EP1414753B1 - Verfahren zur regenerierung verbrauchter halogenidhaltiger flüssigkeiten - Google Patents

Verfahren zur regenerierung verbrauchter halogenidhaltiger flüssigkeiten Download PDF

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EP1414753B1
EP1414753B1 EP02721386A EP02721386A EP1414753B1 EP 1414753 B1 EP1414753 B1 EP 1414753B1 EP 02721386 A EP02721386 A EP 02721386A EP 02721386 A EP02721386 A EP 02721386A EP 1414753 B1 EP1414753 B1 EP 1414753B1
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Prior art keywords
fluid
acid
metallic
alkali
halide
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French (fr)
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EP1414753A2 (de
EP1414753B9 (de
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Raymond D. Symens
Lyle H. Howard
Thomas William Polkinghorn
Surendra Kumar Mishra
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Tetra Technologies Inc
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Tetra Technologies Inc
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    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/06—Arrangements for treating drilling fluids outside the borehole
    • E21B21/068—Arrangements for treating drilling fluids outside the borehole using chemical treatment

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  • the present invention relates to a method for regenerating used halide fluids. More specifically the invention relates to enhancing used halide fluids by removing impurities, increasing the density of the halide fluid, and increasing the concentration of electrolytes and adjusting the true crystallization temperature of the fluid.
  • Clear brine fluids used in deep oil and gas wells or other industrial and agricultural processes become diluted due to the increased concentration of water in the system.
  • these fluids can become contaminated with impurities such as metallic cations, hydrocarbons and organic polymers.
  • impurities such as metallic cations, hydrocarbons and organic polymers.
  • TCT true crystallization temperature
  • Brine fluids are expensive to produce. Due to the high amounts of chlorides, bromides and, in some brines, zinc that are present in the used fluids, the disposal of used clear brine fluids is also very costly. It is highly desirable that a used halide fluid be recuperated, regenerated, and recycled back into operation.
  • the density of the solution that is being regenerated will drop substantially.
  • the change in the density also changes the TCT of the fluid, so that the fluid is unable to meet the specification set by the needs of the oil field for TCT value of the fluid.
  • Using the methods of evaporation or blending to increase density or to adjust the TCT is time consuming, expensive and difficult to control.
  • What is needed is a method that allows for an efficient regeneration of the recuperated used brine fluid in a controlled manner.
  • a method that removes metallic cationic impurities and avoids both precipitation and conditions that increase dilution and adversely affects the TCT of the fluid by addition of water into the recuperated brine fluid is also desirable.
  • the present invention relates to an innovative method for regeneration of used halide fluids that have been recuperated from industrial processes such as oil and gas drilling, agricultural chemical processes, metal plating or water treatment.
  • Used halide fluids, bromide or chloride brines for example are usually contaminated with soluble and insoluble impurities.
  • these recuperated, used fluids typically have a density greater than 1.078 kg/l (9.0 lb/gal) but less than the required density of a desired drilling fluid.
  • one preferred method of regeneration of a used halide fluid comprising soluble and insoluble impurities and having a density greater than 1.078 kg/l (9.0 lb/gal) comprises adding an acid to the used halide fluid.
  • the used halide fluid is then contacted with a halogen, bromine for example, to increase fluid density and oxidize impurities.
  • a halogen-generating species such as oxyhalogen salts, hypochloride, hypobromide and the like can be used to increase density, adjust TCT and oxidize impurities.
  • the used halide fluid if comprising a high solid content, should be filtered to remove the solids prior to acidification.
  • a reducing agent is added to convert halogen to halide ion while maintaining the temperature at a minimum of 10°C.
  • the fluid is then contacted with an alkali to neutralize any excess acid. Any suspended solid impurities remaining can be separated from the fluid.
  • the pH can be maintained within a range of approximately 0.0 to 5.5.
  • the alkali and alkali earth metal cations this range can be from 0.0 to 10.0.
  • the acid used for acidification can comprise hydrobromic acid.
  • the acid can comprise hydrochloric acid or an organic acid.
  • the reducing agent is preferably selected from a group consisting of ammonia, sulfur, hydrogen sulfide, sodium bisulfide, metallic zinc, metallic iron, metallic copper, metallic nickel, metallic cadmium, metallic cobalt, metallic aluminium, metallic chromium, metallic manganese, organic acids, alcohols and aldehydes.
  • the electrolyte to be enhanced in the used fluid is a salt of an alkali metal, an alkali earth metal or a base metal.
  • the alkali earth metal is calcium
  • the alkali used to neutralize excess acid can be calcium hydroxide or calcium oxide.
  • the alkali earth metal in the used fluid is strontium
  • the alkali used to neutralize excess acid is preferably strontium hydroxide or strontium oxide.
  • the alkali used to neutralize excess acid is an alkali metal hydroxide, sodium hydroxide or potassium hydroxide for example.
  • Ammonia can also be used to neutralize excess acid.
  • the alkali used to neutralize excess acid is a base metal hydroxide or base metal oxide, such as zinc hydroxide, zinc oxide, copper hydroxide or copper oxide.
  • the alkali used to neutralize excess acid is aluminium hydroxide or aluminium oxide, manganese hydroxide or manganese oxide, chromium hydroxide or chromium oxide.
  • the recuperated used halide fluid is piped into a reactor after density and chemical composition have been determined according to steps (a) and (b).
  • the acid, halogen, reducing agent and alkali can be piped into reactor along with the fluid.
  • the acid, halogen, reducing agent and alkali can be transported separately to the reactor. Bromine is one preferred halogen used in regeneration.
  • Another preferred method regenerates a used halide fluid comprising a blend of a group of halide salts, such as calcium chloride, calcium bromide, zinc bromide or a combination thereof.
  • the starting brine fluid will typically have a density greater than 1.078 kg/l (9.0 lb/gal) and contain both soluble and insoluble impurities.
  • This method comprises the steps of (1) adding acid to the used halide fluid so that the pH is within a range of approximately 0.0 to 5.5 for a base metal or 0 to 10.0 for alkali and alkali earth metal systems; (2) contacting the used halide fluid with bromine to increase the density to at least 1.198 kg/l (10.0 lb/gal.) and oxidize soluble impurities; (3) adding a reducing agent while maintaining the temperature at a minimum of 10°C; (4) contacting the fluid with an alkali to neutralize excess acid; and (5) separating any suspended solid impurities from the fluid.
  • the Figure is a schematic of one embodiment of the method of the invention.
  • the present invention relates to an innovative method for regeneration of used halide fluids.
  • the used halide fluids calcium or zinc brine for example, have been recuperated from industrial processes such as oil and gas drilling, agricultural chemical processes, metal plating or water treatment.
  • the recuperated halides often contain soluble and insoluble impurities and can be so diluted that the density of the halides and concentrations of the electrolytes are not acceptable for continued industrial operations.
  • brine fluids used in oil and gas drilling For the purpose of illustration, reference hereafter is made, for convenience, to brine fluids used in oil and gas drilling.
  • Clear brine fluids used in deep oil and gas wells become diluted due to the increased concentration of water in the operations system. Additionally, they become contaminated with impurities such as metallic cations, hydrocarbons such as oils, as well as organic polymers, solids, muds and sands. As a result, the overall quality of the brine fluid is reduced; the density in particular drops, and the true crystallization temperature (TCT) changes to a level that does not conform to product specifications.
  • TCT true crystallization temperature
  • Brine fluids are expensive to produce. Also, due to the hazardously high amounts of chlorides, bromides and zinc present in brine fluids, the disposal of used clear brine fluids can be very costly. Regeneration of the used fluids by the method of this invention is performed in a controlled manner so that the regenerated brine can economically be recycled back into the systems.
  • a used halide fluid 60 such as a drilling fluid
  • a used halide fluid 60 can comprise a density above water, 1.078 kg/l (9.0 lb/gal) for example, but nothing enough to perform during the drilling operations, especially in deeper or higher pressure wells.
  • a halide fluid has a specific density targeted to the type of drilling operation and/or pressure of the well.
  • Clear brines used as completion, workover and drilling fluids comprise a density higher than the density of water, 0.995 kg/l (8.3 lb/gal), typically within a range of approximately 1.366 kg/l (11.4 lb/gal) to 1.917 kg/l (16 lb/gal), and even possibly as high as 2.756 kg/l (23.0 lb/gal) depending an the targeted use of the brine.
  • Electrolytes of alkali metals, alkali earth metals and base metals are commonly used in the composition of these brine fluids and are often selected according to their ability to increase the density of the drilling fluid.
  • the density of the used drilling fluids is restored to a density that is necessary for well operations thereby regenerating the fluid to its useful state.
  • the practice of this invention also allows for the adjustment of the true crystallization temperature (TCT) of the fluid.
  • TCT is a function of the density.
  • the operator of the production wells checks the specifications for the TCT of the electrolytes within the fluids being used. These substrates adversely affect the properties of the fluid that are desirable for the oil and gas industries.
  • the Figure illustrates used fluid 60 piped into a reactor 10.
  • the composition and density of the used halide fluid 60 determines the parameters of the method of the reaction. Knowledge of this composition and the properties of the fluid, i.e., electrolytes present, initial pH, density, and impurities present, is critical to determine the procedure and chemicals used during the method.
  • the electrolytes present in the recuperated, used halide fluid 60 can comprise an alkali metal, alkali earth metal or a base metal salt. These salts can be selected from a group of salts comprising sodium chloride, calcium chloride, zinc chloride, sodium bromide, calcium bromide, zinc bromide or blends thereof can be employed. Strontium chloride, strontium bromide, copper chloride, copper bromide, nickel chloride, nickel bromide, aluminium chloride or aluminium bromide can also be considered.
  • a used brine fluid 60 often comprises a blend of any of these metal salts, calcium chloride, calcium bromide and/or zinc bromide for example.
  • metal present in the recuperated used halide can comprise zinc, copper, cobalt, cadmium, nickel, potassium, cesium, lithium, barium, magnesium, aluminium, manganese, chromium or combinations thereof.
  • the halide ions present can comprise bromide or chloride as illustrated above, but iodide ions are also within the scope of this invention.
  • the manner in which these various electrolytes are blended depends largely on the density and crystallization temperature requirements for the particular brine fluid needed. A double or triple electrolyte blend can be used to obtain a higher density clear brine fluid.
  • bromide electrolytes When blending a relatively high-density clear brine fluid, bromide electrolytes provide higher flexibility than the relatively low-density chloride electrolytes.
  • the stability and TCT of the blended finished product also depends on the proportion of the individual electrolytes in the composition.
  • brine fluids with a high concentration of calcium chloride may precipitate carbonates or sulfates, which are often present in formation waters of oil or gas wells.
  • Zinc bromide brines can be used to provide high density, calcium-free brine fluids which do not precipitate anions such as carbonates and sulfates due to the acidic nature of the zinc ion.
  • Such zinc bromide brines can also be used to adjust the TCT of the fluid.
  • the density and TCT of the brine fluid can be adjusted by altering the concentration of the electrolyte or electrolytes in the solution.
  • the parameters, acidity, temperature etc., of the method must be adjusted during the regeneration to encompass the blend of electrolytes present.
  • the used halide fluids should be analyzed and evaluated for their solids content.
  • the solids are removed by a solid-liquid separation method known in the art prior to the treatment of the fluids within the reactor 10. High solid content in the feed to the reactor 10 can result in increased undesirable impurities in the finished product and will also affect other properties of the fluids.
  • the initial used halide fluid 60 piped into the reactor 10 is a fluid that was diluted during well operations and can comprise soluble and insoluble impurities such as metallic cations, hydrocarbons, polymers, suspended solids, drill cuttings and sand or grit. Because of dilution by contact with waters found in wells, these used fluids typically have less than the desired density of the required drilling fluid, but a density greater than 1.078 kg/l (9.0 lb/gal).
  • the used halide fluid if comprising a high solid content, should be filtered to remove the solids prior to acidification. The method operates more efficiently if oil and grease residues and other solids are removed prior to the process.
  • a separation process prior to acidification can remove oil and grease.
  • the separation process can include destabilization of the emulsified oil followed by physical separation of the oily phase by a suitable process known in the art.
  • One primary purpose of regenerating used halide fluids according to the method of this invention is to replace the electrolytes lost during well operations or industrial use of the fluid.
  • the initial density of the recuperated halide fluid is calculated and the chemical composition analyzed. After analysis, the selection and amount of the proper alkali used to neutralize excess acid and restore lost electrolytes can be made. If the recuperated halide fluid is calcium chloride, for example, calcium oxide can be used to neutralize excess acid thereby restoring calcium ions.
  • adding acid 50 to the used halide fluid 60 acidifies the fluid.
  • the composition of the initial used halide fluid 60 can comprise aqueous zinc bromide or aqueous calcium bromide.
  • a blend of chlorides and bromides of calcium and zinc in various proportions can be used.
  • Acidification is required to avoid precipitation of the metallic salts, particularly where zinc and calcium are present.
  • the used halide comprises base metals, a pH within a range of 0 to 6, preferably 0 to 5.5, is therefore preferred.
  • the used halide comprises alkali or alkali earth metals, a pH within a range of 0 to 10, is preferred.
  • the acid 50 used for acidification can comprise hydrobromic acid.
  • the acid can comprise hydrochloric acid or an organic acid.
  • the used halide fluid is then contacted with bromine.
  • Bromine is effective to increase fluid density, adjust true crystallization temperature and removes or destroys impurities.
  • Impurities can comprise metallic cations, hydrocarbons or polymers.
  • the used halide fluid can be contacted with a bromine-generating species.
  • bromine enhances the bromide ions available in the fluid so as to return the used halide fluid to the desired density for its specific use. Bromine also functions to oxidize impurities such as metallic cations, and the polymers and hydrocarbons found in the used fluid. If polymers are present, which is usually the case since various polymers are used as viscosifiers, oxidation is necessary to destroy these polymers.
  • bromine does not increase the pH of the fluids that can promote unwanted precipitation of the metals. Compared to peroxides, bromine increases the density of the fluid rather than reducing it.
  • the bromine is added while maintaining the temperature at a minimum of 10°C, especially when adding bromine to a blend of used halides.
  • a cooler 100 can be used to control the rate of the reaction by maintaining the desired reaction temperature. In another preferred embodiment, the temperature is maintained at a minimum of 20°C. With the addition of bromine, the resulting TCT can be adjusted to avoid the precipitation of electrolytes, which can reduce the density of the fluid.
  • a reducing agent 30 is added in a controlled manner to combine with and remove excess bromine.
  • the addition of the reducing agent is controlled by maintaining the temperature at a minimum of approximately 10°C.
  • the reducing agent is preferably selected from a group consisting of ammonia, sulfur, hydrogen sulfide, sodium bisulfide, metallic zinc, metallic iron, metallic copper, metallic nickel, metallic cadmium, metallic cobalt, metallic aluminium, metallic manganese, metallic chromium, organic acids, alcohols and aldehydes.
  • the fluid is contacted with an alkali 20 to neutralize any excess acid.
  • a base metal, an alkali metal and an alkali earth metal can be present in the used fluid.
  • the composition and density of the base metal is determined prior to the halide fluid 60 entering the reactor 10.
  • the metallic cations must be restored to the original density required for the useful function of the halide brine in the well.
  • the alkali earth metal in the recuperated, halide fluid is calcium
  • the alkali used to neutralize excess acid can be calcium hydroxide or calcium oxide.
  • the alkali used to neutralize excess acid is preferably strontium hydroxide or strontium oxide.
  • the alkali used to neutralize excess acid can be an alkali metal hydroxide. Where sodium is the alkali metal, the alkali used to neutralize excess acid is sodium hydroxide. Where the electrolyte that is to be restored is a base metal salt, the alkali used to neutralize excess acid can be a base metal oxide. When a base metal is used to neutralize excess acid, measures should be taken to vent the hydrogen gas that is emitted from the process. Depending an the composition of the used halide fluid to be regenerated, the base metal oxide is selected from a group consisting of zinc oxide, copper oxide, cobalt oxide, cadmium oxide or nickel oxide.
  • the alkali used to neutralize excess acid is a base metal hydroxide.
  • the base metal hydroxide can be selected from a group of base metals consisting of zinc, copper, cobalt, cadmium or nickel.
  • the alkali used to neutralize excess acid is ammonia.
  • the alkali 20 is a base metal or a base metal oxide
  • the reducing agent 30 is p-formaldehyde
  • the halogen 40 is bromine and the acid 50 used during the method is hydrobromic acid.
  • the alkali is lime
  • the reducing agent is ammonia
  • the halogen is bromine
  • the acid is hydrobromic acid.
  • Ammonia is one preferred reducing agent in an alkali and alkali earth metal system and p-formaldehyde is the preferred reducing agent in a base metal system.
  • the equipment used to perform the method of this invention can be straightforward and quite simple. Basically, a reaction tank or pipe, one or more pumps and storage tanks are required.
  • the steps performed during the method are performed in a mixed reactor, preferably a stirred reactor or a tube reactor 10.
  • the recuperated used halide fluid is piped into the reactor 10 along with the bromine, acid 50, reducing agent 30 and alkali 20 so that the various chemical solutions are combined in the influent pipe and then mixed within the reactor 10.
  • the influent chemical solutions can be piped in separately.
  • the base metals used to enhance the electrolytes can be placed in a reactor along with used halide fluid. Bromine, acid, a reducing agent and alkali can then be piped into the reactor either separately or together in one pipeline.
  • Meters can be strategically placed along the influent pipeline and effluent pipeline to monitor the properties of the solutions: oxidation-reduction potential (ORP), pH and density. Alternatively, the properties can be measured manually.
  • the meters comprise an ORP meter, a pH meter and a density meter.
  • the chemical reaction is continued and the effluent product returned to the reactor until the desired levels of density, oxidation-reduction potential and pH are achieved.
  • the reaction process can be carried out as a batch process or a continuous process.
  • a cooler 100 is used to maintain the lower temperatures. Separation of the resulting fluid from any suspended solid can be performed by several known methods. A gravity settler 90 is one. Alternatively, separation of the resulting fluid from any suspended solid is performed in a clarifier. A centrifuge or pressure filter or vacuum filter can also be used to separate solids from the resulting product, independently or as a subsequent process to a clarifier.
  • a 500 ml sample of a recovered completion fluid from an oil well with density of 1.194 kg/l (15.98 lb/gal) and iron content of 540 mg/kg was placed in a glass beaker and kept stirred using an electrically driven stirrer. To this 10 ml of liquid bromine was introduced. Using a hot plate the temperature of the reaction fluid was raised to 148°F (64.4°C). The solution was kept stirred at this temperature for 1 hour, which followed by addition of 2.9 g of p-formaldehyde as the reducing agent. Zinc oxide was added on as a required base to neutralize the excess acid of the fluid. The final fluid was filtered and analyzed for density and iron content, which respectively were determined to be 2.146 kg/l (17.91 lb/gal) and 35 mg/kg.
  • a 500 ml sample of a recovered completion fluid from an oil well of Example 1 was placed in a glass beaker and kept stirred using an electrically driven stirrer. To this 20 ml of liquid bromine was introduced, while using a hot plate the temperature of the reaction solution was raised to 102°F (38.9°C). The reaction fluid was kept stirred at this temperature for 1 hour, which was followed by addition of 5.9 g of p-formaldehyde as the reducing agent. Zinc oxide was added on as a required base to neutralize the excess acidity of the reaction fluid. The final fluid was filtered and analyzed. The iron content of the final fluid was determined to be 40 mg/kg.
  • Example 4 test On a 500 ml sample of the same fluid that was used in Example 4 test was conducted. In this case, while the liquid bromine addition was maintained at 20 ml, the reaction suspension was heated to about 180°F (82.2°C) for 1.7 hrs. 5.9 g of p-formaldehyde was used as the reducing agent. Similar to Example 4, lime was used for the neutralization of excess acid content. The final reaction fluid was filtered and analyzed. The density and iron content were determined to be 1.605 kg/l (13.4 lb/gal) and 10 mg/kg, respectively.
  • Example 7 Test described in Example 7 was repeated, while in this case zinc oxide was used for the neutralization of excess acid, replacing lime of Example 7.
  • the density and iron content of the final filtered fluid were measured to be 1.926 kg/l (16.08 lb/gal) and 44 mg/kg, respectively.

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Claims (37)

  1. Verfahren zur Regenerierung gebrauchter halogenhaltiger Flüssigkeiten, umfassend lösliche und unlösliche Verunreinigungen und eine Dichte größer als 1,078 kg/l (9,0 lb/gal) aufweisend, wobei das Verfahren umfasst:
    a) Zusetzen von Säure zu der gebrauchten halogenhaltigen Flüssigkeit;
    b) Herstellen des Kontakts der gebrauchten halogenhaltigen Flüssigkeit mit Halogen zum Erhöhen der Flüssigkeitsdichte, Einstellen der zutreffenden Kristallisationstemperatur und Oxidieren von Verunreinigungen;
    c) Zugeben eines Reduktionsmittels unter Halten der Temperatur bei minimal 10 °C;
    d) Herstellen des Kontakts der Flüssigkeit mit einem Alkali zum Neutralisieren des Säureüberschusses;
    e) Abtrennen jeglicher suspendierter fester Verunreinigungen aus der Flüssigkeit.
  2. Verfahren nach Anspruch 1, wobei die gebrauchte halogenhaltige Flüssigkeit mit einer halogenerzeugenden Verbindung in Kontakt gebracht wird.
  3. Verfahren nach einem der vorangehenden Ansprüche, wobei die Temperatur der Flüssigkeit über der zutreffenden Kristallisationstemperatur von Elektrolyten in der Flüssigkeit gehalten wird.
  4. Verfahren nach einem der vorangehenden Ansprüche, wobei der während des Verfahrens gehaltene pH-Wert innerhalb eines Bereiches von ungefähr 0 bis 10,0 liegt.
  5. Verfahren nach einem der vorangehenden Ansprüche, wobei die in Schritt a) zugesetzte Säure Bromwasserstoffsäure umfasst.
  6. Verfahren nach einem der vorangehenden Ansprüche, wobei die in Schritt a) zugesetzte Säure Salzsäure umfasst.
  7. Verfahren nach einem der vorangehenden Ansprüche, wobei die in Schritt a) zugesetzte Säure eine organische Säure umfasst.
  8. Verfahren nach einem der vorangehenden Ansprüche, wobei das Reduktionsmittel ausgewählt ist aus Ammoniak, Schwefel, Schwefelwasserstoff, Natriumhydrogensulfid, metallischem Zink, metallischem Eisen, metallischem Kupfer, metallischem Nickel, metallischem Cadmium, metallischem Cobalt, metallischem Aluminium, metallischem Mangan, metallischem Mangan, metallischem Chrom, organischen Säuren, Alkoholen und Aldehyden.
  9. Verfahren nach einem der vorangehenden Ansprüche, wobei die gebrauchte Flüssigkeit ein Erdalkalimetall umfasst.
  10. Verfahren nach Anspruch 9, wobei das Erdalkalimetall Calcium ist und das zum Neutralisieren des Säureüberschusses verwendete Alkali Calciumhydroxid ist.
  11. Verfahren nach Anspruch 9, wobei das in der gebrauchten Flüssigkeit vorhandene Erdalkalimetall Calcium ist und das zum Neutralisieren des Säureüberschusses verwendete Alkali Calciumoxid ist.
  12. Verfahren nach Anspruch 9, wobei das in der gebrauchten Flüssigkeit vorhandene Erdalkalimetall Strontium ist und das zum Neutralisieren des Säureüberschusses verwendete Alkali Strontiumhydroxid ist.
  13. Verfahren nach Anspruch 9, wobei das in der gebrauchten Flüssigkeit vorhandene Erdalkalimetall Strontium ist und das zum Neutralisieren des Säureüberschusses verwendete Alkali Strontiumoxid ist.
  14. Verfahren nach einem der vorangehenden Ansprüche, wobei das zum Neutralisieren des Säureüberschusses verwendete Alkali ein Alkalimetallhydroxid ist.
  15. Verfahren nach einem der vorangehenden Ansprüche, wobei das zum Neutralisieren des Säureüberschusses verwendete Alkali Natriumhydroxid ist.
  16. Verfahren nach einem der vorangehenden Ansprüche, wobei die gebrauchte halogenhaltige Flüssigkeit ein basisches Metall umfasst und das zum Neutralisieren von Säureüberschuss verwendete Alkali ein basisches Metalloxid ist.
  17. Verfahren nach 16, wobei das basische Metalloxid ausgewählt ist aus einer Gruppe von Oxiden, bestehend aus Zinkoxid, Kupferoxid, Cobaltoxid, Cadmiumoxid oder Nickeloxid.
  18. Verfahren nach einem der vorangehenden Ansprüche, wobei die gebrauchte halogenhaltige Flüssigkeit ein basisches Metall umfasst und das zum Neutralisieren von Säureüberschuss verwendete Alkali ein basisches Metallhydroxid ist.
  19. Verfahren nach Anspruch 18, wobei das basische Metallhydroxid ausgewählt ist aus einer Gruppe von basischen Metallhydroxiden, bestehend aus Zinkhydroxiden, Kupferhydroxiden, Cobalthydroxiden, Cadmiumhydroxiden oder Nickelhydroxiden.
  20. Verfahren nach einem der vorangehenden Ansprüche, wobei ein basische Metall zum Neutralisieren von Säureüberschuss verwendet wird.
  21. Verfahren nach einem der vorangehenden Ansprüche, wobei das zum Neutralisieren von Säureüberschuss verwendete Alkali Ammoniak ist.
  22. Verfahren nach einem der vorangehenden Ansprüche, wobei die Schritte a-d in einem Mischreaktor durchgeführt werden.
  23. Verfahren nach einem der vorangehenden Ansprüche, wobei die Abtrennung der erhaltenen Flüssigkeit von jeglichem suspendierten Feststoff in einem Schwerkraftabscheider durchgeführt wird.
  24. Verfahren nach einem der vorangehenden Ansprüche, wobei die Abtrennung der erhaltenen Flüssigkeit von jeglichem suspendierten Feststoff in einem Klärseparator durchgeführt wird.
  25. Verfahren nach einem der vorangehenden Ansprüche, wobei die Abtrennung der erhaltenen Flüssigkeit von jeglichem suspendierten Feststoff in einer Zentrifuge durchgeführt wird.
  26. Verfahren nach einem der vorangehenden Ansprüche, wobei die Abtrennung der erhaltenen Flüssigkeit von jeglichem suspendierten Feststoff in einem Druckfilter durchgeführt wird.
  27. Verfahren nach einem der vorangehenden Ansprüche, wobei ein Entschäumer zur Kontrolle übermäßigen Schäumens in dem Reaktionsbehälter verwendet wird.
  28. Verfahren nach Anspruch 1, wobei die gebrauchte halogenhaltige Flüssigkeit eine Flüssigkeit mit basischem Metallhalogenid ist und der Schritt des Zusetzens von Säure fortgesetzt wird, bis der pH-Wert innerhalb eines Bereiches von ungefähr 0 bis 5,5 liegt, der Schritt des Herstellens des Kontakts mit Halogen fortgesetzt wird, bis die Dichte auf mindestens 1,198 kg/l (10,0 lb/gal) erhöht ist, die zutreffende Kristallisationstemperatur eingestellt ist und Verunreinigungen oxidiert sind, und der Schritt des Neutralisierens von Säureüberschuss die Verwendung eines basischen Metalloxids umfasst.
  29. Verfahren nach Anspruch 28, wobei das Reduktionsmittel ausgewählt ist aus Ammoniak, Schwefel, Schwefelwasserstoff, Natriumhydrogensulfid, metallischem Zink, metallischem Eisen, metallischem Kupfer, metallischem Nickel, metallischem Cadmium, metallischem Cobalt, metallischem Aluminium, metallischem Mangan, metallischem Mangan, metallischem Chrom, organischen Säuren, Alkoholen oder Aldehyden.
  30. Verfahren nach Anspruch 1, wobei die gebrauchte halogenhaltige Flüssigkeit eine gebrauchte Erdalkalimetallhalogenid-Flüssigkeit ist und der Schritt des Zusetzens von Säure fortgesetzt wird, bis der pH-Wert innerhalb eines Bereiches von ungefähr 0 bis 10,0 liegt, der Schritt des Herstellens des Kontakts mit Halogen fortgesetzt wird, bis die Dichte auf mindestens 1,198 kg/l (10,0 lb/gal) erhöht ist, die zutreffende Kristallisationstemperatur eingestellt ist und die Verunreinigungen oxidiert sind, und der Schritt des Neutralisierens des Säureüberschusses die Verwendung eines Erdalkalimetalloxids umfasst.
  31. Verfahren nach Anspruch 1, wobei die gebrauchte halogenhaltige Flüssigkeit ein Gemisch aus Calciumhalogenid und Zinkhalogenid mit einer Dichte größer als 1,078 kg/l (9,0 lb/gal) umfasst und der Schritt des Zusetzens von Säure fortgesetzt wird, bis der pH-Wert innerhalb eines Bereiches von ungefähr 0 bis 10,0 liegt, der Schritt des Herstellens des Kontakts der Flüssigkeit mit einem Halogen das Herstellen des Kontakts mit Brom umfasst, bis die Dichte auf mindestens 1,198 kg/l (10,0 lb/gal) erhöht ist, die zutreffende Kristallisationstemperatur eingestellt ist und die Verunreinigungen oxidiert sind.
  32. Verfahren nach einem der vorangehenden Ansprüche, weiter umfassend:
    f) Bestimmen der Dichte der gebrauchten halogenhaltigen Flüssigkeit;
    g) Analysieren der chemischen Zusammensetzung und des Feststoffgehaltes der gebrauchten halogenhaltigen Flüssigkeit und
    h) Entfernen des Feststoffanteils aus der gebrauchten halogenhaltigen Flüssigkeit vor dem Zusetzen von Säure zu der gebrauchten halogenhaltigen Flüssigkeit.
  33. Verfahren nach Anspruch 32, weiter umfassend:
    i) Ermitteln der zutreffenden Kristallisationstemperatur;
    j) Analysieren des Öl- und Fettgehaltes der gebrauchten halogenhaltigen Flüssigkeit und
    k) Entfernen des Feststoff-, Öl- und Fettanteils aus der gebrauchten halogenhaltigen Flüssigkeit vor Zusetzen von Säure zu der gebrauchten halogenhaltigen Flüssigkeit.
  34. Verfahren nach den Ansprüchen 32 und 33, weiter umfassend Analysieren des Polymergehaltes der gebrauchten halogenhaltigen Flüssigkeit.
  35. Verfahren nach einem der vorangehenden Ansprüche, wobei die Säure, die der gebrauchten halogenhaltigen Flüssigkeit zugesetzt wird, ausgewählt ist aus Bromwasserstoffsäure, Salzsäure und organischer Säure und das Reduktionsmittel ein p-Formaldehyd ist.
  36. Verfahren nach einem der vorangehenden Ansprüche, wobei die gebrauchte halogenhaltige Flüssigkeit mit einer bromerzeugenden Verbindung in Kontakt gebracht wird, um die Flüssigkeitsdichte zu erhöhen, die zutreffende Kristallisationstemperatur einzustellen und die Verunreinigungen zu oxidieren.
  37. Verfahren nach einem der vorangehenden Ansprüche, wobei die Flüssigkeit mit einem Alkali, ausgewählt aus basischen Metalloxiden, Erdalkalimetalloxiden und basischen Metallen, in Kontakt gebracht wird, um den Säureüberschuss zu neutralisieren.
EP02721386A 2001-03-15 2002-03-14 Verfahren zur regenerierung verbrauchter halogenidhaltiger flüssigkeiten Expired - Lifetime EP1414753B9 (de)

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IL157852A0 (en) 2004-03-28
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GB2388592B (en) 2004-11-24
AU2002252321A1 (en) 2002-10-03
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GB0321133D0 (en) 2003-10-08
IL157852A (en) 2006-07-05

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