CN104583372A - In-situ method and system for removing heavy metals from produced fluids - Google Patents
In-situ method and system for removing heavy metals from produced fluids Download PDFInfo
- Publication number
- CN104583372A CN104583372A CN201380025179.XA CN201380025179A CN104583372A CN 104583372 A CN104583372 A CN 104583372A CN 201380025179 A CN201380025179 A CN 201380025179A CN 104583372 A CN104583372 A CN 104583372A
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- Prior art keywords
- heavy metal
- hydrocarbon
- fixative
- dilution
- stratum
- Prior art date
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 159
- 238000000034 method Methods 0.000 title claims abstract description 85
- 239000012530 fluid Substances 0.000 title abstract description 60
- 238000011065 in-situ storage Methods 0.000 title abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 111
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 94
- 238000010790 dilution Methods 0.000 claims abstract description 85
- 239000012895 dilution Substances 0.000 claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 55
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 42
- 238000011084 recovery Methods 0.000 claims abstract description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims description 110
- 239000000834 fixative Substances 0.000 claims description 100
- 150000004696 coordination complex Chemical class 0.000 claims description 46
- 238000005755 formation reaction Methods 0.000 claims description 39
- 238000004519 manufacturing process Methods 0.000 claims description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 19
- 239000011435 rock Substances 0.000 claims description 15
- 230000000717 retained effect Effects 0.000 claims description 14
- -1 alkali metal hydrosulfide Chemical class 0.000 claims description 13
- 239000003345 natural gas Substances 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 239000005077 polysulfide Substances 0.000 claims description 5
- 229920001021 polysulfide Polymers 0.000 claims description 5
- 150000008117 polysulfides Polymers 0.000 claims description 5
- 229940100892 mercury compound Drugs 0.000 claims description 3
- 150000002731 mercury compounds Chemical class 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical group [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims description 3
- 150000008116 organic polysulfides Chemical group 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims 3
- 239000003208 petroleum Substances 0.000 claims 2
- 229920000642 polymer Polymers 0.000 claims 2
- 150000003464 sulfur compounds Chemical class 0.000 claims 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000002347 injection Methods 0.000 abstract description 17
- 239000007924 injection Substances 0.000 abstract description 17
- 229910052785 arsenic Inorganic materials 0.000 abstract description 14
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 12
- 239000007789 gas Substances 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 abstract 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 28
- 239000010779 crude oil Substances 0.000 description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- 239000013535 sea water Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 229910019093 NaOCl Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910052956 cinnabar Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 244000264242 Descurainia sophia Species 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000003653 coastal water Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008398 formation water Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052569 sulfide mineral Inorganic materials 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000012988 Dithioester Substances 0.000 description 1
- ZQZFYGIXNQKOAV-OCEACIFDSA-N Droloxifene Chemical compound C=1C=CC=CC=1C(/CC)=C(C=1C=C(O)C=CC=1)\C1=CC=C(OCCN(C)C)C=C1 ZQZFYGIXNQKOAV-OCEACIFDSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 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
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 241000872931 Myoporum sandwicense Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 description 1
- 229910052964 arsenopyrite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000009296 electrodeionization Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000450 iodine oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229940074994 mercuric sulfate Drugs 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- ZTEHTGMWGUKFNE-UHFFFAOYSA-N methyl 3-[[2-(diaminomethylideneamino)-1,3-thiazol-4-yl]methylsulfanyl]propanimidate Chemical compound COC(=N)CCSCC1=CSC(N=C(N)N)=N1 ZTEHTGMWGUKFNE-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007843 reactive sulfur species Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 239000011697 sodium iodate Substances 0.000 description 1
- 235000015281 sodium iodate Nutrition 0.000 description 1
- 229940032753 sodium iodate Drugs 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical group [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- XPDICGYEJXYUDW-UHFFFAOYSA-N tetraarsenic tetrasulfide Chemical compound S1[As]2S[As]3[As]1S[As]2S3 XPDICGYEJXYUDW-UHFFFAOYSA-N 0.000 description 1
- MSLRPWGRFCKNIZ-UHFFFAOYSA-J tetrasodium;hydrogen peroxide;dicarbonate Chemical compound [Na+].[Na+].[Na+].[Na+].OO.OO.OO.[O-]C([O-])=O.[O-]C([O-])=O MSLRPWGRFCKNIZ-UHFFFAOYSA-J 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical compound C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/34—Arrangements for separating materials produced by the well
- E21B43/35—Arrangements for separating materials produced by the well specially adapted for separating solids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/22—Compounds containing sulfur, selenium, or tellurium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/06—Metal salts, or metal salts deposited on a carrier
- C10G29/10—Sulfides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/28—Organic compounds not containing metal atoms containing sulfur as the only hetero atom, e.g. mercaptans, or sulfur and oxygen as the only hetero atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4037—In-situ processes
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Abstract
Methods and systems relate to the in-situ removal of heavy metals such as mercury, arsenic, etc., from produced fluids such as gases and crudes from a subterranean hydrocarbon-bearing formation. A sufficient amount of a fixing agent is injected into formation with a dilution fluid. The fixing agent reacts with the heavy metals forming precipitate, or is extracted heavy metals into the dilution fluid as soluble complexes. In one embodiment, the heavy metal precipitates remain in the formation. After the recovery of the produced fluid, the dilution fluid containing the heavy metal complexes is separated from the produced fluid, generating a treated produced fluid having a reduced concentration of heavy metals. In one embodiment, the dilution fluid is water, and the wastewater containing the heavy metal complexes after recovery can be recycled by injection into a reservoir.
Description
Cross-reference to related applications
According to 35USC 119, this application claims the interests that the applying date is the U.S. Patent Application Serial Number 61/647,983 and 61/647,999 on May 16th, 2012.This application claims to above-mentioned priority with from its interests, by reference its disclosure is incorporated herein.
Technical field
The present invention relates generally to removing from hydrocarbon fluid (such as crude oil and gas) and comprise technique, the method and system of the heavy metal of mercury.
Background technology
Heavy metal can be present in various types of produced fluid with trace, such as appropriate hydrocarbon gas and crude oil.Can change from lower than analysis detectable limit to several thousand ppbw (ppb calculated by weight) according to the described amount in source.
Disclose the fluid in-situ treatment method for heavy metals removal.U.S. Patent Publication No. 2011/0253375 discloses from reservoir effluent, remove mercury equipment and correlation technique, and described method by placing the material being designed to be adsorbed onto by mercury near wellbore locations, and makes described reservoir effluent flow through sorbent material.U.S. Patent Publication No. 2012/0073811 discloses the mercury minimizing technology by injecting solid absorbent in the well to the subsurface reservoir crossed containing hydrocarbon products.
The production of oil and natural gas is usually along with the production of water.Production water can be made up of formation water (the natural water be present in described reservoir) or the water be injected in advance in described stratum.Along with the maturation of the reservoir of gathering, the water yield of generation increases.In development and production operation, production water is maximum single fluid stream.Every day, american petroleum and natural gas manufacturer take the production water on 6,000 ten thousand barrels, earth's surface to.
Still need just in the method for production source improvement of removal heavy metal from output stream, especially for the method for the improvement of removing mercury.
Summary of the invention
On the one hand, the present invention relates to recovery of hydrocarbons from underground hydrocarbon formations from described hydrocarbon, remove the method for heavy metal simultaneously.Described method comprises: the fixative be exposed in dilution by the heavy metal in described hydrocarbon, makes described fixative and described heavy metal react the heavy metal complex be formed in described dilution; To gather described hydrocarbon and containing the dilution of described heavy metal complex as mixture from described stratum with via producing well.
On the other hand, the present invention relates to recovery of hydrocarbons from underground hydrocarbon formations from described hydrocarbon, remove the method for heavy metal simultaneously.Described method comprises: the fixative be exposed in dilution by the heavy metal in described hydrocarbon, described fixative and described heavy metal is reacted be formed in described reservoir to precipitate and the insoluble heavy metal complex be retained in described reservoir; To gather described hydrocarbon and containing the dilution of described heavy metal complex as mixture from described stratum with via producing well.
On the other hand, the present invention relates to recovery of hydrocarbons from underground hydrocarbon formations from described hydrocarbon, remove the method for heavy metal simultaneously.Described method comprises: stratum described in pressure break is to produce crack; Dilution containing fixative is provided, described fixative and described heavy metal is reacted in described stratum, is formed in the heavy metal complex in described dilution; The dilution of gathering containing described heavy metal complex; With the hydrocarbon of the heavy metal concentration with reduction of gathering from described stratum via producing well.
On the other hand, the present invention relates to the in-situ method removing heavy metal while recovery of hydrocarbons from underground hydrocarbon formations from described hydrocarbon.Described method comprises: stratum described in pressure break is to produce crack; Dilution containing fixative is provided, makes described fixative at least partially be adsorbed in crack in described stratum or rock; Reducing pressure makes described dilution be refluxed by well; Make described hydrocarbon by having crack and the rock of the fixative be attracted on it, the heavy metal wherein in described hydrocarbon and described fixative react and form heavy metal complex; With described hydrocarbon of gathering from described stratum via well.
On the other hand, the present invention relates to recovery of hydrocarbons from underground hydrocarbon formations from described hydrocarbon, remove the method for heavy metal simultaneously.Described method comprises: stratum described in pressure break is to produce crack; Dilution containing fixative is provided, described fixative is diffused in crack in described stratum or rock to react with the heavy metal in described hydrocarbon; The dilution of gathering containing described heavy metal complex; With the hydrocarbon of the heavy metal concentration with reduction of gathering from described stratum via producing well.
Still on the other hand, the present invention relates to the system at recovery of hydrocarbons situ removal heavy metal hydrocarbon from underground hydrocarbon formations.This system comprises: be drilled into and comprise well in the subsurface formations of hydrocarbon and platform upper production facility.Described platform upper production facility is used for the Storage and Processing production water of gathering from subsurface formations and is injected in described well by the production water of the process containing described fixative.
Accompanying drawing is sketched
Fig. 1 is the schematic diagram of the embodiment of the in-situ system of removal heavy metal from produced fluid.
Fig. 2 be for while recovery of oil and from described oil of gathering the schematic diagram of second embodiment of the in-situ system of removal heavy metal.
Detailed Description Of The Invention
Term below will to be used in whole manual and will to have following implication, except as otherwise noted.
" hydrocarbon " refers to hydrocarbon flow, such as crude oil and/or natural gas.
" produced fluid " refers to appropriate hydrocarbon gas and/or crude oil.Produced fluid can exchange with hydro carbons and use.
" crude oil " refers to hydrocarbon material, comprises the crude oil and condensate that are generally liquid form.Under the formation condition of some temperature and/or pressure, described crude oil can be solid phase.Under certain conditions, described crude oil can be the liquid phase of the very thickness of slowly flowing, if flowing.
" producing well " is produced fluid is transported to earth's surface by the geo-logical terrain from oil-containing well by it, and no matter described surface is water or land.When the described crude oil from stratum arrives ground, provide ground installation for the treatment of with processing it.
" platform upper production facility " refers to the ground hardware at sea oil platform or platform Connecting groups, such as oil production plants and drilling equipment.
" Injection Well " is the well passed into from described ground installation by least one inorganic agent by it described geo-logical terrain.In one embodiment, well is alternately to produce and injection way use.A period of time, described well can be used for material to be injected in described stratum.Then the operating condition adjusted in described well flows in described well to allow crude oil, is recycled to ground installation from it.
" trace " refers to the amount of the heavy metal in produced fluid.Described amount changes according to the source of described fluid and the type of heavy metal, such as, from several ppb to as high as 30,000ppb mercury and arsenic.
" heavy metal " refers to gold, silver, mercury, osmium, ruthenium, uranium, cadmium, tin, lead, selenium and arsenic.Although description in this article refers to mercury and removes, in one embodiment, heavy metal described in one or more is removed in described process.
" recirculation water " refers to the water flowing back into described ground after the part as strengthening oil recovery operation (such as, hydraulic fracturing operations) is placed in subsurface formations.
" production water " refers to the water generated in the production of oil and natural gas, comprise formation water (the natural water be present in reservoir), and the water injecting and be injected into stratum in advance that to be injected by matrix or rupture, it can be any connate water, the water in aquifer, seawater, desalted water, recirculation water, the water byproduct of industry and their combination.
" mercuric sulphide " can exchange with HgS and use, and refers to mercurous sulfide, mercuric sulphide or their mixture, and it can be any common phase of cinnabar, metacinnabarite, super cinnabar and their combination.Usually, mercuric sulphide exists with the form with the mercuric sulphide of the stoichiometric equivalents of every mole of mercury ion 1 mole of sulfidion.
The present invention relates to the method from produced fluid (natural gas and crude oil) situ removing heavy metal (such as mercury, arsenic etc.) from underground hydrocarbon formations.Extracting in the process of described produced fluid from described stratum, be injected into by fixative in described stratum, described fixative and described heavy metal react and form sediment and/or soluble heavy metal compound.The sediment formed and/or the amount of soluble heavy metal compound depend on amount and the type of the type of the mercury be present in described stratum and the fixative of use.
produced fluid containing heavy metal:heavy metal (such as lead, zinc, mercury, silver, selenium, arsenic etc.) can be present in all types of hydrocarbon flow (such as former oil and gas) with trace.The producer can expect removal heavy metal from crude oil, such as mercury and lead.The amount of mercury and/or arsenic can change to several thousand ppb from lower than analysis detectable limit according to raw material sources.
Arsenic species can be present in produced fluid in a variety of manners, include but not limited to: triphenylarsine (Ph
3as), triphenylarsine oxide (Ph
3asO), arsenic sulfide mineral (such as, As
4s
4or AsS or As
2s
3), metallic arsenic sulfide mineral (such as, FeAsS; (Co, Ni, Fe) AsS; (Fe, Co) AsS), selenides (such as, the As of arsenic
2se
5, As
2se
3), the reactive sulfur species of arsenic, organo-arsenic species and the inorganic arsenic that remains in little water droplet.
Mercury can with Elemental Mercury Hg
0, ionic mercury, inorganic mercury compound and/or organomercurial compound be present in produced fluid.Example includes but not limited to: the selenides of mercury halide, mercurous chloride, mercury oxide, mercuric sulphide, mercuric sulfate, mereurous sulfate, mercury, the hydroxide of mercury, organomercurial compound and their mixture.Mercury can as being existed by the particulate Hg of filtration or centrifugal removing from hydro carbons.Described particulate Hg is mainly nonvolatile in one embodiment.
In one embodiment, described produced fluid is the crude oil containing at least 50ppbw mercury.In another embodiment, described mercury level is at least 100ppbw.In an embodiment of mercurous crude oil, the described mercury being less than 50% removes (or being nonvolatile more than the described mercury of 50%) by stripping.In another embodiment, the described mercury of in described crude oil at least 65% is nonvolatile.In the 3rd embodiment, the described mercury of at least 75% is grain type or non-volatile type.
the original position of heavy metal is removed:in one embodiment, removal and the produced fluid in described subsurface reservoir of heavy metal (such as mercury and arsenic) are synchronous by gathering of injecting of thinner.In the method, in described well, produce oil and/or natural gas, the fixative of q.s is joined the removal being used for heavy metal in described stratum.
In one embodiment, described original position is removed and is occurred with water filling simultaneously, in another embodiment, occurs with fracturing process simultaneously.Pressure break is the method increasing the production of former oil and gas from the reservoir of fracture.Crack can be produced in the earth formation by methods known in the art, such as, pulsed power energy, gas pressure break, blast, plasma exciatiaon, fracturing etc.Water filling (Water injection) or water flooding recovery (waterf looding) are the methods of the extensive use improving oil recovery, wherein water is used as dilution, it is injected in rock stratum by Injection Well eye system, to promote that hydrocarbon is from gathering subsurface formations.In one embodiment, by fracturing fluid to be enough to expand the pressure that closes on described well or the crack in described well and speed is injected in described well.Described fracturing fluid is made to be immersed in a period of time in formation rock, from a few hours to a couple of days.Described fracturing fluid is the proppant containing described crack being remained on when impressed pressure alleviates holding state, and the dilution of the fixative for removing heavy metal of q.s.Described fracturing fluid also can be acid (such as HCl), with the fracture faces of etch in described stratum to be formed with the conduction pathway being beneficial to oil recovery.
In one embodiment, described fixative to be at least partially diffused in described formation fracture and to react with the heavy metal be embedded in described stratum, is formed in the heavy metal complex in described pressure break (dilution) fluid.In one embodiment, after the direction reversion that described pressure reduces and described fluid flows, the fluid containing the heavy metal extracted is back to surface for gathering and process subsequently, to remove heavy metal and other pollutants of extraction.In another embodiment, described fixative is at least partially adsorbed onto on reservoir rock in described immersion process, obtains " rock processed " of the fixative with embedding.
When described flow reversal and described hydrocarbon stream crosses the described rock processed time, the fixative of described heavy metal and described embedding reacts and forms heavy metal complex.In some embodiments, described heavy metal complex is embedded into and remains in described formation fracture, making when produced fluid is gathered from described producing well, effectively not having the produced fluid of the well of described fixative to have lower heavy metal concentration than coming in comfortable described fracturing fluid.
In one embodiment, the described heavy metal complex of at least 25% is retained in described formation fracture; In second embodiment, the described heavy metal complex of at least 50% is retained in described formation fracture; And in the 3rd embodiment, at least 75%.When described fixative exhausts from described stratum, the heavy metal amount of increase will be detected in described produced fluid of gathering, to make the supply of new fixative to be injected in described stratum.In one embodiment, the amount being retained in the heavy metal (such as mercury) in described stratum can be measured by the concentration measuring original position ground materials before or after drilling well and punching.Described amount can by measuring the adsorption analysis of the sample (such as hole sample, cutting waste material, production water etc. from described stratum) from described stratum.
In one embodiment, described fixative to be joined in dilution (such as water) to be injected in described well on continuous or intermittent basis in any stage of gathering.Itself and other additive (such as, proppant, surfactant, electrolyte etc.) can be added in described dilution together.Also described fixative can be joined in described producing well as the charging different from described thinner.It or periodically can be injected into described producing well through the cycle of some months, for the immersion of described reservoir in the injection 30 days being less than described dilution.Described fixative can be provided having the dispenser being arranged in the perforation of producing pipe, make the slowly dissolving continuously of the dilution to described injection, as disclosed in U.S. Patent Publication No. 2011/0162841, by reference relevant disclosure is incorporated herein.
In an embodiment after described fixative is injected into described reservoir, can by described well shutting in a period of time, to be absorbed in described matrix rock to make described fixative and optional other additive (such as surfactant etc.) and thus to react with the heavy metal be present in described crude oil along with described oil moves on in described crack by described dilution.In one embodiment, the described shut-in time can be little of hundreds of sky from 2, and 2-10 days in another embodiment, and 30 days are less than in the 3rd embodiment.
Remove in another embodiment of technique in another original position, described fixative flows through underground passage or formation channels along with the dilution being dissolved in injection, react with described heavy metal and generate metal complex, wherein described heavy metal complex is extracted in described dilution from described produced fluid the recovery be used for subsequently.Dilution (such as water) fixative containing q.s of described injection, as long as described water flow through underground passage or formation channels (hole in described formation matrix, crack, space, chamber, perforation can be included in) and fluid by described well (comprise cased well and without cased well), pipeline and other fluid routes in well, the hydrocarbon be captured in described stratum will be caused to move towards described producing well.In this process, react at the fixative of described injection water and described heavy metal extracted the water of described injection from described produced fluid.In one embodiment, the water of described injection passes through described rock stratum with the speed in 0.1-20 rice/sky.In another embodiment, be heated to promote that the original position of heavy metal is removed when described water is in described stratum.
From described reservoir, reclaim described produced fluid at described reaction in-situ and inject after water, waste water containing described heavy metal complex is separated with described crude oil in phase-separating device known in the art, obtains crude oil and the waste water stream with the heavy metal level obviously reduced.In an embodiment after the mixture of produced fluid (such as crude oil) and the dilution containing heavy metal complex of gathering from described stratum, can extra chemical agent (such as compounding ingredient) be joined in described mixture, to promote that oil/water is separated.
For environment on the coast or in the paralic environment of sensitivity, the aqueous phase after being separated is got back to identical reservoir or different reservoir (after dilution) at note again, is reused for boring or excites or be transferred to treatment system before suitable or feasible position unloading.Implement water treatment to control too much solid, the oil of dissolving, burn into chemical reaction or microbial growth.For the application in coastal waters, described waste water can be processed to remove oil and to be then discharged into sea according to relevant regulations.
The process with the aqueous phase of gathering and reclaiming of the crude oil of the process of the heavy metal level of reduction can use methods known in the art and equipment to implement, and comprises the eliminator, hydrocyclone, netted coalescer, strainer, film, centrifuge etc. that are separated for described oil/water; Ion-exchange, electrodialysis, electrodialysis reversal, electrochemistry, deionization, evaporation, electrodeionization effect, counter-infiltration, UF membrane, oxidation reactor, filtration and their combination can be used for the process of the water reclaimed.
dilution for reaction in-situ:the dilution waiting to be used as described reaction in-situ depend on treat by gather produced fluid, the state of product, the position of described producing well and other factors.
Remove the heavy metal in produced fluid in position, wherein said produced fluid comes in an embodiment of the well in comfortable low permeability formation, described dilution is light hydrocarbon, such as, and pentane, diesel oil, gas-oil (gas oil), kerosene, gasoline, benzene, toluene, heptane etc.In one embodiment, described dilution is undrinkable water, the water in such as connate water, aquifer, seawater, desalted water, oil field production water, industrial by-products water or their combination.Such as, the water in connate water, aquifer, seawater, desalted water, oil field production water, industrial by-products water or their combination.In one embodiment, described dilution can be included in the mixture of the mixture of the oil phase in water.Except described fixative, described dilution can be strengthened with other additive (such as antisludging agent, surfactant, proppant etc.).In one embodiment, described dilution, from the water storage/treatment facility be connected with top platform top production facility, is wherein reclaimed production water, seawater etc. and is prepared by the interpolation of additive (fixative that such as described heavy metals removal needs).Described dilution can be injected in described producing well with cold, heat or environment temperature.
In one embodiment, to gather in for described dilution and/or the identical Injection Well of described fixative described produced fluid (such as crude oil).In another embodiment, gather described in by being positioned at second well with above-mentioned Injection Well same distance.In another embodiment, described fixative at least partially can be adsorbed onto rock down-hole or around on the packaging material of described well.When hydrocarbon is by the described rock that processed or described packaging material, described fixative and its reaction and by described landfill to process dilution in, make to remove from identical producing well or be arranged in second well of described Injection Well same distance subsequently.Suppressed again by stratum, described dilution is driven into described producing well by fluid expansion and gravity.
The well servicing amount of dilution injected depends on many factors, includes but not limited to the composition of the described dilution used and salinity, treats by the character of the produced fluid of gathering, to treat by the characteristic sum place of the amount of the produced fluid of gathering, described rock stratum complete.In one embodiment, described well treating capacity with the volume ratio of dilution and produced fluid for 1:3 to 60:1,2:1 to 40:1 in second embodiment and in the 3rd embodiment 10:1 to 30:1.
fixative:in an embodiment of removing arsenic and/or mercury, described fixative is for forming the compound based on sulphur of sulphur complex with described heavy metal.Example comprises organic and inorganic sulphide material (comprising polysulfide), and described heavy metal complex is converted into the form than being dissolved in produced fluid (such as shale oil) dilution more soluble in water by some embodiments.In one embodiment, described fixative be for using mercury as soluble mercury sulphur complex (such as HgS
2 2-) extract water-soluble mono atomic sulfur species in water diluent, such as, the sulfide of sodium and alkaline sulfides (sulfide of such as ammonium and sulfohydrate).In another embodiment, the described compound based on sulphur is any one in hydrogen sulfide, disulfide salts or polysulfide, and the sediment of formation needs to be separated with the described produced fluid processed by filter, centrifugal etc.In still another embodiment, described fixative is organic polysulfide, such as two-uncle-nonyl-polysulfide.In another embodiment, the described compound based on sulphur is the organic compound of the sulphur atom reacted containing at least one and mercury, as disclosed in U.S. Patent number 6685824; By reference relevant disclosure is incorporated herein.Example includes but not limited to: dithiocarbamate, olefine sulfide, mercaptan, thiophene, benzenethiol, single sulfo-organic acid and two sulfo-organic acids and single thioesters and dithioesters.
In another embodiment, described fixative is oxidant, and described heavy metal is converted into water-soluble oxidation state by it.Exemplary fixative comprises elemental halogen or halogen-containing compound (such as, Cl
2, I
2, F
2or Br
2), the alkali metal salt (such as, halide, chlorine dioxide etc.) of halogen; The iodide of heavy metal cation; Ammonium iodide; IKI; Alkaline metal iodide; Ethylene diamine dihydroiodide; Hypochlorite ion (OCl
-such as NaOCl, NaOCl
2, NaOCl
3, NaOCl
4, Ca (OCl)
2, NaClO
3, NaClO
2deng); Vanadium oxytrichloride; Fenton reagent; Hypobromous acid radical ion; Lv Dai bioxin; Acid iodide IO
3(such as Potassiumiodate KIO
3with sodium iodate NaIO
3); Single persulfate; The peroxide alkali metal salt of picture calcium hydroxide; Can the peroxidase of iodine oxide compound; Oxide, the oxide of peroxide and mixing, comprises oxyhalide, their acid and salt thereof.In one embodiment, described fixative is selected from KMnO
4, K
2s
2o
8, K
2crO
7and Cl
2.In another embodiment, described fixative is selected from the group of persulfate.In still another embodiment, described fixative is selected from sodium perborate, potassium perborate, sodium carbonate hydrate, permonosulphuric acid potassium, sodium carbonate peroxide, peroxydicarbonate and their mixture.
In one embodiment, except at least one fixative, also complexant is joined in described fixative with described heavy metal cation (the such as Hg in described produced fluid
2+ion) form strong complex, the interface phase of heavy metal complex from described oil phase and/or oil-in-water emulsions is extracted described dilution by forming soluble complex.The example being added to the complexant in the fixative of oxidation comprises hydrazine, sodium pyrosulfite (Na
2s
2o
5), sodium thiosulfate (Na
2s
2o
3), thiocarbamide, thiosulfate (such as Na
2s
2o
3), ethylenediamine tetra-acetic acid and their combination.Add in the embodiment of complexant at one in fixative, first described fixative being joined for injecting stratum to be oxidized the dilution of described heavy metal, then described complexant being added to form water-soluble complex subsequently.Described complexant can be injected in stratum at interval, or it can be added to after introducing described fixative in the stratum for reaction in-situ.
In one embodiment, described fixative and heavy metal (such as mercury) react, form insoluble heavy metal complex (such as, mercuric sulphide), described insoluble heavy metal complex is precipitated out and is retained at least partially in described reservoir from described hydrocarbon and dilution.The example of the fixative of the type can comprise the polymerizable compound of sodium polysulfide or Sulfide-containing Hindered functional group.
Can by described fixative as in solid form or pulp/be dissolved in dilution (such as, water, alcohols (as methyl alcohol, ethanol, propyl alcohol)) in, the form of form in light hydrocarbon dilution or their combination adds, with enough amounts of fixative and the heavy metal mol ratio of 1:1 to 20,000:1 in one embodiment; In second embodiment, 50:1 to 10,000:1; In the 3rd embodiment, 100:1 to 5000:1; And in the 4th embodiment, 150:1 to 500:1.If complexant is joined in described reaction in-situ effectively soluble heavy metal (such as mercury) is stablized (with its formation complex) in oil-aqueous mixtures, complexant and soluble mercury from an embodiment with 2:1 to about: the amount of the mol ratio of 3,000:1; In second embodiment, 5:1 to about 1000:1; And in the 3rd embodiment, 20:1 to 500:1.
the accompanying drawing of embodiment is described: further illustrate embodiment of the present invention with reference to accompanying drawing.
With reference now to Fig. 1, original position mercury removes the embodiment of system 200.In-situ system 200 comprises waters 202, stratum 204, stratum 206 and stratum 208.Can provide production equipment on the surface in waters 202, it comprises the process equipment be separated with the described crude oil processed by the water containing hydrargyrum complex.Dilution (water such as containing fixative) is pumped into well 232 downwards, to the part 234 of the fracture on stratum 206.Water containing fixative through stratum 206 to help the removal of the original position of mercury and enter well 212 and arrive the production of the oil and natural gas of production equipment 210 subsequently.
Well 212 through waters 202 and stratum 204, and has opening on stratum 206.As shown on 214, formation can be fracture and/or perforation.Water containing fixative can be injected under stress in the injection region 234 formed in subsurface formations 206, to promote that hydrocarbon products passes through producing well in the ground, and promote described produced fluid and the mixing of fixative of removing mercury for original position.Replace water storage facilities 230 or except water storage facilities 230, can by the seawater (for coastal waters well) produced from same formation or neighbouring stratum (for land well) and the salt solution water source accomplishing the well 232 that pumping is downward.Can gather from the produced fluid of the subsurface formations 206 of the earth by production wellbores 212, described production wellbores 212 has the perforation 206 penetrating hydrocarbon containing formation or reservoir, promote described " process " produced fluid flowing and from described hydrocarbon containing formation to the flowing of described production wellbores.
Oil and natural gas is while produce entering part 214 on one side from stratum 206, adjoint mercury is in this process extracted in water 202 by from described oil and natural gas, and is upward through well 212 to separation equipment 210.By gas and fluid separation applications, gas can be sent into pneumatic reservoir 216, and the crude oil processed is sent into liquid storage device 218, and water is sent into reservoir of water 230.
In one embodiment, water production device comprises the equipment of process water, and described water is such as from output waters 202 and/or the waste water containing the mercury extracted carrying out artesian well 212.The water and being stored in reservoir of water 230 of fabrication cycles can be used for circulation, such as, by re-injecting in well 232.
Fig. 2 shows second embodiment for the system 100 from produced fluid situ removing heavy metal.Vertical boreholes 101 (comprise outer sleeve 102 and order about the endoporus 103 entering reservoir 105) is connected to down hole part 106.Described down hole part 106 comprises liner section 107 and the endoporus 108 of perforation.
In operation, dilution (such as from the production water at water source 109) and described fixative are pumped into the liner section 107 of perforation downwards along outer sleeve 102, the water permeation of wherein said injection to reservoir 105 and across-layer material to produce reservoir penetration region.Crude oil in described stratum flows downward and is gathered in around bottom 111 or bottom 111, and be pumped through endoporus 108 and 103 by pump surface, by the motor at well head 114 in production still 115, in described production still 115, be separated oil and the aqueous mixtures containing the heavy metal complex extracted.Described waste water can be processed and be recycled in reservoir as shown in the figure.
Embodiment: provide the following examples for illustration of the present invention.But the present invention is not limited to the actual conditions that describes in these embodiments or details.
Embodiment 1: the sample comminution of the ground materials obtained from drill-well operation by 100g soaks at least 48 hours to 8-16 order and the sodium sulfide solution (being equivalent to the sulphur of 0.4wt%) of 1wt%.Described sample is placed in teat glass, and the crude oil containing 444ppb mercury is at room temperature pumped across described test tube with the equivalent rate of 0.1 meter/day.Collect the sample of the described crude oil processed and analyze mercury.Can expect, the mercury content in described crude oil reduces at least 75%.
Claims (33)
1. from described hydrocarbon, remove the method for heavy metal from underground hydrocarbon formations recovery of hydrocarbons, described method comprises simultaneously:
By the fixative that the heavy metal in described hydrocarbon is exposed in dilution, described fixative and described heavy metal is made to react the heavy metal complex be formed in described dilution; With
Via producing well from described stratum as mixture gather the heavy metal concentration with reduction hydrocarbon and containing the dilution of described heavy metal complex.
2. the method for claim 1, also comprises:
The described dilution containing described heavy metal complex is separated with described hydrocarbon, obtains the hydrocarbon of the process of the heavy metal concentration with reduction.
3. the method for claim 2, reclaims described dilution for being injected in petroleum reservoir or natural gas reservoirs after being also included in separating step.
4. the process of claim 1 wherein that described heavy metal complex at least partially comprises insoluble heavy metal complex, it is precipitated out from the mixture of hydrocarbon and dilution.
5. the method for claim 4, wherein described insoluble heavy metal complex is at least partially retained in described stratum.
6. the process of claim 1 wherein that described heavy metal complex comprises soluble mercury compound.
7. the process of claim 1 wherein that the described heavy metal in described hydrocarbon is exposed to described fixative with the mol ratio of fixative and heavy metal 1:1 to 20,000:1.
8. the method for claim 7, the described heavy metal wherein in described hydrocarbon is exposed to described fixative with the mol ratio of fixative and heavy metal 5:1 to 10,000:1.
9. the method for claim 1, wherein said heavy metal contains mercury, described dilution is water, described fixative is selected from organic polysulfide, alkali metal sulphide, alkali metal hydrosulfide, the sulfide of ammonium and their mixture, and wherein said fixative and mercury react the soluble mercury compound be formed in water.
10. the method for claim 9, wherein said fixative is selected from NaSH, the sulfide of ammonium and their mixture.
11. the process of claim 1 wherein that described heavy metal contains mercury and the hydrocarbon of described process has the mercury concentration being less than 100ppbw.
12. from underground hydrocarbon formations recovery of hydrocarbons from described hydrocarbon, remove the method for heavy metal simultaneously, described method comprises:
With stratum described in the dilution pressure break containing fixative to produce crack, make described fixative and described heavy metal in described stratum, react the heavy metal complex be formed in described dilution;
The dilution of gathering containing described heavy metal complex; With
To gather from described stratum via producing well the hydrocarbon of the heavy metal concentration with reduction.
13. from underground hydrocarbon formations recovery of hydrocarbons from described hydrocarbon, remove the method for heavy metal simultaneously, described method comprises:
Stratum described in pressure break is to produce crack;
There is provided the dilution containing fixative to flow through the crack in described stratum;
Make described hydrocarbon by having the crack of absorption fixative thereon, the heavy metal wherein in described hydrocarbon and described fixative react and form heavy metal complex and wherein described heavy metal complex is at least partially retained in described stratum; With
To gather from described stratum described hydrocarbon via well.
The method of 14. claims 13, is wherein adsorbed onto described fixative at least partially in described crack.
The method of 15. claims 13, wherein said heavy metal complex is retained in described stratum as insoluble heavy metal complex.
16. from underground hydrocarbon formations recovery of hydrocarbons from described hydrocarbon, remove the method for heavy metal simultaneously, described method comprises:
Stratum described in pressure break is to produce crack;
There is provided the dilution containing fixative to be diffused in the crack in described stratum, wherein described dilution at least partially and described heavy metal react, and form heavy metal complex;
The dilution of gathering containing described heavy metal complex; With
To gather from described stratum via producing well the hydrocarbon of the heavy metal concentration with reduction.
The method of 17. claims 16, also comprises:
React at least 2 hours with described heavy metal in the crack making described fixative be diffused in described stratum.
18. from underground hydrocarbon formations recovery of hydrocarbons from described hydrocarbon, remove the method for heavy metal simultaneously, described method comprises:
By the fixative that the heavy metal in described hydrocarbon is exposed in dilution, the insoluble heavy metal compound described fixative and described heavy metal at least partially being reacted formed and be retained in described stratum and react the heavy metal compound being formed and dissolve in described dilution with described heavy metal at least partially; With
To gather described hydrocarbon and containing the dilution of soluble heavy metal compound as mixture from described stratum via producing well;
The hydrocarbon of wherein gathering has the heavy metal concentration of the heavy metal concentration in the hydrocarbon be less than in described stratum.
The method of 19. claims 18, the heavy metal wherein in described hydrocarbon is exposed to described fixative with the mol ratio of fixative and heavy metal 1:1 to 20,000:1.
The method of 20. claims 19, wherein said heavy metal contains mercury, described dilution is water, described fixative is selected from sodium polysulfide, ammonium polysulfide, the polymer of sulfur compound, alkali metal sulphide, alkali metal hydrosulfide, the sulfide of ammonium and their mixture, and wherein said fixative and mercury react and forms the insoluble hydrargyrum complex be deposited in described reservoir and remove from the original position output hydrocarbon to carry out mercury.
The method of 21. claims 18, also comprises the dilution being separated described hydrocarbon and containing soluble heavy metal compound has the heavy metal concentration of reduction hydrocarbon with recovery.
22. for removing the method for mercury from described hydrocarbon while of recovery of hydrocarbons from underground hydrocarbon formations, described method comprises:
Stratum described in pressure break is to produce crack;
There is provided the dilution containing fixative to described stratum, described fixative is reacted with the heavy metal in described stratum, forms heavy metal complex;
To gather from described stratum described dilution; With
To gather from described stratum the hydrocarbon of the heavy metal concentration with reduction;
Wherein described heavy metal complex is at least partially retained in described stratum.
The method of 23. claims 22, wherein said dilution of gathering contains described heavy metal complex at least partially.
The method of 24. claims 22, wherein after described dilution of gathering from described stratum, described fixative at least partially remains in described stratum.
25. for removing the method for mercury from hydrocarbon while of recovery of hydrocarbons from underground hydrocarbon formations, described method comprises:
With stratum described in the dilution pressure break containing fixative to produce crack;
Described dilution is refluxed by well, and wherein described fixative is at least partially retained in described stratum;
Make described hydrocarbon by having crack and the rock of the fixative be attracted on it, the heavy metal wherein in described hydrocarbon and the fixative be retained in described stratum react and form heavy metal complex; With
To gather from described stratum described hydrocarbon via well.
The method of 26. claims 25, is wherein adsorbed onto described fixative at least partially in the crack in described stratum.
The method of 27. claims 25, wherein said heavy metal complex is retained in described stratum as insoluble heavy metal complex.
28. from underground hydrocarbon formations recovery of hydrocarbons from described hydrocarbon, remove the method for heavy metal simultaneously, described method comprises:
Stratum described in pressure break is to produce crack;
Dilution containing fixative is provided, makes described fixative be diffused in crack in described stratum and rock;
The dilution of gathering containing described heavy metal complex; With
To gather from described stratum via producing well the hydrocarbon of the heavy metal concentration with reduction.
29. from underground hydrocarbon formations recovery of hydrocarbons from described hydrocarbon, remove the method for heavy metal simultaneously, described method comprises:
Described heavy metal in described hydrocarbon is exposed to the fixative in dilution, described fixative and described heavy metal is reacted and forms insoluble heavy metal complex; With
To gather described hydrocarbon and described dilution as mixture from described stratum via producing well;
Wherein described insoluble heavy metal complex is at least partially retained in described reservoir, makes the hydrocarbon phase of gathering have lower heavy metal concentration for the hydrocarbon in described stratum of the fixative be not exposed in dilution.
The method of 30. claims 29, also comprises and is separated to produce the hydrocarbon processed with described hydrocarbon by described dilution.
The method of 31. claims 30, reclaims described dilution for being injected in petroleum reservoir or natural gas reservoirs after being also included in separating step.
The method of 32. claims 31, wherein said dilution comprises production water, and described heavy metal comprises mercury.
The method of 33. claims 29, wherein said heavy metal contains mercury, described dilution is water, described fixative is selected from sodium polysulfide, ammonium polysulfide, the polymer of sulfur compound, alkali metal sulphide, alkali metal hydrosulfide, the sulfide of ammonium and their mixture, and wherein said fixative and mercury react and forms the insoluble hydrargyrum complex be deposited in described reservoir and remove from the original position output hydrocarbon to carry out mercury.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261647983P | 2012-05-16 | 2012-05-16 | |
| US201261647999P | 2012-05-16 | 2012-05-16 | |
| US61/647,999 | 2012-05-16 | ||
| US61/647,983 | 2012-05-16 | ||
| PCT/US2013/041433 WO2013173634A1 (en) | 2012-05-16 | 2013-05-16 | In-situ method and system for removing heavy metals from produced fluids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104583372A true CN104583372A (en) | 2015-04-29 |
Family
ID=49584302
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|---|---|---|---|
| CN201380025179.XA Pending CN104583372A (en) | 2012-05-16 | 2013-05-16 | In-situ method and system for removing heavy metals from produced fluids |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP2850157A4 (en) |
| CN (1) | CN104583372A (en) |
| AR (1) | AR093279A1 (en) |
| AU (1) | AU2013262645A1 (en) |
| BR (1) | BR112014026597A2 (en) |
| CA (1) | CA2872808A1 (en) |
| CL (1) | CL2014003083A1 (en) |
| WO (1) | WO2013173634A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106398748A (en) * | 2015-07-27 | 2017-02-15 | 中国石油化工股份有限公司 | Hydrocarbon oil deferrization agent and hydrocarbon oil deferrization method |
| CN106701151A (en) * | 2015-07-27 | 2017-05-24 | 中国石油化工股份有限公司 | Hydrocarbon oil iron-removing agent and hydrocarbon oil iron-removing method |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10202834B2 (en) | 2013-10-25 | 2019-02-12 | Flex-Chem Holding Company, Llc | Method for remediation of subterranean-formed metal-polymer complexes using a metal complexing agent |
| EP3132112A4 (en) | 2014-04-14 | 2017-10-04 | Flex-chem Holding Company LLC | Stimulation of wells in nano-darcy shale formations |
| CA2959664C (en) | 2014-09-04 | 2023-09-26 | Andrew Bryce Conway | Slick-water fracturing using time release metal-complexing agent |
| EP4041843A1 (en) | 2019-10-10 | 2022-08-17 | Flex-Chem Holding Company, LLC | Method for remediation of subterranean-formed metal-polymer complexes using peracetic acid |
| WO2021159072A1 (en) | 2020-02-07 | 2021-08-12 | Flex-Chem Holding Company, Llc | Iron control as part of a well treatment using time-released agents |
| EP4100484A1 (en) | 2020-02-07 | 2022-12-14 | Flex-Chem Holding Company, LLC | Iron control as part of a well treatment using time-released agents |
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- 2013-05-16 AU AU2013262645A patent/AU2013262645A1/en not_active Abandoned
- 2013-05-16 AR ARP130101704A patent/AR093279A1/en unknown
- 2013-05-16 WO PCT/US2013/041433 patent/WO2013173634A1/en active Application Filing
- 2013-05-16 CA CA2872808A patent/CA2872808A1/en not_active Abandoned
- 2013-05-16 BR BR112014026597A patent/BR112014026597A2/en not_active IP Right Cessation
- 2013-05-16 EP EP13791572.4A patent/EP2850157A4/en not_active Withdrawn
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Also Published As
| Publication number | Publication date |
|---|---|
| BR112014026597A2 (en) | 2017-06-27 |
| WO2013173634A1 (en) | 2013-11-21 |
| CA2872808A1 (en) | 2013-11-21 |
| AR093279A1 (en) | 2015-05-27 |
| AU2013262645A1 (en) | 2014-11-06 |
| CL2014003083A1 (en) | 2015-02-13 |
| EP2850157A1 (en) | 2015-03-25 |
| EP2850157A4 (en) | 2016-03-02 |
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