IL157852A

IL157852A - Method for regeneration of used halide fluids

Info

Publication number: IL157852A
Application number: IL157852A
Authority: IL
Inventors: Lyle H Howard; Raymond D Symens; Thomas William Polkinghorn; Surendra Kumar Mishra
Original assignee: Tetra Tech; Lyle H Howard; Raymond D Symens; Thomas William Polkinghorn; Surendra Kumar Mishra
Priority date: 2001-03-15
Filing date: 2003-09-10
Publication date: 2006-07-05
Also published as: CN1278949C; GB0321133D0; WO2002074699A2; NO324398B1; IL157852A0; GB2388592A; EP1414753B1; CN1630618A; NO20034061L; EP1414753A2; WO2002074699A3; EP1414753B9; NO20034061D0; AU2002252321A1; GB2388592B

Description

D'wniyn τ,ι7π ,lmi wrm1? no'w METHOD FOR REGENERATION OF USED HALIDE FLUIDS METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 ' METHOD FOR REGENERATION OF USED HALIDE FLUIDS FIELD OF THE INVENTION 1. 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.

BACKGROUND OF THE INVENTION 2. 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. In addition, these fluids can become contaminated with impurities such as metallic cations, hydrocarbons and organic polymers. At some point, the overall quality of the brine, density and true crystallization temperature (TCT) in particular, changes to . a level that does not conform to product specifications. 3. 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 < >. that is being regenerated will drop substantially. The ehm es jn 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.

SUMMARY OF THE INVENTION 6. 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 facilities. Used halide fluids, bromide or chloride brines for example, are usually contaminated with soluble and insoluble impurities. For example, during well operation procedures, because of the continuous contact with water, these recuperated, used fluids typically have a density METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 greater than <1.078 Kg/I> (9.0 lbs/gal) but less than the required density of a desired drilling fluid. To remove impurities, increase the density, adjust the resulting TCT and enhance the concentration of electrolytes, one preferred method of regeneration of a used halide fluid comprising soluble and insoluble impurities and having a density greater than < 1.078 Kg/I> (9.0 lbs/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. Alternatively, 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 can be added to convert halogen to halide ion while maintaining the temperature at a minimum of 10°C. Preferably, the fluid is then contacted with an alkali to neutralize any excess acid. Any suspended solid impurities remaining can be separated from the fluid. During the method, it is preferred that if the metallic.cations are from a base metal group, the pH can be maintained within a range of approximately 0.0 to 5.5, For 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. Alternatively the acid can comprise hydrochloric acid or an organic acid. The reducing agent is preferably selected from a group consisting of anhydrouo ammonia, sulfur, hydrogen sulfide, sodium bisulfide, metallic zinc, metallic iron, metallic copper, metallic nickel, metallic cadmium, metallic cobalt, metallic aluminum, metallic chromium, metallic manganese, organic acids, alcohols and aldehydes.

In one aspect, the electrolyte to be enhanced in the used fluid is ■<∞ alkali metal, an alkali earth metal or a base metal. If the alkali METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 earth metal is calcium, the alkali used to neutralize excess acid can be calcium hydroxide or calcium oxide. Alternatively, if the alkali earth metal in the used fluid is strontium, the alkali used to neutralize excess acid is preferably strontium hydroxide or strontium oxide.

In another preferred method, the alkali used to neutralize excess acid is an alkali metal hydroxide, sodium hydroxide or potassium hydroxide for example. Anhydrous ammonia can also be used to neutralize excess acid.

In another preferred method 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; In another preferred method, the alkali used to neutralize excess acid is aluminum hydroxide or aluminum oxide, manganese hydroxide or manganese oxide, chromium hydroxide or chromium oxide.

One embodiment of the method for regeneration of used halide fluids comprising soluble and insoluble impurities comprises the steps of: a) determining density of the used halide fluid; b) analyzing chemical composition, the suspended solids content and the 6il and grease content of the used halide fluid; c) separating the suspended solids and oil and grease < >; d) adding acid to the used halide fluid; e) contacting the used halide fluid with halogen or halogen- generating species to increase fluid density and oxidize impurities; f) adding a reducing agent while maintaining the temperature at a minimum of 10°C; g) contacting the fluid with an alkali to neutralize excess acid; h) separating any suspended solid impurities from the fluid.

METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 13. In one preferred embodiment, the recuperated used halide fluid is piped into a reactor after density and chemical composition have been determined according to steps (a) and (b). In one aspect of the practice of this invention, the acid, halogen, reducing agent and alkali can be piped into reactor along with the fluid. Alternatively, the acid, halogen, reducing agent and alkali can be transported separately to the reactor. Bromine is one preferred halogen used in regeneration. 14. 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/I> (9.0 lbs/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 js 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/I> (10.0 Ibs./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.

BRIEF DESCRIPTION OF THE DRAWINGS . The Figure is a schematic of one embodiment of the method of the invention.

DETAILED DESCRIPTION OF INVENTION The present invention relates to an innovative method for regeneration of used halide fluids. Typically, the used halide fluids, calcium or zinc brine for example, have been recuperated from METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 industrial processes such as oil and gas drilling, agricultural chemical processes, metal plating or water treatment facilities. 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. 17. For the purpose of illustration, reference hereafter is made, for convenience, to brine fluids used in oil and gas drilling without limiting the scope of the invention. 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. 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. 18. In the practice of one embodiment of this invention according to the Figure, a used halide fluid 60, such as a drilling fluid, can comprise a density above water, <1.078 Kg/I> (9.0 lbs/gal) for example, but not high enough to perform during the drilling operations, especially in deeper or higher pressure wells. For use in well operations, 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 METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 of water, <0.995 Kg/I> (8.3 lbs/gal), typically within a range of approximately < 1.366 Kg/I> (11.4 lbs/gal) to < 1.917 Kg/I> (16 lbs/gal), and even possibly as high as <2.756 Kg/I> (23.0 lbs/gal) depending on 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. During the method of this invention, 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. During oil and gas operations, the operator of the production wells checks the specifications for the TCT of the electrolytes within the fluids being used. These porcipitatoo adversely affect the properties of the fluid that are desirable for the oil arid 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 ] 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 of thereof can be employed. Strontium chloride, strontium bromide, copper chloride, copper bromide, nickel chloride, nickel bromide, aluminum chloride or aluminum bromide can also be considered.

METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 . 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. In one embodiment metal present in the recuperated used halide can comprise zinc, copper cobalt, cadmium, nickel, potassium, cesium, lithium, barium, magnesium, aluminum, 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. When blending a relatively high- density clear brine fluid, bromide electrolytes provide higher flexibility than the relatively low-density chloride electrolytes. In addition, the stability and TCT of the blended finished product also depends on the proportion of the individual electrolytes in the composition. For example, 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, on the other hand, 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. 21. During the regeneration of used halide fluids, 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. Preferably, the solids are removed by a solid-liquid METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 < known > separation method ¼*ew 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. 22. During one method for regenerating used halide 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/I> (9.0 lbs/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. 23. " One primary purpose of regenerating used halide fluids according to the method of this invention is to efihartee the electrolytes lost during well operations or industrial use of the fluid. In one preferred method, prior to addition of the chemicals to restore the electrolyte content of the used halide 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 a calcium chloride, for example, a calcium oxide can be used to neutralize excess acid thereby restoring calcium ions.

METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 24. In one preferred method of the practice of this invention, 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. Alternatively, a blend of chlorides and bromides of calcium and zinc in various proportions can be used. For example, aqueous zinc bromide and calcium bromide, zinc bromide and calcium chloride or zinc chloride and calcium bromide. Acidification is required to avoid precipitation of the metallic salts, particularly where zinc and calcium are present. If the used halide comprises base metals, a pH within a range of. O to 6, preferably 0 to 5.5, is therefore preferred. If 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. Alternatively 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 metallic cation s> comprise metaie , hydrocarbons or polymers. Alternatively, the used halide fluid can be contacted with a bromine-generating species. 26. The addition of bromine enhances the bromide ions available in the fluid so as to return the used halide fluid to the desired density for it's 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, tbe« oxidation is necessary to destroy these polymers. If the used brine is not viscosified, however, acidification is not necessary to oxidize the polymer. That METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 step can be eliminated so that the process next comprises the addition of a halogen. 27. Unlike peroxides, 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. Preferably 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 eemte* 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. - 28. A reducing agent 30 can be added in a controlled manner to combine with and remove excess bromine. Preferably 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 aluminum, metallic manganese, metallic chromium, organic acids, alcohols and aldehydes. 29. In a further step of this method, the fluid is preferably contacted with an alkali 20 to neutralize any excess acid. In one aspect, 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. To regenerate the used halide fluid, the metal ions must be restored to the original density required for the useful function of the halide brine in the well. In one embodiment, the alkali earth metal in the -METHOD FOR REGENERATION OF USED HALiDE FLUIDS - 21 January 2003 recuperated halide fluid is calcium, in this embodiment, the alkali used to neutralize excess acid can be calcium hydroxide or calcium oxide. Alternatively, if the alkali earth metal in the used fluid is strontium, the alkali used to neutralize excess acid is preferably strontium hydroxide or strontium oxide.

. If the electrolyte to be restored is an alkali metal , 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 orbaoo motai, the alkali used to neutralize excess acid can be a base metal oxide. In this case, 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 on 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. Alternatively, the alkali used to neutralize excess acid is a base metal hydroxide. The base metal hydroxide can be selected from a group of base motai consisting of zinc, copper, cobalt, cadmium or nickel. In an alternative embodiment, the alkali used to neutralize excess acid is ammonia 31. In one specific embodiment of the method of this invention, 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. In another embodiment of the method of this invention, the alkali is lime, the reducing agent is ammonia, the halogen is bromine and the acid is hydrobromic acid. Ammonia is one preferred reducing agent in an alkali and alkali earth ■METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 metal systems and p-formaldehyde is the preferred reducing agent in a base metal system. 32. 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. In one aspect of the method of this invention, the steps performed during the method are performed in a mixed reactor, preferably a stirred reactor or a tube reactor 10. In one embodiment, 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 m the reactor 10. Alternatively, the influent chemical solutions can be piped in separately. In another preferred embodiment, 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. 33. 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. In one embodiment, the meters comprise an ORP meter, a pH meter and a density meter In one preferred method of this invention, 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 on as a batch process or a continuous process. 34. In one aspect, 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 ETHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 suspended solid is performed in a clarifer. 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.

Example 1 : . A 500 ml sample of a recovered completion fluid from an oil well with density of < 1.194 Kg/1> (15.98 lb/gallon) 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 required basis 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 I> (17.91 lb/gallon) and 35 mg/kg.

Example 2: 36. 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 a 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 METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 added on as required basis 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 3: 37. This test was conducted on a 500 ml sample of the same fluid as described in Example 1. In this case, 10 ml of liquid bromine was introduced to the fluidr while it was kept stirred and using a hot plate the temperature of the reaction solution was raised to 80°F (26.7°C). The reaction fluid was kept stirred at this temperature for 1 hour, which was followed by addition of 13 g of metallic zinc as the reducing, agent. In this test no basic material was added for the neutralization of excess acid. The final fluid was filtered and analyzed. The density and iron content of the final product ½»- determined to be <2.39 Kg/1> ( 19,95 lb/gallon) and 32 mg/kg, respectively.

Example 4: 38. 500 ml of a recovered drill-in fluid from an oil well, that contained polymer and solid material such as calcium carbonate, with density of < 1.5.45 Kg/I> (12.9 lb/gallon) and iron content of 115.3 mg/kg 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 fluid was raised to 160°F (71.1°C). The reaction fluid was kept stirred at this temperature for 1 hour, which was followed by addition of 29 ml of formalin (37% formaldehyde solution in water stabilized with 12-14% methanol). The excess acid generated in the reaction was neutralized by the addition METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 of lime on required basis (29 gm). The final reaction fluid was filtered and analyzed. The density and iron content of the filtered fluid were measured to be <1.593 Kg 1> (13.3 lb/gallon) and 14 mg/kg, respectively.

Example 5: 39. 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/I> (13.4 lb/gallon) and 10 mg/kg, respectively.

Example 6: 40. 500 ml sample of a drill-in fluid recovered from -eH oil well with density of < 1.894 Kg I> (15.81 lb/gallon) and iron content of 105 mg/kg was placed in a glass beaker and kept stirred with an electrically driven stirrer. To this 10 ml of liquid bromine was introduced and the temperature of the reaction fluid was raised and maintained at 152°F (66.7°C) for 1 hour using a hot plate. 12.8 g of metallic zinc was added as the reducing agent. In this case, no base was added for the neutralization of excess acid that was §eeerafeft during the course of reaction. The final reaction suspension was filtered and analyzed. The density and iron content were measured to be <1.911 Kg/I> (15.95 lb/gallon) and 38 mg/kg, respectively.

METHOD FOR REGENERATION OF USED HALIDE FLUIDS - 21 January 2003 Example 7: 41. On a 500 ml of the same fluid that was used in Example 6, the addition of liquid bromine in this test was increased to 30 ml. The temperature of the reaction fluid was maintained at 150°F (65.6°C) for 0.5 hour. In this case, 8.8 g of p-formaldehyde was added as the reducing agent, while lime was used for the neutralization of excess acid content of the reaction. The density and iron content of the final filtered fluid were measured to be <1.932 Kg/I> (16.13 lb/gallon) and 42 mg/kg, respectively.

Example 8: 42. 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/gallon) and 44 mg/kg, respectively. . 43. The foregoing description is illustrative and explanatory of preferred embodiments of the invention, and variations in the size, shape, materials and other details will become apparent to those skilled in the art. It is intended that all such variations and modifications which fall within the scope or spirit of the appended claims be embraced thereby.

Claims

METHOD FOR REGENERATION OF USED HALIDE FLUIDS Amended Claims:

1. 1. A method for regeneration of used halide fluids comprising soluble

2. And insoluble impurities and having a density greater than 9.0 Ibs./gal, the

3. Method comprising:

4. A) adding acid to the used halide fluid;

5. B) contacting the used halide fluid with halogen to increase fluid

6. Density, adjust the true crystallization temperature and

7. Oxidize impurities;

8. C) adding a reducing agent while maintaining the temperature 9 at a minimum of 10°C; 10 d) contacting the fluid with an alkali to neutralize excess acid; 11 e) separating any suspended solid impurities from the fluid. 1 2. The method for claim 1 wherein the used halide fluid is contacted 2 with a halogen-generating species. 1 3. The method for any of the preceding claims wherein the temperature 2 of the fluid is maintained above the true crystallization temperature 3 of electrolytes within fluid. 1 4. The method of any of the preceding claims wherein the pH 2 maintained during the method is within a range of approximately 0 to 3 10.0. 1 5. The method of any of the preceding claims wherein the acid added 2 in step 1 comprises hydrobromic acid. 1 6. The method of any of the preceding claims wherein the acid added 2 in step 1 comprises hydrochloric acid. 1 7. he method of any of the preceding claims wherein the acid added in 2 step 1 comprises an organic acid. 1 8. The method of any of the preceding claims wherein the reducing 2 agent is selected from a group consisting of ammonia, sulfur, , 3 hydrogen sulfide, sodium bisulfide, metallic zinc, metallic iron, METHOD FOR REGENERATION OF USED HALIDE FLUIDS metallic copper, metallic nickel, metallic cadmium, metallic cobalt, metallic aluminum, metallic manganese, metallic chromium, organic acids, alcohols and aldehydes.

9. The method of any of the preceding claims wherein the used fluid comprises an alkali earth metal.

10. The method of claim 9 wherein the alkali earth metal is calcium and the alkali used to neutralize excess acid is calcium hydroxide.

11. The method of claim 9 wherein the alkali earth metal present in the used fluid is calcium and the alkali used to neutralize excess, acid is calcium oxide.

12. The method of claim 9 wherein the alkali earth metal present in the used fluid is strontium and the alkali used to neutralize excess acid is strontium hydroxide.

13. The method of claim 9 wherein the alkali earth metal present in the used fluid is strontium and the alkali used to neutralize excess acid is strontium oxide.

14. The method of any of the preceding claims wherein the alkali used to neutralize excess acid is an alkali metal hydroxide.

15. The method of any of the preceding claims wherein the alkali used to neutralize excess acid is sodium hydroxide.

16. The method of any of the preceding claims wherein the used halide fluid comprises a base metal and the alkali used to neutralize excess acid is a base metal oxide.

17. The method of 16 wherein the base metal oxide is selected from a group of oxides consisting of zinc oxide, copper oxide, cobalt oxide, cadmium oxide or nickel oxide.

18. The method of any of the preceding claims wherein the used halide fluid comprises a base metal and the alkali used to neutralize excess METHOD FOR REGENERATION OF USED HALIDE FLUIDS

19. The method of claim 18 wherein base metal hydroxide is selected from a group of base metal hydroxides consisting of zinc hydroxides, copper hydroxides, cobalt hydroxides, cadmium hydroxides or nickel hydroxides.

20. The method of any of the preceding claims wherein a base metal is used to neutralize excess acid.

21. The method of any of the preceding claims wherein the alkali used to neutralize excess acid is ammonia

22. The method of any of the preceding claims wherein steps a-d are performed in a mixed reactor.

23. The method of any of the preceding claims wherein separation of the resulting fluid from any suspended solid is performed in a gravity settler.

24. The method of any of the preceding claims wherein separation of the resulting fluid from any suspended solid is performed in a clarifer.

25. The method of any of the preceding claims wherein separation of the resulting fluid from any suspended solid is performed in a centrifuge.

26. The method of any of the preceding claims wherein separation of the resulting fluid from any suspended solid is performed in a pressure filter.

27. The method of any of the preceding -claims wherein a defoaming agent is used to control excessive foaming in the reaction vessel.

28. The method of claim 1 wherein the used halide fluid is a base metal halide fluid and the step of adding acid continues until the pH is within a range of approximately 0 to 5.5, the step of contacting with halogen continues until the density is increased to at least 10.0 Ibs./gal., the true crystallization temperature is adjusted and impurities oxidized, and the step of neutralizing excess acid comprises using a base metal oxide.

29. The method of claim 28 wherein the reducing agent is 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 aluminum, metallic manganese, metallic chromium, organic acids, alcohols or aldehydes.

30. The method of claim 1 wherein, the used halide fluid is a used alkali earth metal halide fluids and the step of adding acid continues until the pH is within a range of approximately O o 10.0, the step of contacting with halogen continues until the density is increased to at least 10.0 Ibs./gal., the true crystallization temperature is adjusted and impurities oxidized, and the step of neutralizing excess acid comprises using an alkali earth metal oxide.

31. . The method of claim 1 wherein the used halide fluid comprises a blend of calcium halide and zinc halide having a density greater than 9.0 Ibs./gal., and the step of adding acid continues until the pH is within a range of approximately 0 to 10.0, the step of contacting the fluid with a halogen comprises contacting with bromine until the density is increased to at least 10.0 Ibs./gal., the true crystallization temperature is adjusted and impurities oxidized.

32. The method of any one of the preceding claims further comprising: f) determining density of the used halide fluid; g) analyzing chemical composition and solids content of the used halide fluid; and h) removing solids content from the used halide fluid prior to adding acid to the used halide fluid.

33. The method of claim 32 further comprising: i) determining the true crystallization temperature; j) analyzing oil and grease content of the used halide fluid; and , k) removing solids, oil and grease content from the used halide fluid prior to adding acid to the used halide fluid.

34. The method of claims 32 and 33 further comprising the polymer content of the used halide fluid.

35. The method of any of the preceding claims wherein the acid added to the used halide fluid is selected from a group consisting of hydrobromic acid, hydrochloric acid and organic acid and the reducing agent is a p-formaldehyde

36. The method of any of the preceding claims wherein the used halide fluid is contacted with bromine-generating species to increase fluid density, adjust true crystallization temperature and oxidize impurities.

37. The method of any of the preceding claims wherein the fluid is contacted with an alkali selected from a group consisting of base metal oxides, alkali earth metals oxides and base metals to neutralize excess acid.