect the permeability of the rock and damage the formation.
Compatibility considerations involve minimizing filtrate intrusion and the potential for clay swelling or migration of fines. In particular, wellbore stability must be maintained in applications where work is being performed in shales. Compatibility with formation water helps prevent swelling or fracturing of shale formations.
À static stability test can be performed to ensure that the formation can be combined. The potential drilling fluid is mixed in various ratios with simulated formation water as it occurs in natural rock formations. Preferably, the mixing ratios can be 25:75, 50:50, and 75:25. The mixtures are then thoroughly mixed and allowed to settle for a specified time, such as 3 hours and 48 hours. As a result of the test, there should be little or no evidence of segregation, gelation or settling.
In a preferred embodiment of the present invention, the liquid composition according to the present invention exhibits high compatibility with formation water in a static stability test and shows little or no evidence of segregation, gelation or settling after 3 or 48 hours, preferably in any mixing ratio, more preferably in ratios of 1:3 to 3:1.
By ensuring drilling fluids are compatible with formation water, operators can mitigate drilling challenges, reduce the risk of formation damage, optimize drilling performance and maintain wellbore integrity throughout the drilling process.
Furthermore, drilling in sandstone or clay formation requires inhibition control, such as clay swelling control, clay dispersion control sand stabilization and formation damage prevention.
Therefore, a liquid composition in accordance with the current invention shows clay and sandstone inhibition, providing a recovery rate (RR) of preferably of 98%, more preferably of 99%, most preferably of 100%.
The recovery rate can be determined with the following formula: RR = m4/Mo * 100%.
Sandstone materials and clay cuttings are treated with a 3% hydrogen peroxide solution, breaking them into smaller pieces, exposing them to the liquid composition and fresh water for reference, heated to 80°C for 30 minutes, and allowed to sit at room temperature for 7 days. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
After thoroughly rinsing and drying for 20 minutes at 130°C, the weight of the samples was LU103163 then measured, and the recovery rate was calculated.
Furthermore, this disclosure comprises a method for preparing a composition according to the current invention, wherein the liquid composition is made in-situ by a) formulating a alkali phosphate solution under stirring b) adding an additional component, preferably an carboxylic acid according to claims 2 or 3 under stirring, c) then cooling the solution to obtain a liquid composition in accordance with the current invention.
This method enables the preparation of an essentially solids-free, cold-stable liquid composition with exceptionally high densities as described herein. The addition of a carboxylic acid as an additional component makes this possible in comparison to the properties of alkali phosphate salt solutions known in the prior art, particularly potassium phosphate solutions, and is an extraordinary achievement of the inventors. Advantageously, the addition of the additional component during heating allows the solution to be prepared without precipitation, which would be possible because an alkali phosphate solution having the desired properties would precipitate at room temperature without the additional component.
An alkali phosphate solution in the spirit of the current invention is a solution of at least one alkali phosphate salt and/or a mixture of different alkali phosphate salts. It may be prepared by dissolving alkali phosphate salts in a solvent, preferably water, or particularly preferably by adding basic alkali salts, more preferably alkali hydroxides to phosphor-based acids, preferably orthophosphoric acid (HsPO4). An alkali phosphate solution may be stable only at elevated temperatures, such as 100 °C, or above 100 °C in an autoclave and precipitate at lower temperatures without the addition of the additional component in the spirit of the current invention.
In a preferred embodiment of the present invention, the method comprises heating the composition after addition of the additional component (step b) preferably to 70-120 °C, more preferably to 85-110 °C, for less than one hour, preferably less than 30 minutes.
This allows homogenization of the solution and production of a solids-free, substantially clear liquid composition. In some embodiments, an autoclave may be used to achieve temperatures above 100 °C. In a preferred embodiment, the composition is stirred during addition and heating to reduce the risk of agglomeration and to homogenize the liquid. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
Preferably, in an aspect of the invention related to the method of preparing the liquid composition, the alkali phosphate solution from step a) is prepared preferably from alkali phosphate salts and/or aqueous alkali metal phosphate salt solutions and/or by reacting basic alkali metal salts, more preferably alkali metal hydroxides, and phosphor-based acids, more preferably phosphoric acids and/or orthophosphoric acid. Advantageously, this may allow for a solvent free synthesis from readily available materials. The reaction of basic alkali salts and phosphorus-based acids is generally exothermic, which can be used as preheat, reducing the cost of heating the liquid composition during its preparation.
Basic alkali metal salts are salts of alkali metals with anions from weak bases, which react in turn basic. Examples may include but are not limited to alkali hydroxides, alkali carbonates, alkali hydrides. In a preferred embodiment, the basic alkali salts are preferably alkali hydroxides, since stoichiometric amounts of water are released in an exothermic reaction with acids, resulting in a highly concentrated alkali salt solution, while eliminating or reducing the need for additional external heating.
Phosphor-based acids are acids that contain phosphorus as the central element in their chemical structure. These acids are characterized by their ability to release hydrogen ions (protons) in aqueous solutions, making them acidic. Examples of phosphorus-based acids are orthophosphoric acid, pyrophosphoric acid, triphosphoric acid, and/or oligio- and polyphosphoric acids.
In a preferred embodiment of the present invention, the phosphorus-based acid is preferably orthophosphoric acid. The technical advantages of using orthophosphoric acid are that it is readily available.
In an alternative preferred embodiment, pyro- and triphosphoric acid are also preferably used.
Pyro- and triphosphoric acid are hygroscopic, which has the advantage of further increasing the concentration of a liquid composition containing alkali phosphate salts by reducing the water content due to chemical reactions.
In one embodiment of the current invention the stoichiometric ratio between phosphor-based acids, preferably phosphoric acid and basic alkali metal salts, preferably alkali metal hydroxides, is preferably in the range of 0.1 to 1.5, more preferably between 0.33 to 1. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
The stoichiometric ratio between the phosphorus-based acids is calculated using the acidic LU103163 protons of the phosphorus-based acids and dividing the number by the basic groups of the basic metal salt, i.e. the groups capable of accepting a proton. For example, orthophosphoric acid (HsPO4) has three acidic protons (3 H*), pyrophosphoric acid (H4P2O07) has 4 acidic protons (4 HY), and potassium hydroxide has one basic group (OH). Therefore, reacting one mole of orthophosphoric acid (HsPO4) with one mole of potassium hydroxide (KOH) leads to an stoichiometric ratio of 1, while reacting 1 mole HsPO4 with 3 moles of KOH leads to an ratio of 0.33. This has the effect of producing mixed alkali phosphate salts during the preparation of the liquid composition that can be used to optimize pH, densities, and other factors during the process without the need for additional components or expensive pre-made pure alkali phosphate solutions.
In a preferred embodiment the composition is stirred in total for up to 120 minutes. This allows for a homogenization and quick batch times, therefore reducing the reaction time and increasing the batch throughput.
In some embodiments, the invention provides the means for preparing a solid form of the composition by a) drying the liquid composition according to claims 1 to 19 at temperatures around 100°C until the water content is less than 10% w/w, b) grinding the solid composition to obtain a free flowing solid, thus yielding a solid form of the liquid composition according to claim 1 to 12.
Advantageously, this allows for improved transportation and storage by reducing the mass of the composition and eliminating the need for liquid handling containers. In some embodiments, after drying the liquid composition, a dried and sized free-flowing powder of the invention is produced by further crushing and sieving to provide a commercially available particulate free- flowing product.
The invention provides a method for preparing a composition from a solid form of the liquid composition, wherein the solid form is dissolved in a suitable amount of water to obtain a liquid composition according to the present invention.
The method includes dissolving the solid composition in a suitable amount of liquid, preferably water, moreover preferably between 10% and 70% w/w, to obtain a liquid composition having asolids content as described herein. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
Some applications may require different concentrations of liquid composition, for example, thawing ice may require a more dilute liquid composition than drilling applications, so dilution with water at the point of application dramatically reduces transportation costs.
According to the invention, the liquid composition can be used as a drilling, completing, or workover liquid in oil, gas and mining applications.
The advantageous physical and chemical properties of the liquid composition, especially the high, novel density combined with good environmental compatibility, stability, essential clarity of the liquid, formation compatibility and other advantages outlined herein predispose the composition for use in drilling applications.
Particularly preferably, a liquid composition based on alkali phosphate salts, most preferably potassium phosphate salts and gluconic acid and/or derivatives thereof as an additive having a density of at least 1.80 g/l can be used as a drilling, completion or processing fluid in oil, gas and mining applications. This high density was previously unattainable with potassium phosphate salts in the prior art, and it is a great achievement of the inventors to have found a high-density, sub-freezing stable, essentially solids-free fluid with the advantages described herein that is very attractive for this application.
Furthermore, the use of the liquid as a deicing agent is disclosed herein. Deicing agents are substances or chemical compounds used to remove or prevent the formation of ice and snow on surfaces, especially on transportation infrastructure such as roads, runways and sidewalks.
They are used to reduce hazards associated with ice formation and improve traction for vehicles and pedestrians. The excellent melting properties of the solution demonstrated in the embodiments predispose the liquid composition to compounding as a deicing agent. Above all, the good environmental compatibility should be emphasized at this point, especially in comparison with the frequently used calcium chloride.
In an aspect of the invention relating to heat transfer capability, the liquid composition can be used as a heat transfer fluid in industrial, pharmaceutical, food, feed and cosmetic applications.
The high density and viscosity, paired with the low corrosiveness enable the liquid composition to be used in a number of different industrial, pharmaceutical, food, feed, and cosmetic applications. Heat transfer fluids, also referred to as heat transfer liquids or thermofluids, are substances used in various pharmaceutical and industrial applications to transfer thermal energy from one location to another. These fluids are specifically designed to absorb, transport white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023 and release heat efficiently. A number of challenges are associated with this application, such LU103163 as a high heat tolerance, safety, and health considerations, especially in food and pharmaceutical applications.
Therefore, the fluid composition according to the invention may be effectively used as a heat transfer fluid due to its high temperature resistance and generally harmless environmental and health properties.
TPPG is the abbreviation of the liquid composition in accordance with the current invention.
Each instance of TPPG is an aspect of the current invention. In some examples of the invention, the amount of dissolved solids will be denotated behind TPPG, for example TPPG- 77 is a 77% w/w composition according to the current invention.
Each instance of TPPG is another aspect of the current invention and may be used for a range of applications, such as high w/w TPPGs, preferably TPPG-60 to TPPG-85, may be used as drilling fluid and are associated with high densities.
TKP is an abbreviation for tripotassium phosphate (KsPO4), also referred to as potassium phosphate, potassium phosphate tribasic, orthophosphoric acid tripotassium salt.
GDL is an abbreviation for glucono-5-lactone (alternatively: glucono-delta-lactone or glucono-1,5- lactone), which is the lactone (cyclic ester) of gluconic acid, a sugar acid, which may be an additional component in accordance with the current invention.
Room temperature according to the current invention is defined as 20 °C, unless stated otherwise.
The weight percentages are given as weight fractions of the dissolved solids and the total weight of the liquid composition according to the following formula: m . ww = —Msolids 1000
Mcomposition
Itis given in %, and may be referenced to as “w/w”, “wt%” and “by weight”. It may be calculated from the stoichiometric values from the used precursors and solutions or by gravimetric methods such as titration. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
EXAMPLES LU103163
The present invention is further described and illustrated in the following comparatives, experiments, drawings and examples, which are not intended to limit the scope of the invention in any manner.
Herein shows
Fig. 1: Relationship between mass fraction and density for a 77% w/w solution of a disclosed clear brine solution (TPPG-77)
Fig. 2: Relationship between temperature and density and temperature and viscosity for a 77% w/w solution of a disclosed clear brine solution (TPPG-77)
Fig. 3: Low temperature experiment for a 77% w/w solution of a disclosed clear brine solution (TPPG-77)
Fig. 4: Low temperature / TCT experiment for a 15.4% w/w solution of a disclosed clear brine solution (TPPG-77 (20%))
Fig. 5: Recovery rates as part of a formation inhibition experiment for a 70% w/w solution of a disclosed clear brine solution (TPPG-70)
Fig. 6: Biotoxicity evaluation of EC10, EC20 and EC50 values for a 77% w/w solution of a disclosed clear brine solution (TPPG-77)
Fig. 7: High temperature experiment for a 70% w/w solution of a disclosed clear brine solution (TPPG-70)
Fig. 8: Deicing efficacy experiment for a 40% w/w solution of a disclosed clear brine solution (TPPG-40)
Example 1 — Preparation of Composition
The preparation process of TPPG, a high-density, sub-zero stable clear liquid composition, according to the invention is outlined in this example.
As starting materials for the synthesis of this embodiment of TPPG, technical grade potassium hydroxide (KOH) with a purity of >90%, technical grade orthophosphoric acid (H3PO4) with a purity of >85%, and food grade D-Glucono-1,5-lactone or GDL (CeH+00s) with a purity of >99% were used. 35.689 of KOH was added to 24.449 of H3PO4 in a 5dl sealed thermo-glass beaker over 30 minutes with continuous stirring, resulting in an exothermic reaction. After completion of dosing the mixture was agitated for 15 minutes, then 5.00g of GDL was added. The mixture was white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023 heated with stirring for 15 minutes until reaching a temperature of 85°C to 110°C, becoming a LU103163 clear, light-yellow solution with a sweet scent. The mixture was stirred and cooled for 20 minutes, yielding a total reaction time of 80 minutes.
The final product was an aqueous, solid-free, light-yellow solution with a 76.78% w/w solid content, devoid of any scent.
Example 2 — Preparation of Salt
The preparation process of the TPPG salt, as an embodiment of the high-density, sub-zero stable clear liquid composition according to the invention, is outlined in this example. TPPG was formulated according to Example 1, then dehydrated in an oven at 110°C for 50 minutes.
The product was further crushed and sieved through a 1mm mesh to produce a white to off- white, odorless, dry, and free-flowing powder with a 91.59% w/w assay.
To verify the possibility of in situ preparation of the disclosed aqueous fluid at for instance a wellsite, the powder was rehydrated with agitation and minimal heating to achieve a 69.37% w/w assay. The powder fully dissolved, and the resulting aqueous solution had the desired visual properties of the disclosed fluid. The density of the solution at room temperature was around 1.790 g/cm*, which matched the predicted density of 1.797 g/cm?.
Thus, the (nearly) anhydrous, solid form of the disclosed high-density, sub-zero stable clear liquid composition can be used to easily create the desired fluid in situ on site, potentially offering storage and handling benefits compared to the aqueous solution.
Example 3 — Density Measurements
The density measurements of TPPG, a high-density, sub-zero stable clear liquid composition, according to the invention is outlined in this example. For the density measurements a TPPG preparation as described in Example 1 was used.
The relationship between solid concentration and density of TPPG was established through pycnometric analysis. The results are presented in Figure 1, showing the correlation between solid concentration and density in the range of 0% to 77% w/w. The highest density, 1.925 g/cm*, was reached at 77% w/w solid concentration and room temperature (25°C). The relationship can be approximated with a second-degree polynomial equation: white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023 p(E) = 0.00007 * € + 0.0066 * € + 1.0024, LU103163 where p is the density and § is the solid concentration expressed in percent (w/w). For example, a 70% (w/w) solution would have a density of 1.8074 g/cm?, calculated as follows: p(70) = 0.00007*70° + 0.0066*70 + 1.0024 = 1.8074.
The relationship between temperature and density of a 77% w/w solution of TPPG (TPPG-77) was established through measurements using a Westphal balance. Table 1 displays the density values of TPPG-77 at 9 temperature points ranging from 5°C to 85°C. These results are also illustrated in Figure 2.
Table 1. Density values for a 77% w/w solution of TPPG for different temperatures
Temperature / °C Density / g/cm? 5 1.947 1.936 25 1.925 35 1.920 45 1.913 55 1.907 65 1.899 75 1.894 85 1.892 15 The relationship between density and the weight percentage of GDL in the formulation of a 73.57% w/w solution of TPPG (TPPG-73.57) was established. Table 2 displays the density values of TPPG-73.57 for the two formulations 80:20 and 95:5 (TKP:GDL).
Table 2. Relationship between density and the weight percentage of GDL in the formulation of a 73.57% w/w solution of TPPG.
TKP/% GDL/% Density / g/cm? 80 20 1.745 95 5 1.852 white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
The density measurements results reveal that TPPG exhibits high density levels relative to the LU103163 amount of gluconic acid or its cyclic esters used, making it a suitable choice as a high-density completion fluid.
Example 4 — Viscosity Measurements
The viscosity measurements of TPPG, a high-density, sub-zero stable clear liquid composition, according to the invention is outlined in this example. For the viscosity measurements a TPPG preparation as described in Example 1 was used.
The relationship between temperature and viscosity of a 77% w/w solution of TPPG (TPPG- 77) was established through measurements using a falling ball viscometer, based on DIN 53015. Table 3 displays the viscosity values of TPPG-77 at 9 temperature points ranging from 5°C to 85°C. These results are also illustrated in Figure 2.
Table 3. Viscosity values for a 77% w/w solution of TPPG for different temperatures
Temperature / °C Viscosity / mPa*s 5 161715.4 15 31991.8 25 7818.8 35 2632.2 45 1076.8 55 519.6 65 284.5 75 168.6 85 106.2
The results of density measurements indicate that TPPG has relatively high viscosity levels, making it an excellent option for demanding well operations or certain heat transfer processes.
By reducing the solids content to 70% w/w, the viscosity of TPPG significantly decreases while still retaining a suitable high density of approximately 1.80 g/cm*. This makes the product suitable for a wide range of well conditions. By adjusting the solid content in the fluid, the viscosity can be altered to meet the specific conditions needed in the oil, gas and mining industry, as well as in deicing or heat transfer operations. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
Example 5 — pH Measurement LU103163
The pH measurements of TPPG, a high-density, sub-zero stable clear liquid composition, according to the invention is outlined in this example. For the pH measurements a TPPG preparation as described in Example 1 was used.
The pH value was determined using a Hanna Instruments Edge HI2020. A 10% solution of a 77% w/w solution of TPPG (TPPG-77) was made prior to the measurements. The results of the pH determination are presented in Table 4.
Table 4. pH values of a 10% TPPG-77 solution.
PH Temperature/°C
Measurement 1 11.95 233 0000
Measurement 2 11.94 23.2
Measurement 3 11.94 23.3
Average 11.94 23.3 -
Further, the relationship between pH and the weight percentage of GDL in the formulation of a 73.57% w/w solution of TPPG (TPPG-73.57) was established. The pH values of TPPG-73.57 for the two formulations 80:20 and 95:5 (TKP:GDL) were 11.64 and 12.47, indicating that a higher amount of GDL lowers the pH of the solution.
The pH measurements reveal that TPPG exhibits an apt pH value in the range of 11.5 to 12.5, making it a suitable choice as a high-density clear liquid composition for various industrial applications.
Example 6 — Turbidity Measurements
The turbidity of TPPG, a high-density, sub-zero stable clear liquid composition, according to the invention is outlined in this example. For the turbidity analysis, a TPPG preparation as described in Example 1 was used.
The Nephelometric Turbidity Unit (NTU) method was used to measure the turbidity of a 60% w/w solution of TPPG (TPPG-60). The process involved shining a light source onto the sample and measuring the amount of light that was scattered by suspended particles in the solution.
This measurement was taken by a photodetector at a 90-degree angle from the light source.
The greater the amount of scattered light, the higher the turbidity of the sample. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
The sample showed a NTU value of 20.7, signifying a relatively low number of solids. This LU103163 makes TPPG suitable for use in completion and workover operations as well as for heat transfer processes that require clear liquid compositions.
Example 7 — Temperature Tolerance Evaluation
The temperature tolerance of TPPG, a high-density, sub-zero stable clear liquid composition, according to the invention is outlined in this example. For the temperature tolerance analysis, a TPPG preparation as described in Example 1 was used. Low and high temperature tests and TCT (true crystallization temperature) assessments were performed.
Low temperature testing of a 77% w/w solution of TPPG (TPPG-77) was conducted by exposing the sample to 4°C for 30 days and to -18°C for 72 hours. During low temperature testing, no crystallization, solidification, separation, or visual changes were observed in the samples, with only an increase in viscosity noticeable in comparison to TPPG at room temperature. Upon returning to room temperature, the samples resumed their original physical properties.
The true crystallization temperature of a clear liquid composition determines the lowest temperature at which the fluid will start to solidify, which can affect its performance and cause operational difficulties during drilling. A test rig was established in accordance with EN ISO 13503-3:2005 to determine the crystallization temperature of a 15.4% w/w TPPG solution by preparing a 20% solution of TPPG-77 (TPPG-15.4). A double-walled glass reactor served as the core and contained isopropanol as a cooling medium. Samples (25 mL each) were placed in a thick-walled test tube in the cooling medium and stirred continuously using a magnetic stirrer plate. Two Pt100 thermal sensors automatically recorded the temperatures of both the sample and the cooling medium. A cryostat from Julabo was used to control the cooling of the double-walled reactor. The TCT of TPPG-15.4 was determined to be -3.9°C. For a 77% w/w solution of TPPG (TPPG-77) no crystallization was observed even at temperatures as low as -28.6°C. The TCT of TPPG-15.4 is depicted in Figure 4, and the low temperature analysis of
TPPG-77 is shown in Figure 3.
The results of the low temperature tests and TCT analyses indicate that TPPG has exceptional tolerance to low temperatures, making it suitable for use and storage in low temperature conditions.
High temperature testing of a 70% w/w solution of TPPG containing 5% GDL on a dry assay was conducted by exposing the sample to 150°C for 90 minutes and to a maximum white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023 temperature of 175°C. The results of the high temperature testing can be found in Table 5. LU103163
The temperature curve of the fluid is depicted in Figure 7.
Table 5. Results of the high temperature test. “Temperature / Density / LL pHi. Coloration Turbidity Result °C g/cm?
Safe Operating < 150 1.8083 12.47 Off-white Low
Temperature 150 - 170 1.7982 12.45 Yellow to Medium Maximum brown Temperature > 170 1.7921 12.36 Brown to High Unstable black
According to the results of the high temperature tests conducted on TPPG, it is safe to operate at temperatures up to 150°C, with maximum temperatures of 170°C. Although operations may be maintained even at temperatures above 170°C as only minor changes in density and pH occur, it should be noted that the fluid's performance may be compromised, affecting factors such as color and turbidity.
Example 8 — Environmental Toxicity Evaluation
The environmental toxicity evaluation of TPPG, a high-density, sub-zero stable clear liquid composition, according to the invention is outlined in this example. For the environmental toxicity evaluation, a TPPG preparation as described in Example 1 was used.
The acute environmental toxicity was assessed using a bioluminescence test in accordance with DIN EN ISO 11348-3, which measured the inhibition of the light emission of the marine bioluminescent bacterium Vibrio fischeri. The toxicity level was expressed using the half- maximal effective concentration (ECso). Typically, the biotoxicity of industrial chemicals can be classified into five levels based on ECso values: extremely toxic (ECso < 1 mg/L), highly toxic (1 mg/L < ECso < 100 mg/L), moderately toxic (100 mg/L < ECso < 1000 mg/L), slightly toxic (1000 mg/L < ECso < 30000 mg/L), and non-toxic (ECso > 30000 mg/L). The biotoxicity levels of TPPG are shown in Table 6.
Table 6. Summary of results for all endpoints at the end of exposure period: Critical effect and threshold concentration as observed at end of experimental time; EC: Effective concentration for XX% reduction; 95%-CL: 95% Confidence limits white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
ECio/ g/L EC2/g/L ECso/ g/L | Biotoxicity 52.50 65.12 98.31 Non-toxic 95%-CL lower 36.18 51.40 90.18 upper 62.09 73.13 111.58
The environmental toxicity assessment shows that TPPG with an ECso value of 98.31 g/L showcases low to no toxicity to aquatic life and is suitable for use in industrial on- and offshore operations. The results of this assessment are illustrated in Figure 6.
Example 9 — Corrosion Evaluation
The corrosion evaluation to drilling equipment of TPPG, a high-density, sub-zero stable clear liquid composition, according to the invention is outlined in this example. For the corrosion evaluation, a TPPG preparation as described in Example 1 was used.
The corrosion evaluation was performed by immersing a metal sample into a 64% TPPG solution and subjecting it to a temperature of 180°C for 72 hours in an autoclave. The evaluation was conducted on AISI 316L, an austenitic steel typically used in oil drilling applications for downhole equipment, wellheads, and subsea components as well as in the chemical, pharmaceutical, and food and beverage industry. The composition of AISI 316L can be found in Table 7, which provides a breakdown of its chemical elements and their respective percentages.
Table 7. Chemical composition of AISI 316L.
Cr/% Ni / % Mn/% Si/% C/% Mo/% P/% S/% N/% 16.00-18.00 10.00-14.00 2.00 1.00 0.03 2.00-3.00 0.045 0.03 0.10
To avoid galvanic effects between the metal sample and the autoclave, the contact points were insulated. The corrosion was determined using the mass loss according to
CR = (Mioss * 8.76 * 104) / (Pre * A * t), where CR is the calculated corrosion rate (mm/yr), miss is the mass loss of the sample (measured in grams), pre is the density of iron (equal to 7.85 g/cm°), A is the surface area (in cm?), and t is the exposure time (in hours). A corrosion rate of less than 0.1 mm/yr is generally considered not severe, while a corrosion rate between 0.1 and 1.0 mm/yr is considered white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023 moderate. A corrosion rate exceeding 1.0 mm/yr is usually considered severe. The corrosion LU103163 rate for TPPG can be found in Table 8.
Table 8. Corrosion evaluation.
Density / Temperature / Steel Corrosion Rate / Corrosion g/cm? °C Type mm/yr Result 1.712 180 AISI 316L 0.034 Low/Not severe
Based on the results, it can be concluded that TPPG has low corrosiveness towards industrial equipment and infrastructure, making it a suitable choice as an oil servicing fluid. Therefore,
TPPG can be considered a viable option for use in oil drilling, deicing and heat transfer operations.
Example 10 — Compatibility with Formation
The compatibility of the formation water and formation sediments with TPPG, a high-density, sub-zero stable clear liquid composition, according to the invention is outlined in this example.
For the compatibility analysis a TPPG preparation as described in Example 1 was used.
To assess the compatibility of a 60% w/w solution of TPPG (TPPG-60) with formation water, a static stability test was performed. Three mixtures were prepared by combining TPPG-60 and simulated formation water in ratios of 25:75, 50:50, and 75:25, then thoroughly mixed and allowed to settle for 3 hours and 48 hours. The appearance and physical properties of each fluid mixture were closely monitored and recorded. The composition of the simulated formation water can be found in Table 9.
Table 9. Simulated formation water composition.
Na*/K* Ca?/Mg? CI HCOs SO, | Salinity pH 3110 300 4949 500 100 | 8959 8.13 mg/L mg/L mg/L mg/L mg/L | mg/L
The results of the formation water compatibility test, especially of the 50:50 and 75:25 mixture, show that TPPG displayed no or minimal signs of separation, gelation, or scaling after 3 hours or 48 hours, demonstrating its compatibility with formation water and suitability as a high- density completion fluid. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
To evaluate the compatibility of a 70% w/w solution of TPPG (TPPG-70) with formation clay minerals and sandstone, an inhibition assessment was performed. This involved treating sandstone and clay cuttings with a 3% hydrogen peroxide solution, breaking them into smaller pieces, exposing them to TPPG-70 and fresh water, heating them to 80°C for 30 minutes, and allowing them to sit at room temperature for 7 days. After thoroughly rinsing and drying for 20 minutes at 130°C, the weight of the samples was then measured, and the recovery rate was calculated using:
RR=m4/Mo* 100% where RR represents the recovery rate, mg the mass of the sample prior to the inhibition assessment and my the mass of the dried sample after the inhibition assessment. In both sandstone and clay formations, TPPG exhibited a recovery rate (RR) exceeding 100%, indicating that no cutting minerals underwent solution transition. Furthermore, some TPPG or its constituents were absorbed into the formation and could not be removed despite thorough rinsing. The results of the inhibition assessment can be found in Table 10. These results are also illustrated in Figure 5.
Table 10. Results of Assessment on Inhibition.
Nr. Fluid Cutting Type _ mo/g mi/g RR/% 1 TPPG-70 Sandstone 47.07 48.50 103.04 2 Fresh water Sandstone 45.95 45.57 99.17 3 TPPG-70 Clay 27.45 27.70 100.91 4 Fresh water Clay 28.84 19.18 66.50
The results of the formation cuttings compatibility test showed that TPPG displays good clay- inhibition performance.
Example 11 - Thermal conductivity
The thermal conductivity of TPPG, a high-density, sub-zero stable clear liquid composition, according to the invention is outlined in this example. For the thermal conductivity evaluation, a TPPG preparation as described in Example 1 was used.
To assess the efficacy of TPPG-40, a 40% w/w solution of TPPG, as a heat transfer fluid, a thermal conductivity evaluation using the transient hot bridge (THB) method was conducted. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
A THB/B/Metal sensor calibrated at PMMA (A = 0.194 W/mK) was used to establish the thermal LU103163 conductivity.
The measurements show that TPPG-40 has a thermal conductivity of 0.558 W/mK at 20°C, indicating that it is well-suited for use as a heat transfer fluid.
Example 12 — Ice thawing capacity
The ice thawing evaluation of TPPG, a high-density, sub-zero stable clear liquid composition, according to the invention is outlined in this example. For the ice thawing evaluation, a TPPG preparation as described in Example 1 was used.
To determine the efficacy of ice thawing, various amounts of deicing agents were added to a beaker containing ice, and the weight loss after thawing was measured after a 10-minute period. A TPPG solution was compared to industry-standard deicing agents, calcium chloride, and potassium acetate. All samples were diluted to a 40% w/w solution. The mean thawing efficacy was determined according to n Mio Min
ATE = ye n wi i=1 A where ATE is the calculated mean thawing efficacy (measured in (%*m°)/g), Mio is the initial mass of the ice (measured in grams), mi; is the mass of the ice post melting (measured in grams), wi is the mass of the applied deicing agent (measured in grams) and A is the surface area of the ice were the deicing agent was applied to (measured in m2). The formula can be interpreted as the average fraction of ice that has melted due to the deicing agent, normalized by the mass of the deicing agent applied per unit area of ice surface, with the resulting unit representing the percentage of ice melted per gram of deicing agent applied per unit area of ice surface. A higher ATE value indicates greater effectiveness of a deicing agent in melting ice per unit mass and area of application within a specific time period. The ATE values for the studied deicing agents can be found in Table 11. Further Figure 8 depicts the relationship between the mass per unit area of ice surface and the thawing rate for the three deicing agents potassium acetate, TPPG, and calcium chloride. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
Table 11. ATE values for different commonly used deicing agents and TPPG. LU103163
Deicing agent ATE / %*m?/g
Potassium Acetate 0.05
TPPG 0.10
Calcium chloride 0.11
W
The evaluation of the ice thawing capacity revealed that TPPG exhibits ATE values twice as high as potassium acetate and comparable to calcium chloride expressing a high deicing efficacy, while avoiding the environmental downsides associated with calcium chloride. white ip | Patent & Legal
BRAL-0007-P-LU 30.06.2023
Claims (24)
1. A liquid composition, wherein the composition is essentially clear and comprises at least one alkali phosphate salt in an aqueous solution, wherein the alkali phosphate salt comprises a potassium counter cation, characterized in that the composition comprises at least one additional component, wherein the additional component is a solubilizing agent, which increases the solubility of the alkali phosphate salt, and wherein the additional component is a carboxylic acid RCO»Y, RCO,Y = (MO LR Y=Li, Na, K, H, T R, -C(O)OR oO wherein the carboxylic acid RCO-Y is a hydroxy acid, wherein the acid is provided in its free form and/or its alkali salts and/or its cyclic esters and/or its anhydrides, and wherein R is an optionally substituted C- to Ce linear, branched or cyclic alkyl group or an optionally substituted aryl group, and wherein the total solids in solution are between 10% to 90% by weight of the composition.
2. Composition according to claim 1, wherein the additional component is a sugar acid and/or its derivates.
3. Composition according to claim 2, wherein the sugar acid and/or its derivates is a gluconic acid and/or its alkali salts and/or its cyclic esters and/or its anhydrides.
4. Composition according to any claims 1 to 3, wherein the alkali phosphate salt comprising a potassium counter cation is selected from the list consisting of dipotassium phosphate and/or, tripotassium phosphate and/or potassium pyrophosphate.
5. Composition according to any claims 1 to 4, wherein the additional component is added in a fraction between 1% to 30% of the alkali phosphate salt.
6. Composition according to claims 1 to 5, wherein the composition has a density LU103163 between 1.20 g/cm? and 2.40 g/cm? as a clear solution at 20°C.
7. Composition according to claim 1 to 6, wherein the composition has a pH value in the range of 7.0 to 13.0.
8. Composition according to claims 1 to 7, wherein the working temperature of the liquid, where it does not precipitate or thermally degrade, is between -20 to 180 °C.
9. Composition according to claims 1 to 8, wherein the liquid composition does not form precipitates when stored at a temperature of at preferably at least -5 °C to room temperature.
10. Composition according to claims 1 to 9, wherein the liquid composition is a clear liquid with an NTU less than 40.
11. Composition according to claims 1 to 10, wherein the liquid composition comprises at least one further component, such as corrosion inhibitors, viscosity-enhancing agents, surfactants, pH stabilizers, biocides, and clay inhibitors.
12. Composition according to claims 1 to 11, wherein the composition exhibits minimal impact to its environment, specifically inhibiting a low ECso value between 50 and 250 g/L.
13. Composition according to claims 1 to 12, wherein the liquid composition exhibits specialized drilling features, such as low corrosiveness to drilling equipment and periphery infrastructure with a corrosion rate of less than 0.01 mm/yr, a good inhibition performance with clay minerals, with an retention rate of 98%, and high compatibility with formation water.
14. A method for preparing a composition according to claims 1 to 13, wherein the liquid composition is made in-situ by a) formulating a alkali phosphate solution under stirring b) adding an additional component, preferably an carboxylic acid according to claims 2 or 3 under stirring, c) then cooling the solution to obtain a liquid composition in accordance with any of the claims 1 to 14.
15. Method according to claim 14, wherein said composition is heated after the addition of the additional component (step b) to 70-120 °C for less than one hour.
16. Method according to claims 14 or 15, where the alkali phosphate solution from claim 15, a) is prepared from alkali phosphate salts and/or aqueous alkali phosphate salt solutions and/or by reacting basic alkali metal salts, and phosphor-based acids, selected from phosphoric acids and/or orthophosphoric acid.
17. Method according to claim 16, wherein the stoichiometric ratio between phosphor- based acids and basic alkali metal salts is in the range of 0.1 to 1.5.
18. Method according to any claims 14 to 17, wherein said composition is stirred in total for up to 120 minutes.
19. A method for preparing a solid form of the composition according to claims 1 to 13 by a) drying the liquid composition according to claims 1 to 13 at temperatures around 100°C until the water content is less than 10% w/w, b) grinding the solid composition to obtain a free flowing solid, thus yielding a solid form of the liquid composition according to claim 1 to 12.
20. A method for preparing a composition according to claim 1 to 13, wherein the solid form of the liquid composition is dissolved in an appropriate amount of water to yield a liquid composition with solids contend according to claim 5, to yield a liquid composition according to claim 1 to 13.
21. Use of a composition according to any of the claims 1 to 13 as a drilling, completing, or workover liquid in oil, gas and mining applications.
22. Use of a composition according to any of the claims 1 to 13 as a deicing agent.
23. Use of a composition according to any of the claims 1 to 13 as a heat transfer liquid in industrial, pharmaceutical, food, feed, and cosmetic applications.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU103163A LU103163B1 (en) | 2023-06-30 | 2023-06-30 | High-density, sub-zero stable clear liquid composition and the method for producing thereof |
| PCT/EP2024/068122 WO2025003322A1 (en) | 2023-06-30 | 2024-06-27 | High-density, sub-zero stable clear liquid composition and the method for producing thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU103163A LU103163B1 (en) | 2023-06-30 | 2023-06-30 | High-density, sub-zero stable clear liquid composition and the method for producing thereof |
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| Publication Number | Publication Date |
|---|---|
| LU103163B1 true LU103163B1 (en) | 2024-12-30 |
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| LU103163A LU103163B1 (en) | 2023-06-30 | 2023-06-30 | High-density, sub-zero stable clear liquid composition and the method for producing thereof |
Country Status (2)
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| LU (1) | LU103163B1 (en) |
| WO (1) | WO2025003322A1 (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986001253A1 (en) | 1984-08-07 | 1986-02-27 | The Dow Chemical Company | High-density brine fluid and use in servicing wellbores |
| EP0375214A1 (en) | 1988-12-20 | 1990-06-27 | BP Chemicals Limited | Deicing compositions |
| US5104562A (en) | 1988-11-03 | 1992-04-14 | Eszakmagyarorszagi Vegyimuvek | Coolant composition containing potassium formate and potassium acetate and method of use |
| EP0572113A1 (en) | 1992-05-29 | 1993-12-01 | BP Chemicals Limited | Aqueous brines |
| WO1999023188A1 (en) | 1997-11-05 | 1999-05-14 | Great Lakes Chemical Corporation | Novel carboxylate-based well bore treatment fluids |
| US6015535A (en) | 1995-04-06 | 2000-01-18 | Cabot Corporation | Process for producing purified cesium compound from cesium alum |
| EP0922079B1 (en) | 1996-08-27 | 2000-05-24 | Verdugt B.V. | Well servicing fluids |
| US6149834A (en) | 1998-10-27 | 2000-11-21 | The Dow Chemical Company | Corrosion inhibited chloride salt de-icers |
| US6616739B1 (en) | 2002-10-29 | 2003-09-09 | General Chemical Industrial Products Inc. | Corrosion inhibited chloride salt compositions |
| CN1794924A (en) * | 2003-03-26 | 2006-06-28 | 诺维信公司 | Method of preparing vegetable puree |
| US20100305010A1 (en) | 2009-05-28 | 2010-12-02 | Clearwater International, Llc | High density phosphate brines and methods for making and using same |
| US9090807B2 (en) | 2010-12-17 | 2015-07-28 | Halliburton Energy Services, Inc. | Phosphate based blend for drilling and completion fluid |
| EP3178901A1 (en) | 2015-12-07 | 2017-06-14 | Addcon Europe GmbH | High density borehole fluids having low crystallization temperatures |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8435896B2 (en) * | 2011-03-03 | 2013-05-07 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Stable, concentratable chemical mechanical polishing composition and methods relating thereto |
| CN110872570B (en) * | 2019-10-22 | 2024-03-19 | 广东第二师范学院 | Solution formula for efficiently producing sulfide by utilizing different soils and method for preparing sulfide |
-
2023
- 2023-06-30 LU LU103163A patent/LU103163B1/en active IP Right Grant
-
2024
- 2024-06-27 WO PCT/EP2024/068122 patent/WO2025003322A1/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986001253A1 (en) | 1984-08-07 | 1986-02-27 | The Dow Chemical Company | High-density brine fluid and use in servicing wellbores |
| US5104562A (en) | 1988-11-03 | 1992-04-14 | Eszakmagyarorszagi Vegyimuvek | Coolant composition containing potassium formate and potassium acetate and method of use |
| EP0375214A1 (en) | 1988-12-20 | 1990-06-27 | BP Chemicals Limited | Deicing compositions |
| EP0572113A1 (en) | 1992-05-29 | 1993-12-01 | BP Chemicals Limited | Aqueous brines |
| US6015535A (en) | 1995-04-06 | 2000-01-18 | Cabot Corporation | Process for producing purified cesium compound from cesium alum |
| EP0922079B1 (en) | 1996-08-27 | 2000-05-24 | Verdugt B.V. | Well servicing fluids |
| WO1999023188A1 (en) | 1997-11-05 | 1999-05-14 | Great Lakes Chemical Corporation | Novel carboxylate-based well bore treatment fluids |
| US6149834A (en) | 1998-10-27 | 2000-11-21 | The Dow Chemical Company | Corrosion inhibited chloride salt de-icers |
| US6616739B1 (en) | 2002-10-29 | 2003-09-09 | General Chemical Industrial Products Inc. | Corrosion inhibited chloride salt compositions |
| CN1794924A (en) * | 2003-03-26 | 2006-06-28 | 诺维信公司 | Method of preparing vegetable puree |
| US20100305010A1 (en) | 2009-05-28 | 2010-12-02 | Clearwater International, Llc | High density phosphate brines and methods for making and using same |
| US9090807B2 (en) | 2010-12-17 | 2015-07-28 | Halliburton Energy Services, Inc. | Phosphate based blend for drilling and completion fluid |
| EP3178901A1 (en) | 2015-12-07 | 2017-06-14 | Addcon Europe GmbH | High density borehole fluids having low crystallization temperatures |
Non-Patent Citations (1)
| Title |
|---|
| XIA GUOBIN ET AL: "Simultaneous preparation of naturally abundant and rare catechins by tannase-mediated biotransformation combining high speed counter current chromatography", FOOD CHEMISTRY, ELSEVIER LTD, NL, vol. 151, 26 November 2013 (2013-11-26), pages 380 - 384, XP028668516, ISSN: 0308-8146, DOI: 10.1016/J.FOODCHEM.2013.11.090 * |
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|---|---|
| WO2025003322A1 (en) | 2025-01-02 |
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