WO1985001722A1 - Method for removing insoluble sulfide pads at oil/water interfaces - Google Patents
Method for removing insoluble sulfide pads at oil/water interfaces Download PDFInfo
- Publication number
- WO1985001722A1 WO1985001722A1 PCT/US1984/001335 US8401335W WO8501722A1 WO 1985001722 A1 WO1985001722 A1 WO 1985001722A1 US 8401335 W US8401335 W US 8401335W WO 8501722 A1 WO8501722 A1 WO 8501722A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oil
- chlorine dioxide
- sulfide
- water
- pads
- Prior art date
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 27
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 60
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 60
- 239000003208 petroleum Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 description 55
- 229940099041 chlorine dioxide Drugs 0.000 description 49
- 239000000243 solution Substances 0.000 description 20
- 150000004763 sulfides Chemical class 0.000 description 18
- 230000008569 process Effects 0.000 description 15
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 7
- 235000010446 mineral oil Nutrition 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000012267 brine Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 229910001919 chlorite Inorganic materials 0.000 description 3
- 229910052619 chlorite group Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- JJHVYBKFCASXME-UHFFFAOYSA-M [Cl+].[O-]Cl=O Chemical compound [Cl+].[O-]Cl=O JJHVYBKFCASXME-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- JFBJUMZWZDHTIF-UHFFFAOYSA-N chlorine chlorite Inorganic materials ClOCl=O JFBJUMZWZDHTIF-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001504 inorganic chloride Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- VCTOKJRTAUILIH-UHFFFAOYSA-N manganese(2+);sulfide Chemical class [S-2].[Mn+2] VCTOKJRTAUILIH-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
-
- 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
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
Definitions
- Solid metallic sulfides are frequently encountered in petroleum processing equipment. In operations involving water and oil phase separations, such as in field dehydration systems, desalting plants, and the like, these solid metallic sulfides are particularly troublesome. They have low solubility in water or brines. The oleophilic characteristics of sulfides cause them to collect at the oil/water interface, to form sludges of a complicated nature. These sludges are generally referred to as "pads". The pads caused by the presence of the troublesome metallic sulfides drastically interfere with the efficient separation of crude oil from the associated aqueous medium.
- inorganic chlorine-containing chemicals are required in relatively high concentrations and are very corrosive to the steels and other metals used in the construction of typical petroleum producing equipment.
- the pH's of the treated media are typically low under these conditions.
- the chemicals may also react with the petroleum, yielding hydrochloric acid and organic chlorides by decomposition. This alteration of the petroleum composition creates products that are poisonous to catalysts used in che refining process, which seriously affects refinery operations.
- the rate of solid metallic sulfide removal by hydrochloric acid and chlorine can be economically rapid enough, the action of hypochlorous acid and hypochlorite salts is quite slow.
- Acrolein can be quite useful in removing insoluble metallic sulfides.
- typical applications of acrolein generally require long contact periods with the pads at the oil/water interface.
- several applications of acrolein are required to eliminate the total insoluble metallic sulfide pad.
- the large amounts of acrolein chemical consumed under these circumstances can become quite expensive.
- Most applications involving nonionic, cationic, and anionic surfactants tend to remove the oil adhering to the solid metallic sulfide pad present in the oil/water interface but do not eliminate the solid metallic sulfides, so the interfacial pads reform quickly.
- Chlorine dioxide has been known to successfully remove hydrogen sulfide from aqueous media for many decades.
- Patent 4,077,879 discloses a process using chlorine dioxide to remove undesirable soluble sulfides from aqueous systems contaminated with small amounts of petroleum oils.
- removal of oil/water interfacial pads in bulk oil/water systems by chlorine dioxide in order to improve oil recovery has not previously been known.
- any use of chlorine dioxide to treat soluble metallic sulfides is limited to aqueous media. It is generally known that the effects of solvents on chemical reactions can greatly alter observations. Chlorine dioxide is not known to be effective in treating insoluble metallic sulfides in the presence of oils.
- inventive process described hereinafter utilizes a chlorine dioxide application to treat the bulk properties of the oil/water interfacial pad caused by the solid metallic sulfides. This process is especially useful in that it allows rapid and low cost phase separations in treatment of crude oil to remove water, solids, salts, and other impurities. These steps are required before the petroleum can be sold, transported, and refined.
- Chlorine dioxide is used in a process for eliminating the effects of insoluble metallic sulfides in impeding the separation of oils from aqueous phases encountered in petroleum processing systems. This process involves adding aqueous chlorine -dioxide solution to the oil/water mixture containing an insoluble metallic sulfide interfacial pad. The process results in a clearly defined oil/water interface.
- Insoluble metallic sulfide interfacial pads are defined as interfacial interferences caused when metals and metallic ions combine with sulfur, hydrogen sulfide, or soluble sulfide salts to form insoluble metallic sulfides.
- metals and ions include, but are not limited by, Ag, Ca, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sn, Ti, and Sn, separately or in any combined ratio.
- Typical oils found in oil field practices combined with these insoluble metallic sulfide pads can experience troublesome interfacial interferences in contact with aqueous media. This situation can also arise when dissolved gases and undissolved gases are present. Troublesome interfacial sulfide pads can be found in oil field tanks, free-water-knockouts, heater treaters, desalters, refinery distillate receivers, sumps, pits, and the like. These pieces of equipment can be involved in constant-flowing, intermittent-flowing, and static fluid conditions.
- Chlorine dioxide solutions can be obtained from a variety of manufacturing processes. Typical processes include acid-chlorite, acid-chlorate, acid-hypochlorous acid-chlorite, acid-hypochlorite salts-chlorite, chlorine-chlorite, and the like, and any variation of these systems comprised of process adjuvants.
- the application of chlorine dioxide can be made into quiet, nonagitated petroleum processing equipment. Additionally, applications of chlorine dioxide can be accompanied by agitation of fluids within such equipment.
- the temperature of the systems to which chlorine dioxide may be applied varies widely.
- the effectiveness of the inventive process is not very dependent on the temperature, and is found to be useful in petroleum-water separations at temperatures from low ambient to 200°C, or thereabouts.
- Some systems are operated under pressures to allow higher temperatures and lower fluid viscosities, which is helpful in the sedimentation and separation of phases. Higher temperatures appear to lessen somewhat the amount of chlorine dioxide required.
- insoluble metal sulfides are converted to a soluble form.
- the petroleum oil that wets, i.e., clings to the surface of, the insoluble metal sulfide is able, after chlorine dioxide treatment, to migrate to the petroleum oil phase and is no longer a component of the emulsion. This then permits the clean separation of the petroleum oil from water phases.
- the mode of action of chlorine dioxide as described is believed to be correct and is given for better understanding, but is not intended to limit the scope of the invention.
- Aqueous chlorine dioxide solutions can. be added to oil/water systems in a variety of different ways in order to remove insoluble interfacial sulfide pads.
- the chlorine dioxide may be added into the inlet lines upstream of the equipment containing the troublesome interfacial sulfide pads, Applications may also be made directly into the individual oil field equipment. The more cost effective applications appear to be those made into the oil phase proper.
- chlorine dioxide can be made into oil field vessels experiencing continuous flowing, intermittent flowing, and stagnant fluid conditions.
- the time required for complete pad removal is lessened if the vessel can be agitated, e.g., such as rolling tank contents with gas.
- Ten screw cap test tubes were each filled with 1.0 mL ferric chloride solution (0.037M) and 1.0mL freshly prepared sodium sulfide solution (0.037M). Black iron sulfide precipitates formed immediately. These heterogeneous mixtures were diluted with 5.0 mL ASTM brine solution (4.2%, American Society Testing Materials, formula a, A.S.T.M. D-1141-52, Table 1, section 4). These solutions gave 3.7x10 -5 moles of sulfide and had a pH of 7.0. Then, 1.0 mL Nujol (trademark) mineral oil was added, the tubes were capped, and shaken vigorously for one minute. A heavy iron suifide pad formed at the oil/water interface in all tubes. Next, various amounts of chlorine dioxide solution (0.0266M) were added to each of the tubes and the results recorded.
- EXAMPLE 2 Three screw cap test tubes were each filled with 0.5 mL ferric chloride solution (0.037M) and 0.5 mL freshly prepared sodium sulfide solution (0.037M). The black iron sulfide precipitates were diluted with 2.0 mL deionized water and vigorously shaken with 0.5 mL various oils to provide a heavy pad at the oil/water interfaces. Then, 3.0x10 -6 moles chlorine dioxide were added. The initial pH of 6.5 fell to 6.0 after treatment with the chlorine dioxide, at a ratio of 0.62 moles of sulfide to 1.0 moles of chlorine dioxide.
- EXAMPLE 3 Eight screw cap test tubes were charged with equal amounts of 0.037M ferric chloride and 0.037M sodium sulfide solutions. Then, 4.2% ASTM brine solution and mineral oil were added. The tubes were capped and shaken to obtain a heavy oil/water interfacial pad. These solutions had an initial pH of 7.0. Then, 1.11x10 -5 M chlorine dioxide solution was added, and the observations recorded.
- EXAMPLE- 4 The ability of chlorine dioxide to remove oil/water interfacial sulfide pads in systems with varying pH's can also be demonstrated.
- Several screw cap test tubes were charged with 1.48x10 moles of ferric chloride and 1.48x10 -6 moles sodium sulfide. Each of these mixtures was diluted with 1.0mL various .pH buffer solutions and 0.5mL mineral oil. Upon shaking, heavy interfacial pads formed. Then, 0.037M chlorine dioxide solution was added and, in all cases, the pad was removed.
- Chlorine dioxide can remove oil/water interfacial sulfide pads under a wide variety of temperatures.
- Several screw cap test tubes were charged with 1.0mL ferric chloride (0.037M) and 1.0mL freshly prepared sodium sulfide (0.037M). The resulting mixtures were diluted with 5.0mL of aqueous medium and 1.0mL mineral oil. Upon vigorous shaking, heavy sulfide interfacial pads formed. Then, the tubes were heated to various temperatures. Chlorine dioxide solution was then added at the elevated temperature and, in all cases, the sulfide interfacial pad was removed.
- EXAMPLE 6 Agitation of the oil/water system can greatly decrease the time required for a given amount of chlorine dioxide to remove an interfacial sulfide pad.
- Two 250mL flasks were charged with 5.0mL each of ferric chloride (0.037M) and sodium sulfide (0.037M) solutions. These mixtures were then diluted with 100ml ASTM brine (4.2%) and 50ml mineral oil. These systems were shaken to create a heavy interfacial sulfide pad. Then, 8.1 x 10 -6 moles of chlorine dioxide solution was added to the top portion of one flask without agitation. Six minutes were required to completely remove the pad under the undisturbed conditions. Again, 8.1x10 -6 moles chlorine dioxide was added to top portion of the other flask. A magnetic stirring bar was used to create a minor agitation condition at a spinning rate of 20 cps. Under these conditions, the pad disappeared in 30 seconds.
- Chlorine dioxide can be used to remove oil/water interfacial sulfide pads containing metals other than iron.
- Several screw cap test tubes were charged with a soluble metallic salt and an equimolar amount of freshly prepared sodium sulfide solution. These mixtures were diluted with 4.2% ASTM brine and mineral oil. Then, chlorine dioxide solution was added which caused removal of the interfacial sulfide pad in all cases. The data are displayed below.
- Chlorine dioxide is effective when added to oil/water systems at pH 1 to pH 11 in ratios of from as low as Is 100 moles of chlorine dioxide per mole of sulfide to as high as three moles of chlorine dioxide per mole of sulfide. These are not necessarily critical upper and lower limits, but generally define the most effective range of chlorine dioxide to sulfide ratios suitable for use in this invention.
- the concept of the invention contemplates the use of effective amounts of chlorine dioxide being added to oil/water systems either in the oil phase or the water phase, or both, to contact the sulfide oil/water pad and to thereby eliminate the pad or prevent the formation of the sulfide pad.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Removal Of Floating Material (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54110483A | 1983-10-12 | 1983-10-12 | |
| US541,104 | 1983-10-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1985001722A1 true WO1985001722A1 (en) | 1985-04-25 |
Family
ID=24158188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1984/001335 WO1985001722A1 (en) | 1983-10-12 | 1984-08-20 | Method for removing insoluble sulfide pads at oil/water interfaces |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0157793A4 (ja) |
| JP (1) | JPS60501496A (ja) |
| CA (1) | CA1222714A (ja) |
| WO (1) | WO1985001722A1 (ja) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8609594B2 (en) | 2011-03-22 | 2013-12-17 | Sabre Intellectual Property Holdings Llc | Chlorine dioxide precursor and methods of using same |
| US9238587B2 (en) | 2013-03-15 | 2016-01-19 | Sabre Intellectual Property Holdings Llc | Method and system for the treatment of water and fluids with chlorine dioxide |
| US10442711B2 (en) | 2013-03-15 | 2019-10-15 | Sabre Intellectual Property Holdings Llc | Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4077879A (en) * | 1976-06-04 | 1978-03-07 | Olin Corporation | Treatment of sulfide-bearing waters with chlorine dioxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US310049A (en) * | 1884-12-30 | granger |
-
1984
- 1984-08-15 CA CA000461045A patent/CA1222714A/en not_active Expired
- 1984-08-20 EP EP19840903311 patent/EP0157793A4/en not_active Ceased
- 1984-08-20 WO PCT/US1984/001335 patent/WO1985001722A1/en not_active Application Discontinuation
- 1984-08-20 JP JP59503285A patent/JPS60501496A/ja active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4077879A (en) * | 1976-06-04 | 1978-03-07 | Olin Corporation | Treatment of sulfide-bearing waters with chlorine dioxide |
Non-Patent Citations (3)
| Title |
|---|
| COCHELI et al., "Removal of Cyanide from Waste Water" CHEM ABSTR, Volume 74, 74: 79296k, issued 1971. * |
| GENZO, "Reactions of Chlorine Dioxide in Sodium Sulfide and Sodium Sulfite" CHEM ABSTR, Volume 58, 58:5369h, issued 1963. * |
| See also references of EP0157793A4 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8609594B2 (en) | 2011-03-22 | 2013-12-17 | Sabre Intellectual Property Holdings Llc | Chlorine dioxide precursor and methods of using same |
| US8703656B2 (en) | 2011-03-22 | 2014-04-22 | Sabre Intellectual Property Holdings Llc | Chlorine dioxide precursor and methods of using same |
| US9238587B2 (en) | 2013-03-15 | 2016-01-19 | Sabre Intellectual Property Holdings Llc | Method and system for the treatment of water and fluids with chlorine dioxide |
| US10308533B2 (en) | 2013-03-15 | 2019-06-04 | Sabre Intellectual Property Holdings Llc | Method and system for the treatment of water and fluids with chlorine dioxide |
| US10442711B2 (en) | 2013-03-15 | 2019-10-15 | Sabre Intellectual Property Holdings Llc | Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6333404B2 (ja) | 1988-07-05 |
| JPS60501496A (ja) | 1985-09-12 |
| EP0157793A1 (en) | 1985-10-16 |
| CA1222714A (en) | 1987-06-09 |
| EP0157793A4 (en) | 1986-08-21 |
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