EP1414753B1 - Procede de regeneration de fluides halogenes uses - Google Patents
Procede de regeneration de fluides halogenes uses Download PDFInfo
- Publication number
- EP1414753B1 EP1414753B1 EP02721386A EP02721386A EP1414753B1 EP 1414753 B1 EP1414753 B1 EP 1414753B1 EP 02721386 A EP02721386 A EP 02721386A EP 02721386 A EP02721386 A EP 02721386A EP 1414753 B1 EP1414753 B1 EP 1414753B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluid
- acid
- metallic
- alkali
- halide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000012530 fluid Substances 0.000 title claims description 180
- 238000000034 method Methods 0.000 title claims description 84
- 150000004820 halides Chemical class 0.000 title claims description 73
- 230000008929 regeneration Effects 0.000 title claims description 11
- 238000011069 regeneration method Methods 0.000 title claims description 11
- 239000002253 acid Substances 0.000 claims description 65
- 239000003513 alkali Substances 0.000 claims description 38
- 239000010953 base metal Substances 0.000 claims description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 239000012535 impurity Substances 0.000 claims description 30
- 239000003792 electrolyte Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 26
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 25
- 239000003638 chemical reducing agent Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 18
- 229910052794 bromium Inorganic materials 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- -1 calcium halide Chemical class 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 230000001965 increasing effect Effects 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004519 grease Substances 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- IHYNKGRWCDKNEG-UHFFFAOYSA-N n-(4-bromophenyl)-2,6-dihydroxybenzamide Chemical compound OC1=CC=CC(O)=C1C(=O)NC1=CC=C(Br)C=C1 IHYNKGRWCDKNEG-UHFFFAOYSA-N 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical class [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical class [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims 2
- 150000005309 metal halides Chemical class 0.000 claims 2
- 230000003472 neutralizing effect Effects 0.000 claims 2
- 239000002518 antifoaming agent Substances 0.000 claims 1
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical class [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical class [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims 1
- 238000005187 foaming Methods 0.000 claims 1
- 229910001507 metal halide Inorganic materials 0.000 claims 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical class [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims 1
- 239000012267 brine Substances 0.000 description 28
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 28
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 18
- 238000005553 drilling Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 229940102001 zinc bromide Drugs 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 7
- 239000001110 calcium chloride Substances 0.000 description 7
- 229910001628 calcium chloride Inorganic materials 0.000 description 7
- 150000001457 metallic cations Chemical class 0.000 description 7
- 229910001622 calcium bromide Inorganic materials 0.000 description 6
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 6
- 230000020477 pH reduction Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003129 oil well Substances 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001649 bromium compounds Chemical class 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- 229910001625 strontium bromide Inorganic materials 0.000 description 1
- 229940074155 strontium bromide Drugs 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
- E21B21/06—Arrangements for treating drilling fluids outside the borehole
- E21B21/068—Arrangements for treating drilling fluids outside the borehole using chemical treatment
Definitions
- the present invention relates to a method for regenerating used halide fluids. More specifically the invention relates to enhancing used halide fluids by removing impurities, increasing the density of the halide fluid, and increasing the concentration of electrolytes and adjusting the true crystallization temperature of the fluid.
- Clear brine fluids used in deep oil and gas wells or other industrial and agricultural processes become diluted due to the increased concentration of water in the system.
- these fluids can become contaminated with impurities such as metallic cations, hydrocarbons and organic polymers.
- impurities such as metallic cations, hydrocarbons and organic polymers.
- TCT true crystallization temperature
- Brine fluids are expensive to produce. Due to the high amounts of chlorides, bromides and, in some brines, zinc that are present in the used fluids, the disposal of used clear brine fluids is also very costly. It is highly desirable that a used halide fluid be recuperated, regenerated, and recycled back into operation.
- the density of the solution that is being regenerated will drop substantially.
- the change in the density also changes the TCT of the fluid, so that the fluid is unable to meet the specification set by the needs of the oil field for TCT value of the fluid.
- Using the methods of evaporation or blending to increase density or to adjust the TCT is time consuming, expensive and difficult to control.
- What is needed is a method that allows for an efficient regeneration of the recuperated used brine fluid in a controlled manner.
- a method that removes metallic cationic impurities and avoids both precipitation and conditions that increase dilution and adversely affects the TCT of the fluid by addition of water into the recuperated brine fluid is also desirable.
- the present invention relates to an innovative method for regeneration of used halide fluids that have been recuperated from industrial processes such as oil and gas drilling, agricultural chemical processes, metal plating or water treatment.
- Used halide fluids, bromide or chloride brines for example are usually contaminated with soluble and insoluble impurities.
- these recuperated, used fluids typically have a density greater than 1.078 kg/l (9.0 lb/gal) but less than the required density of a desired drilling fluid.
- one preferred method of regeneration of a used halide fluid comprising soluble and insoluble impurities and having a density greater than 1.078 kg/l (9.0 lb/gal) comprises adding an acid to the used halide fluid.
- the used halide fluid is then contacted with a halogen, bromine for example, to increase fluid density and oxidize impurities.
- a halogen-generating species such as oxyhalogen salts, hypochloride, hypobromide and the like can be used to increase density, adjust TCT and oxidize impurities.
- the used halide fluid if comprising a high solid content, should be filtered to remove the solids prior to acidification.
- a reducing agent is added to convert halogen to halide ion while maintaining the temperature at a minimum of 10°C.
- the fluid is then contacted with an alkali to neutralize any excess acid. Any suspended solid impurities remaining can be separated from the fluid.
- the pH can be maintained within a range of approximately 0.0 to 5.5.
- the alkali and alkali earth metal cations this range can be from 0.0 to 10.0.
- the acid used for acidification can comprise hydrobromic acid.
- the acid can comprise hydrochloric acid or an organic acid.
- the reducing agent is preferably selected from a group consisting of ammonia, sulfur, hydrogen sulfide, sodium bisulfide, metallic zinc, metallic iron, metallic copper, metallic nickel, metallic cadmium, metallic cobalt, metallic aluminium, metallic chromium, metallic manganese, organic acids, alcohols and aldehydes.
- the electrolyte to be enhanced in the used fluid is a salt of an alkali metal, an alkali earth metal or a base metal.
- the alkali earth metal is calcium
- the alkali used to neutralize excess acid can be calcium hydroxide or calcium oxide.
- the alkali earth metal in the used fluid is strontium
- the alkali used to neutralize excess acid is preferably strontium hydroxide or strontium oxide.
- the alkali used to neutralize excess acid is an alkali metal hydroxide, sodium hydroxide or potassium hydroxide for example.
- Ammonia can also be used to neutralize excess acid.
- the alkali used to neutralize excess acid is a base metal hydroxide or base metal oxide, such as zinc hydroxide, zinc oxide, copper hydroxide or copper oxide.
- the alkali used to neutralize excess acid is aluminium hydroxide or aluminium oxide, manganese hydroxide or manganese oxide, chromium hydroxide or chromium oxide.
- the recuperated used halide fluid is piped into a reactor after density and chemical composition have been determined according to steps (a) and (b).
- the acid, halogen, reducing agent and alkali can be piped into reactor along with the fluid.
- the acid, halogen, reducing agent and alkali can be transported separately to the reactor. Bromine is one preferred halogen used in regeneration.
- Another preferred method regenerates a used halide fluid comprising a blend of a group of halide salts, such as calcium chloride, calcium bromide, zinc bromide or a combination thereof.
- the starting brine fluid will typically have a density greater than 1.078 kg/l (9.0 lb/gal) and contain both soluble and insoluble impurities.
- This method comprises the steps of (1) adding acid to the used halide fluid so that the pH is within a range of approximately 0.0 to 5.5 for a base metal or 0 to 10.0 for alkali and alkali earth metal systems; (2) contacting the used halide fluid with bromine to increase the density to at least 1.198 kg/l (10.0 lb/gal.) and oxidize soluble impurities; (3) adding a reducing agent while maintaining the temperature at a minimum of 10°C; (4) contacting the fluid with an alkali to neutralize excess acid; and (5) separating any suspended solid impurities from the fluid.
- the Figure is a schematic of one embodiment of the method of the invention.
- the present invention relates to an innovative method for regeneration of used halide fluids.
- the used halide fluids calcium or zinc brine for example, have been recuperated from industrial processes such as oil and gas drilling, agricultural chemical processes, metal plating or water treatment.
- the recuperated halides often contain soluble and insoluble impurities and can be so diluted that the density of the halides and concentrations of the electrolytes are not acceptable for continued industrial operations.
- brine fluids used in oil and gas drilling For the purpose of illustration, reference hereafter is made, for convenience, to brine fluids used in oil and gas drilling.
- Clear brine fluids used in deep oil and gas wells become diluted due to the increased concentration of water in the operations system. Additionally, they become contaminated with impurities such as metallic cations, hydrocarbons such as oils, as well as organic polymers, solids, muds and sands. As a result, the overall quality of the brine fluid is reduced; the density in particular drops, and the true crystallization temperature (TCT) changes to a level that does not conform to product specifications.
- TCT true crystallization temperature
- Brine fluids are expensive to produce. Also, due to the hazardously high amounts of chlorides, bromides and zinc present in brine fluids, the disposal of used clear brine fluids can be very costly. Regeneration of the used fluids by the method of this invention is performed in a controlled manner so that the regenerated brine can economically be recycled back into the systems.
- a used halide fluid 60 such as a drilling fluid
- a used halide fluid 60 can comprise a density above water, 1.078 kg/l (9.0 lb/gal) for example, but nothing enough to perform during the drilling operations, especially in deeper or higher pressure wells.
- a halide fluid has a specific density targeted to the type of drilling operation and/or pressure of the well.
- Clear brines used as completion, workover and drilling fluids comprise a density higher than the density of water, 0.995 kg/l (8.3 lb/gal), typically within a range of approximately 1.366 kg/l (11.4 lb/gal) to 1.917 kg/l (16 lb/gal), and even possibly as high as 2.756 kg/l (23.0 lb/gal) depending an the targeted use of the brine.
- Electrolytes of alkali metals, alkali earth metals and base metals are commonly used in the composition of these brine fluids and are often selected according to their ability to increase the density of the drilling fluid.
- the density of the used drilling fluids is restored to a density that is necessary for well operations thereby regenerating the fluid to its useful state.
- the practice of this invention also allows for the adjustment of the true crystallization temperature (TCT) of the fluid.
- TCT is a function of the density.
- the operator of the production wells checks the specifications for the TCT of the electrolytes within the fluids being used. These substrates adversely affect the properties of the fluid that are desirable for the oil and gas industries.
- the Figure illustrates used fluid 60 piped into a reactor 10.
- the composition and density of the used halide fluid 60 determines the parameters of the method of the reaction. Knowledge of this composition and the properties of the fluid, i.e., electrolytes present, initial pH, density, and impurities present, is critical to determine the procedure and chemicals used during the method.
- the electrolytes present in the recuperated, used halide fluid 60 can comprise an alkali metal, alkali earth metal or a base metal salt. These salts can be selected from a group of salts comprising sodium chloride, calcium chloride, zinc chloride, sodium bromide, calcium bromide, zinc bromide or blends thereof can be employed. Strontium chloride, strontium bromide, copper chloride, copper bromide, nickel chloride, nickel bromide, aluminium chloride or aluminium bromide can also be considered.
- a used brine fluid 60 often comprises a blend of any of these metal salts, calcium chloride, calcium bromide and/or zinc bromide for example.
- metal present in the recuperated used halide can comprise zinc, copper, cobalt, cadmium, nickel, potassium, cesium, lithium, barium, magnesium, aluminium, manganese, chromium or combinations thereof.
- the halide ions present can comprise bromide or chloride as illustrated above, but iodide ions are also within the scope of this invention.
- the manner in which these various electrolytes are blended depends largely on the density and crystallization temperature requirements for the particular brine fluid needed. A double or triple electrolyte blend can be used to obtain a higher density clear brine fluid.
- bromide electrolytes When blending a relatively high-density clear brine fluid, bromide electrolytes provide higher flexibility than the relatively low-density chloride electrolytes.
- the stability and TCT of the blended finished product also depends on the proportion of the individual electrolytes in the composition.
- brine fluids with a high concentration of calcium chloride may precipitate carbonates or sulfates, which are often present in formation waters of oil or gas wells.
- Zinc bromide brines can be used to provide high density, calcium-free brine fluids which do not precipitate anions such as carbonates and sulfates due to the acidic nature of the zinc ion.
- Such zinc bromide brines can also be used to adjust the TCT of the fluid.
- the density and TCT of the brine fluid can be adjusted by altering the concentration of the electrolyte or electrolytes in the solution.
- the parameters, acidity, temperature etc., of the method must be adjusted during the regeneration to encompass the blend of electrolytes present.
- the used halide fluids should be analyzed and evaluated for their solids content.
- the solids are removed by a solid-liquid separation method known in the art prior to the treatment of the fluids within the reactor 10. High solid content in the feed to the reactor 10 can result in increased undesirable impurities in the finished product and will also affect other properties of the fluids.
- the initial used halide fluid 60 piped into the reactor 10 is a fluid that was diluted during well operations and can comprise soluble and insoluble impurities such as metallic cations, hydrocarbons, polymers, suspended solids, drill cuttings and sand or grit. Because of dilution by contact with waters found in wells, these used fluids typically have less than the desired density of the required drilling fluid, but a density greater than 1.078 kg/l (9.0 lb/gal).
- the used halide fluid if comprising a high solid content, should be filtered to remove the solids prior to acidification. The method operates more efficiently if oil and grease residues and other solids are removed prior to the process.
- a separation process prior to acidification can remove oil and grease.
- the separation process can include destabilization of the emulsified oil followed by physical separation of the oily phase by a suitable process known in the art.
- One primary purpose of regenerating used halide fluids according to the method of this invention is to replace the electrolytes lost during well operations or industrial use of the fluid.
- the initial density of the recuperated halide fluid is calculated and the chemical composition analyzed. After analysis, the selection and amount of the proper alkali used to neutralize excess acid and restore lost electrolytes can be made. If the recuperated halide fluid is calcium chloride, for example, calcium oxide can be used to neutralize excess acid thereby restoring calcium ions.
- adding acid 50 to the used halide fluid 60 acidifies the fluid.
- the composition of the initial used halide fluid 60 can comprise aqueous zinc bromide or aqueous calcium bromide.
- a blend of chlorides and bromides of calcium and zinc in various proportions can be used.
- Acidification is required to avoid precipitation of the metallic salts, particularly where zinc and calcium are present.
- the used halide comprises base metals, a pH within a range of 0 to 6, preferably 0 to 5.5, is therefore preferred.
- the used halide comprises alkali or alkali earth metals, a pH within a range of 0 to 10, is preferred.
- the acid 50 used for acidification can comprise hydrobromic acid.
- the acid can comprise hydrochloric acid or an organic acid.
- the used halide fluid is then contacted with bromine.
- Bromine is effective to increase fluid density, adjust true crystallization temperature and removes or destroys impurities.
- Impurities can comprise metallic cations, hydrocarbons or polymers.
- the used halide fluid can be contacted with a bromine-generating species.
- bromine enhances the bromide ions available in the fluid so as to return the used halide fluid to the desired density for its specific use. Bromine also functions to oxidize impurities such as metallic cations, and the polymers and hydrocarbons found in the used fluid. If polymers are present, which is usually the case since various polymers are used as viscosifiers, oxidation is necessary to destroy these polymers.
- bromine does not increase the pH of the fluids that can promote unwanted precipitation of the metals. Compared to peroxides, bromine increases the density of the fluid rather than reducing it.
- the bromine is added while maintaining the temperature at a minimum of 10°C, especially when adding bromine to a blend of used halides.
- a cooler 100 can be used to control the rate of the reaction by maintaining the desired reaction temperature. In another preferred embodiment, the temperature is maintained at a minimum of 20°C. With the addition of bromine, the resulting TCT can be adjusted to avoid the precipitation of electrolytes, which can reduce the density of the fluid.
- a reducing agent 30 is added in a controlled manner to combine with and remove excess bromine.
- the addition of the reducing agent is controlled by maintaining the temperature at a minimum of approximately 10°C.
- the reducing agent is preferably selected from a group consisting of ammonia, sulfur, hydrogen sulfide, sodium bisulfide, metallic zinc, metallic iron, metallic copper, metallic nickel, metallic cadmium, metallic cobalt, metallic aluminium, metallic manganese, metallic chromium, organic acids, alcohols and aldehydes.
- the fluid is contacted with an alkali 20 to neutralize any excess acid.
- a base metal, an alkali metal and an alkali earth metal can be present in the used fluid.
- the composition and density of the base metal is determined prior to the halide fluid 60 entering the reactor 10.
- the metallic cations must be restored to the original density required for the useful function of the halide brine in the well.
- the alkali earth metal in the recuperated, halide fluid is calcium
- the alkali used to neutralize excess acid can be calcium hydroxide or calcium oxide.
- the alkali used to neutralize excess acid is preferably strontium hydroxide or strontium oxide.
- the alkali used to neutralize excess acid can be an alkali metal hydroxide. Where sodium is the alkali metal, the alkali used to neutralize excess acid is sodium hydroxide. Where the electrolyte that is to be restored is a base metal salt, the alkali used to neutralize excess acid can be a base metal oxide. When a base metal is used to neutralize excess acid, measures should be taken to vent the hydrogen gas that is emitted from the process. Depending an the composition of the used halide fluid to be regenerated, the base metal oxide is selected from a group consisting of zinc oxide, copper oxide, cobalt oxide, cadmium oxide or nickel oxide.
- the alkali used to neutralize excess acid is a base metal hydroxide.
- the base metal hydroxide can be selected from a group of base metals consisting of zinc, copper, cobalt, cadmium or nickel.
- the alkali used to neutralize excess acid is ammonia.
- the alkali 20 is a base metal or a base metal oxide
- the reducing agent 30 is p-formaldehyde
- the halogen 40 is bromine and the acid 50 used during the method is hydrobromic acid.
- the alkali is lime
- the reducing agent is ammonia
- the halogen is bromine
- the acid is hydrobromic acid.
- Ammonia is one preferred reducing agent in an alkali and alkali earth metal system and p-formaldehyde is the preferred reducing agent in a base metal system.
- the equipment used to perform the method of this invention can be straightforward and quite simple. Basically, a reaction tank or pipe, one or more pumps and storage tanks are required.
- the steps performed during the method are performed in a mixed reactor, preferably a stirred reactor or a tube reactor 10.
- the recuperated used halide fluid is piped into the reactor 10 along with the bromine, acid 50, reducing agent 30 and alkali 20 so that the various chemical solutions are combined in the influent pipe and then mixed within the reactor 10.
- the influent chemical solutions can be piped in separately.
- the base metals used to enhance the electrolytes can be placed in a reactor along with used halide fluid. Bromine, acid, a reducing agent and alkali can then be piped into the reactor either separately or together in one pipeline.
- Meters can be strategically placed along the influent pipeline and effluent pipeline to monitor the properties of the solutions: oxidation-reduction potential (ORP), pH and density. Alternatively, the properties can be measured manually.
- the meters comprise an ORP meter, a pH meter and a density meter.
- the chemical reaction is continued and the effluent product returned to the reactor until the desired levels of density, oxidation-reduction potential and pH are achieved.
- the reaction process can be carried out as a batch process or a continuous process.
- a cooler 100 is used to maintain the lower temperatures. Separation of the resulting fluid from any suspended solid can be performed by several known methods. A gravity settler 90 is one. Alternatively, separation of the resulting fluid from any suspended solid is performed in a clarifier. A centrifuge or pressure filter or vacuum filter can also be used to separate solids from the resulting product, independently or as a subsequent process to a clarifier.
- a 500 ml sample of a recovered completion fluid from an oil well with density of 1.194 kg/l (15.98 lb/gal) and iron content of 540 mg/kg was placed in a glass beaker and kept stirred using an electrically driven stirrer. To this 10 ml of liquid bromine was introduced. Using a hot plate the temperature of the reaction fluid was raised to 148°F (64.4°C). The solution was kept stirred at this temperature for 1 hour, which followed by addition of 2.9 g of p-formaldehyde as the reducing agent. Zinc oxide was added on as a required base to neutralize the excess acid of the fluid. The final fluid was filtered and analyzed for density and iron content, which respectively were determined to be 2.146 kg/l (17.91 lb/gal) and 35 mg/kg.
- a 500 ml sample of a recovered completion fluid from an oil well of Example 1 was placed in a glass beaker and kept stirred using an electrically driven stirrer. To this 20 ml of liquid bromine was introduced, while using a hot plate the temperature of the reaction solution was raised to 102°F (38.9°C). The reaction fluid was kept stirred at this temperature for 1 hour, which was followed by addition of 5.9 g of p-formaldehyde as the reducing agent. Zinc oxide was added on as a required base to neutralize the excess acidity of the reaction fluid. The final fluid was filtered and analyzed. The iron content of the final fluid was determined to be 40 mg/kg.
- Example 4 test On a 500 ml sample of the same fluid that was used in Example 4 test was conducted. In this case, while the liquid bromine addition was maintained at 20 ml, the reaction suspension was heated to about 180°F (82.2°C) for 1.7 hrs. 5.9 g of p-formaldehyde was used as the reducing agent. Similar to Example 4, lime was used for the neutralization of excess acid content. The final reaction fluid was filtered and analyzed. The density and iron content were determined to be 1.605 kg/l (13.4 lb/gal) and 10 mg/kg, respectively.
- Example 7 Test described in Example 7 was repeated, while in this case zinc oxide was used for the neutralization of excess acid, replacing lime of Example 7.
- the density and iron content of the final filtered fluid were measured to be 1.926 kg/l (16.08 lb/gal) and 44 mg/kg, respectively.
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Claims (37)
- Procédé de régénération de fluides halogénures usés contenant des impuretés solubles et insolubles et présentant une densité supérieure à 1,078 kg/l (9,0 lb/gal), ce procédé comportant :a) l'addition d'acide au fluide halogénure usé ;b) la mise en contact du fluide halogénure usé avec un halogène afin d'augmenter la densité du fluide, d'ajuster la température réelle de cristallisation et d'oxyder les impuretés ;c) l'addition d'un agent réducteur tout en maintenant la température à une valeur minimale de 10°C ;d) la mise en contact du fluide avec de l'alcali pour neutraliser l'excès d'acide ;e) la séparation de toutes les impuretés solides en suspension du fluide.
- Procédé selon la revendication 1 dans lequel le fluide halogénure usé est mis en contact avec une espèce générant des halogènes.
- Procédé selon l'une quelconque des revendications précédentes dans lequel la température du fluide est maintenue au-dessus de la température réelle de cristallisation des électrolytes à l'intérieur du fluide.
- Procédé selon l'une quelconque des revendications précédentes dans lequel le pH maintenu pendant le procédé est dans une plage d'environ 0 à 10,0.
- Procédé selon l'une quelconque des revendications précédentes dans lequel l'acide ajouté à l'étape a) contient de l'acide hydrobromique.
- Procédé selon l'une quelconque des revendications précédentes dans lequel l'acide ajouté à l'étape a) contient de l'acide chlorhydrique.
- Procédé selon l'une quelconque des revendications précédentes dans lequel l'acide ajouté à l'étape a) contient un acide organique.
- Procédé selon l'une quelconque des revendications précédentes dans lequel l'agent réducteur est sélectionné dans un groupe comprenant : ammoniac, soufre, hydrogène sulfuré, bisulfure de sodium, zinc, fer, cuivre, nickel, cadmium, cobalt, aluminium, manganèse, chrome, acides organiques, alcools et aldéhydes.
- Procédé selon l'une quelconque des revendications précédentes dans lequel le fluide usé contient un métal alcalino-terreux.
- Procédé selon la revendication 9 dans lequel le métal alcalino-terreux est du calcium et l'alcali utilisé pour la neutralisation de l'acide en excès est de l'hydroxyde de calcium.
- Procédé selon la revendication 9 dans lequel le métal alcalino-terreux présent dans le fluide usé est du calcium et l'alcali utilisé pour la neutralisation de l'acide en excès est de l'oxyde de calcium.
- Procédé selon la revendication 9 dans lequel le métal alcalino-terreux présent dans le fluide usé est du strontium et l'alcali utilisé pour la neutralisation de l'acide en excès est de l'hydroxyde de strontium.
- Procédé selon la revendication 9 dans lequel le métal alcalino-terreux présent dans le fluide usé est du strontium et l'alcali utilisé pour la neutralisation de l'acide en excès est de l'oxyde de strontium.
- Procédé selon l'une quelconque des revendications précédentes dans lequel l'alcali utilisé pour la neutralisation de l'acide en excès est un hydroxyde de métal alcalin.
- Procédé selon l'une quelconque des revendications précédentes dans lequel l'alcali utilisé pour la neutralisation de l'acide en excès est un hydroxyde de sodium.
- Procédé selon l'une quelconque des revendications précédentes dans lequel le fluide halogénure usé contient un métal basique et l'alcali utilisé pour la neutralisation de l'acide en excès est un oxyde de métal basique.
- Procédé selon la revendication 16 dans lequel l'oxyde de métal basique est sélectionné dans un groupe d'oxydes comprenant l'oxyde de zinc, l'oxyde de cuivre, l'oxyde de cobalt, l'oxyde de cadmium ou l'oxyde de nickel.
- Procédé selon l'une quelconque des revendications précédentes dans lequel le fluide halogénure usé contient un métal basique et l'alcali utilisé pour la neutralisation de l'acide en excès est un hydroxyde de métal basique.
- Procédé selon la revendication 18 dans lequel l'hydroxyde de métal basique est sélectionné dans un groupe d'hydroxydes de métal basique comprenant des hydroxydes de zinc, de cuivre, de cobalt, de cadmium ou de nickel.
- Procédé selon l'une quelconque des revendications précédentes dans lequel un métal basique est utilisé pour neutraliser l'acide en excès.
- Procédé selon l'une quelconque des revendications précédentes dans lequel l'alcali utilisé pour la neutralisation de l'acide en excès est de l'ammoniac.
- Procédé selon l'une quelconque des revendications précédentes dans lequel les étapes a) à d) se déroulent dans un réacteur mixte.
- Procédé selon l'une quelconque des revendications précédentes dans lequel la séparation du fluide résultant des corps solides en suspension s'effectue dans un décanteur par gravité.
- Procédé selon l'une quelconque des revendications précédentes dans lequel la séparation du fluide résultant des corps solides en suspension s'effectue dans un clarificateur.
- Procédé selon l'une quelconque des revendications précédentes dans lequel la séparation du fluide résultant des corps solides en suspension s'effectue dans une centrifugeuse.
- Procédé selon l'une quelconque des revendications précédentes dans lequel la séparation du fluide résultant des corps solides en suspension s'effectue dans un filtre sous pression.
- Procédé selon l'une quelconque des revendications précédentes dans lequel un agent antimousse est utilisé pour contrôler la mousse en excès dans le conteneur de réaction.
- Procédé selon la revendication 1 dans lequel le fluide halogénure usé est un fluide halogénure de métal basique et dans lequel l'étape consistant à ajouter de l'acide se poursuit jusqu'à ce que le pH se situe dans une plage comprise entre 0 et 5,5, l'étape consistant en une mise en contact avec un halogène se poursuit jusqu'à ce que la densité ait augmenté pour atteindre au moins 1,198 kg/l (10 lb/gal), la température réelle de cristallisation soit ajustée et les impuretés oxydées, et l'étape de neutralisation de l'acide en excès comprend l'utilisation d'un oxyde de métal basique.
- Procédé selon la revendication 28 dans lequel l'agent réducteur est sélectionné dans un groupe comprenant : ammoniac, soufre, hydrogène sulfuré, bisulfure de sodium, zinc, fer, cuivre, nickel, cadmium, cobalt, aluminium, manganèse, chrome, acides organiques, alcools et aldéhydes.
- Procédé selon la revendication 1 dans lequel le fluide halogénure usé est un fluide halogénure usé de métal alcalino-terreux et dans lequel l'étape consistant à ajouter de l'acide continue jusqu'à ce que le pH se situe dans une plage comprise entre 0 et 10,0, l'étape de mise en contact avec un halogène se poursuit jusqu'à ce que la densité ait augmenté pour atteindre au moins 1,198 kg/l (10 lb/gal), la température réelle de cristallisation soit ajustée et les impuretés oxydées, et l'étape de neutralisation de l'acide en excès comprend l'utilisation d'un oxyde de métal alcalino-terreux.
- Procédé selon la revendication 1 dans lequel le fluide halogénure usé contient un mélange d'halogénure de calcium et d'halogénure de zinc d'une densité supérieure à 1,078 kg/l (9,0 lb/gal), et dans lequel l'étape consistant à ajouter de l'acide continue jusqu'à ce que le pH se situe dans une plage comprise entre 0 et 10,0, l'étape de mise en contact avec du brome se poursuit jusqu'à ce que la densité ait augmenté pour atteindre au moins 1,198 kg/l (10 lb/gal), la température réelle de cristallisation soit ajustée et les impuretés soient oxydées.
- Procédé selon l'une quelconque des revendications précédentes comprenant en outre :f) la détermination de la densité du fluide halogénure usé ;g) l'analyse de la composition chimique et de la teneur en corps solides du fluide halogénure usé ; eth) l'élimination des corps solides contenus dans le fluide halogénure usé avant l'addition d'acide au fluide halogénure usé.
- Procédé selon la revendication 32 comprenant en outre :i) la détermination de la température réelle de cristallisation ;j) l'analyse de la teneur en huiles et graisses du fluide halogénure usé ; etk) l'élimination des corps solides, huiles et graisses du fluide halogénure usé avant l'addition d'acide au fluide halogénure usé.
- Procédé selon les revendications 32 et 33 comprenant en outre l'analyse de la teneur en polymère du fluide halogénure usé.
- Procédé selon l'une quelconque des revendications précédentes dans lequel l'acide ajouté au fluide halogénure usé est sélectionné dans un groupe comprenant de l'acide hydrobromique, de l'acide chlorhydrique et de l'acide organique et dans lequel l'agent réducteur est un p-formaldéhyde.
- Procédé selon l'une quelconque des revendications précédentes dans lequel le fluide halogénure usé est mis en contact avec une espèce générant du bromure afin d'augmenter la densité du fluide, d'ajuster la température réelle de cristallisation et d'oxyder les impuretés.
- Procédé selon l'une quelconque des revendications précédentes dans lequel le fluide est mis en contact avec un alcali sélectionné dans un groupe comprenant des oxydes de métal basique, des oxydes de métal alcalino-terreux et des métaux basiques pour la neutralisation de l'acide en excès.
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PCT/US2002/007622 WO2002074699A2 (fr) | 2001-03-15 | 2002-03-14 | Procede de regeneration de fluides halogenes uses |
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CN109020001A (zh) * | 2018-09-10 | 2018-12-18 | 青海瑞能新型燃料科技有限公司 | 一种锂电池生产过程中含醇废液综合回收方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4895665A (en) * | 1989-04-26 | 1990-01-23 | George D. Smith | Method for treating and reclaiming oil and gas well working fluids and drilling pits |
US5254257A (en) * | 1993-01-19 | 1993-10-19 | Culligan International Company | Reclaiming of spent brine |
-
2002
- 2002-03-14 WO PCT/US2002/007622 patent/WO2002074699A2/fr not_active Application Discontinuation
- 2002-03-14 CN CN02809287.2A patent/CN1278949C/zh not_active Expired - Fee Related
- 2002-03-14 AU AU2002252321A patent/AU2002252321A1/en not_active Abandoned
- 2002-03-14 EP EP02721386A patent/EP1414753B9/fr not_active Expired - Lifetime
- 2002-03-14 GB GB0321133A patent/GB2388592B/en not_active Revoked
- 2002-03-14 IL IL15785202A patent/IL157852A0/xx active IP Right Grant
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2003
- 2003-09-10 IL IL157852A patent/IL157852A/en unknown
- 2003-09-12 NO NO20034061A patent/NO324398B1/no not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
WO2002074699A3 (fr) | 2004-02-19 |
AU2002252321A1 (en) | 2002-10-03 |
WO2002074699A2 (fr) | 2002-09-26 |
IL157852A (en) | 2006-07-05 |
GB2388592B (en) | 2004-11-24 |
NO324398B1 (no) | 2007-10-01 |
EP1414753B9 (fr) | 2006-08-23 |
EP1414753A2 (fr) | 2004-05-06 |
NO20034061L (no) | 2003-11-14 |
GB0321133D0 (en) | 2003-10-08 |
NO20034061D0 (no) | 2003-09-12 |
CN1278949C (zh) | 2006-10-11 |
IL157852A0 (en) | 2004-03-28 |
CN1630618A (zh) | 2005-06-22 |
GB2388592A (en) | 2003-11-19 |
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