US20090183922A1 - Method of removing dissolved iron in aqueous systems - Google Patents
Method of removing dissolved iron in aqueous systems Download PDFInfo
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- US20090183922A1 US20090183922A1 US12/009,915 US991508A US2009183922A1 US 20090183922 A1 US20090183922 A1 US 20090183922A1 US 991508 A US991508 A US 991508A US 2009183922 A1 US2009183922 A1 US 2009183922A1
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
Definitions
- Dissolved iron is removed from an aqueous solution by passing the solution through a cavitation device while feeding an oxidizing agent into the solution, mixing and heating the solution in the cavitation device to oxidize ferrous iron to ferric iron, optionally increasing the pH to form solid iron oxide, and separating the solid iron oxide from the solution in a filter.
- the process is particularly useful for removing iron from oilfield completion, drilling, and workover fluids
- iron which has historically been extremely difficult to remove in the process of cleaning and preserving the fluids for reuse.
- Iron is generally in the form of FeO, which is soluble in the low pH common in completion fluids. Dissolved iron in the form of FeO cannot be filtered unless it is oxidized to a higher oxidative state. Simply raising the pH means the useful zinc and calcium bromide salts will also precipitate.
- the fluid incorporates dissolved oxygen from the air with normal pumping and handling, which converts the iron to Fe 2 O 3 in the form of a 0.5 micron colloidal suspension, but the quantity of oxygen dissolved in this manner is seldom enough. Such small colloidal suspensions are very difficult to filter.
- the invention involves passing the iron-containing completion, drilling, or workover solution, in the presence of added oxidizing agent, through a cavitation device, followed by filtration using a filter capable of removing particles as small as 0.5 micrometers.
- Concentration of dissolved oxygen or other oxidizing agent is maintained within the cavitation device at levels of at least 2 mg./L, and the temperature within the cavitation device is maintained at least at 60° C.
- the elevated temperature promotes iron oxidation.
- the pH is beneficially increased by any convenient means, such as the addition of lime or alkali metal hydroxides, to at least 2.5.
- the cavitation device is operated so that oxygen or other oxidizing agent is thoroughly mixed and/or dissolved in the fluid and the temperature of the fluid is increased to the point at which the ferrous iron is converted to ferric iron, forming a colloidal-size precipitate of Fe 2 O 3 , which may be in hydroxide form—Fe 2 O 3 .xH 2 O.
- Colloidal iron is typically about 1 micron in size. Residence time in the cavitation device may be enhanced by recycling.
- the solution, now containing colloidal solids, is removed from the cavitation device and the solids are separated by a filter, preferably capable of removing particles as small as 0.5 micrometers.
- the solution may be monitored for iron content before entering the cavitation device, and the introduction of oxygen controlled to supply the amount required to oxidize the iron or slightly more.
- the oxygen may be introduced in the form of air, oxygen, ozone, or a chemical oxidizing agent such as hydrogen peroxide, chlorine-containing bleaches, various carbamates, or any other suitable oxidizing agent.
- air may enter the system through seals and/or the ordinary action of centrifugal or other pumps that move the fluid into the cavitation device and elsewhere in the system; the pumps may introduce air into the fluid in amounts approaching or even in excess of the 2 milligrams per liter usually sufficient to oxidize the iron present.
- a coarse filter may be used to remove larger particles before iron is removed in a microfilter.
- the cavitation device has a distinct advantage in the common situation where polymeric viscosifiers, or other polymers, are present in the fluid to be treated for iron removal.
- Water-soluble polymers of almost all varieties are notorious for their tendency to plug filters, and this is especially true where the pore size of the filter is small.
- Subjecting the viscosity-enhancing polymers to the cavitation process and its accompanying temperature increase, however, will physically destroy the polymer molecules and render their remnants filterable without plugging the filters.
- the heat generated within the cavitation device during its normal operation also assists in reducing the detrimental effects of polymers via breakdown and/or viscosity reduction.
- Our invention benefits from the additional use of certain types of activated carbon which have been found to rapidly decompose peroxides or otherwise catalytically enhance the oxidation rate of the iron species in the liquid.
- the liquid is beneficially contacted with the activated carbon immediately downstream from the cavitation device, but may be used anywhere in the system to enhance the reaction of a peroxide with the iron species in the liquid.
- FIGS. 1 a and 1 b are views of slightly different cavitation devices useful in our invention.
- FIG. 2 is a flow sheet showing the use of a cavitation device for treatment of a used oilfield fluid to remove iron.
- FIG. 3 is a flow sheet which includes an activated carbon unit.
- a cavitation device heats a solution within it by generating shock waves within the solution and also by friction within the device.
- the term “cavitation” derives from pockets or cavities which are filled by shock waves of fluid.
- cavitation device or to mean and include any device which will impart thermal energy to flowing liquid by causing bubbles or pockets of partial vacuum to form within the liquid it processes, the bubbles or pockets of partial vacuum being quickly imploded and filled by the flowing liquid.
- the bubbles or pockets of partial vacuum have also been described as areas within the liquid which have reached the vapor pressure of the liquid.
- the turbulence and/or impact, which may be called a shock wave, caused by the implosion imparts thermal energy to the liquid, which, in the case of water, may readily reach boiling temperatures.
- the bubbles or pockets of partial vacuum are typically created by flowing the liquid through narrow passages which present side depressions, cavities, pockets, apertures, or dead-end holes to the flowing liquid; hence the term “cavitation effect” is frequently applied.
- Steam or vapor generated in the cavitation device can be separated from the remaining, now concentrated, water and/or other liquid which frequently will include significant quantities of solids small enough to pass through the reactor.
- cavitation devices made by Hydro Dynamics, Inc., of Rome, Ga., most preferably the device described in U.S. Pat. Nos. 5,385,298, 5,957,122 6,627,784 and particularly U.S. Pat. No. 5,188,090, all of which are incorporated herein by reference in their entireties.
- cavitation device includes not only all the devices described in the above itemized patents U.S. Pat. Nos. 5,385,298, 5,957,122 6,627,784 and 5,188,090 but also any of the devices described by Sajewski in U.S. Pat. Nos. 5,183,513, 5,184,576, and 5,239,948, Wyszomirski in U.S. Pat. No. 3,198,191, Selivanov in U.S. Pat. No.
- FIGS. 1 a and 1 b show two slightly different variations, and views, of a cavitation devices sometimes known as a cavitation pump, or a cavitation regenerator, and sometimes referred to herein as an SPR, which we use in our invention to regenerate solutions comprising heavy brine components.
- a cavitation device sometimes known as a cavitation pump, or a cavitation regenerator, and sometimes referred to herein as an SPR, which we use in our invention to regenerate solutions comprising heavy brine components.
- FIGS. 1 a and 1 b are adapted from FIGS. 1 and 2 of Griggs U.S. Pat. No. 5,188,090, which is incorporated herein by reference along with related U.S. Pat. Nos. 5,385,298, 5,957,122, and 6,627,784.
- U.S. Pat. No. 5,188,090 patent and elsewhere in the referenced patents liquid is heated and mixed in the device without the use of a heat transfer surface, thus avoiding the usual scaling problems common to boilers and distillation apparatus.
- a housing 10 in FIGS. 1 a and 1 b encloses cylindrical rotor 11 leaving only a small clearance 12 around its curved surface and clearance 13 at the ends.
- the rotor 11 is mounted on a shaft 14 turned by motor 15 .
- Cavities 17 are drilled or otherwise cut into the surface of rotor 11 . As explained in the Griggs patents, other irregularities, such as shallow lips around the cavities 17 , may be placed on the surface of the rotor 11 . Some of the cavities 17 may be drilled at an angle other than perpendicular to the surface of rotor 11 —for example, at a 15 degree angle.
- Liquid (fluid) in the case of the present invention, a used workover, drilling, or completion fluid containing iron,—is introduced through port 16 under pressure and enters clearances 13 and 12 .
- a used workover, drilling, or completion fluid containing iron is introduced through port 16 under pressure and enters clearances 13 and 12 .
- areas of vacuum are generated and heat is generated within the fluid from its own turbulence, expansion and compression (shock waves).
- shock waves shock waves.
- “(T)he depth, diameter and orientation of (the cavities) may be adjusted in dimension to optimize efficiency and effectiveness of (the cavitation device) for heating various fluids, and to optimize operation, efficiency, and effectiveness . . .
- Rotational velocity may be on the order of 5000 rpm (col 4 line 13).
- the diameter of the exhaust ports 18 may be varied also depending on the fluid treated. Pressure at entrance port 16 may be 75 psi, for example, and the temperature at exit port 18 may be as high as 300° F.
- the heavy brine components containing solution may be flashed or otherwise treated in and/or following the cavitation device to remove excess water as steam or water vapor.
- exit port 18 is somewhat different in FIGS. 1 a and 1 b; likewise the position of entrance port 16 differs in the two versions and may also be varied to achieve different effects in the flow pattern within the SPR.
- Another variation which can lend versatility to the SPR is to design the opposing surfaces of housing 10 and rotor 11 to be somewhat conical, and to provide a means for adjusting the position of the rotor within the housing so as to increase or decrease the width of the clearance 12 . This can allow for different sizes of solids present in the fluid, to reduce the shearing effect if desired (by increasing the width of clearance 12 ), to vary the velocity of the rotor as a function of the fluid's viscosity, or for any other reason.
- Operation of the SPR is as follows. A shearing stress is created in the solution as it passes into the narrow clearance 12 between the rotor 11 and the housing 10 . This shearing stress causes an increase in temperature. The solution quickly encounters the cavities 17 in the rotor 11 , and tends to fill the cavities, but the centrifugal force of the rotation tends to throw the fluid back out of the cavity, which creates a vacuum. The vacuum in the cavities 17 draws fluid back into them, and accordingly “shock waves” are formed as the cavities are constantly filled, emptied and filled again. Small bubbles, some of them microscopic, are formed and imploded. All of this stress on the fluid mixes the constituents of the fluid and generates heat which increases the temperature of the fluid dramatically. The design of the SPR ensures that, since the bubble collapse and most of the other stress takes place in the cavities, little or no erosion of the working surfaces of the rotor 11 takes place, and virtually all of the heat generated remains within the fluid.
- the rotor and housing indeed tend to be lower in temperature than the liquid in clearances 12 and 13 . There is little danger of scale formation even with high concentrations of heavy brine components in the solution being processed.
- any solids present in the solution having dimensions small enough to pass through the clearances 12 and 13 may pass through the SPR unchanged. This may be taken into account when using the reconstituted solution in for oil well purposes. Subjecting water-soluble polymers that may be present in the solution to the localized cavitation process and heating will tend to break them down, shear them, or otherwise completely destroy them; in any case they will not be likely to foul or plug the filters set up to remove precipitated iron compounds.
- the iron-containing used completion, drilling or workover fluid enters cavitation device 30 through conduit 31 , being propelled by a pump not shown.
- An oxidizing agent is introduced to conduit 31 through line 32 .
- the oxidizing agent may be oxygen, air, a solution of hydrogen peroxide, sodium or ammonium persulfate, or any of various carbamates known as oxidizing agents, or any other convenient oxidizing agent such as a chlorine-containing bleach.
- the oxidizing agent immediately begins mixing with the fluid and the mixing effect is greatly enhanced within the cavitation device as explained above, bringing about intimate contact between the oxidizing agent and the iron species in the fluid under elevated temperatures due to the cavitation effect.
- the oxidizing agent is a gas, such as air or oxygen
- bubbles formed in the conduit 31 will immediately be dispersed and greatly divided into microbubbles, to the point of dissolution, similar to the effect described in the above cited Hudson et al patent U.S. Pat. No. 6,627,784.
- the dispersion and intimate contact of the oxidizing agent with the iron species causes oxidation and formation of Fe 2 O 3 , which may be in hydroxide form—Fe 2 O 3 .xH 2 O.
- These oxides are in solid or colloidal form, generally from 0.5 to 1.5 micron in size and are filtered out by a filter 33 capable of removing such materials. Where chloride oxidizing agents are used, the precipitates may be somewhat larger.
- Filter 33 is desirably a nanofiber medium of Nylon 66 or materials having similar properties, and desirably such a filter medium made and sold by DuPont under the trademark HMT.
- the filter may be operated in the dead-end or cross-flow mode.
- a beneficial filter medium is a sintered 904 stainless steel metallic membrane or a sintered ceramic membrane; porous plastic filters having a membrane coating of an appropriate pore size may also be used.
- Membrane and other filters able to remove particles of size 0.5 are readily available commercially. We may use any filter capable of removing particles as small as one micron and preferably as small as 0.5 micron.
- the retentate in filter 33 may be disposed of in any convenient manner; desirably the filter will be capable of convenient cleaning or backwashing for reuse, but disposable filters are also contemplated. Permeate of greatly reduced iron content passing through filter 33 is taken in line 29 to a holding tank for reuse or recirculation as a workover or completion fluid, or can be sent directly to such use.
- the system also utilizes flash tank 36 .
- Flash tank 36 is used to enhance the removal of water from the completion, drilling or workover fluid in a manner similar to that shown and described by Smith and Sloan in U.S. Pat. No. 7,201,225.
- upper outlet 39 from flash tank 36 contains vapor or steam which may be vented or condensed to make clean water for use elsewhere; its removal may be enhanced by an applied vacuum. Removal of water from the input solution in conduit 31 means that less fluid must be handled by the filters.
- This somewhat concentrated fluid 37 is supplied through line 34 b from flash tank 36 to filter 33 . Liquid in line 34 can be sent entirely to the flash tank through line 34 a, or directly to the filters, or partially to each, within the discretion of the operator.
- the flash tank 36 oxygen from the air will be entrained in the somewhat concentrated fluid 37 in the bottom of the flash tank, and this fluid 37 may be recycled to the cavitation device through line 38 , thus providing more oxygen for use in oxidizing the iron in the liquid while also providing another opportunity for oxidation of any yet unoxidized iron.
- the flash tank may be used as the source of all the oxygen in the system.
- the system of FIG. 2 is provided with recycle capabilities as well as pH-adjusting capabilities.
- the pH is generally beneficially increased by introducing a base through line 35 , so that it will be intimately mixed along with the oxidizing agent.
- a pH higher than about 2.5 is necessary for ferrous oxide to achieve a colloidal, filterable state. Accordingly, where the pH is lower than 2.5, addition of a pH-increasing agent is recommended.
- FIG. 3 in many respects similar to FIG. 2 , is a flow sheet illustrating the use of activated carbon to enhance the oxidation reaction.
- An alternate line 40 carries the output liquid from an exhaust port 18 ( FIG. 1 a or 1 b ) of cavitation device 30 directly to a container 41 for a bed of activated carbon capable of enhancing the oxidation of the iron species present in the liquid by an oxidizing agent in the liquid.
- a catalytic activated carbon made by Calgon Carbon Corporation and sold under the trademark CENTAUR has been found satisfactory. See U.S. Pat. No. 5,356,849, which explains that activated carbon made in a certain way will accelerate the decomposition of hydrogen peroxide, thus making the reactive oxygen more readily available for reaction with ferrous iron.
- the activated carbon container 41 may also be fed by line 27 from the flash tank 36 , which has the advantage that less liquid must be handled by the activated carbon than otherwise would be the case, since fluid 37 is somewhat concentrated. After passing through the activated carbon bed in container 41 , where additional colloidal iron is created, the liquid is passed through line 43 to the filter 33 , similar to the filter 33 in FIG. 2 .
- FIG. 3 The configuration of FIG. 3 is not the only one in which an activated carbon unit may be used.
- a unit such as activated carbon container 41 could be placed upstream of cavitation device 30 at any point along conduit 31 . If it is placed upstream of line 32 , which introduces the oxidizing agent, it could have its own intake for oxidizing agent.
- An activated carbon container 41 could be placed in recycle line 28 or 38 as well—it should be remembered that performance of the cavitation unit 30 is not impaired by the presence of solids in the fluid it handles.
- our invention comprises a method of treating a used oilfield fluid containing iron to remove iron therefrom comprising (a) passing the used oilfield fluid through a cavitation device in the presence of added oxygen, thereby mixing the oxygen with the oilfield fluid, elevating the temperature of the oilfield fluid and forming iron oxide solids therein, and (b) passing the used oilfield fluid through a filter capable of removing the iron oxide solids.
- It also includes a method of treating an oilfield drilling, workover or completion fluid to remove iron therefrom comprising adding an oxidizing agent to the fluid and passing the fluid through a bed of activated carbon capable of enhancing the oxidation of ferrous iron.
- our invention includes a method of removing iron from an oilfield drilling, completion or workover fluid containing iron comprising (1) passing the fluid through a cavitation device in the presence of an oxidizing agent (2) controlling the operation of the cavitation device to maintain it effective to (a) elevate the temperature, (b) dissolve and mix the oxidizing agent with the fluid, and (c) achieve the reaction of the oxidizing agent and the iron to form insoluble iron oxide, and (3) separating the insoluble iron oxide from the fluid in a filter.
Abstract
Description
- Dissolved iron is removed from an aqueous solution by passing the solution through a cavitation device while feeding an oxidizing agent into the solution, mixing and heating the solution in the cavitation device to oxidize ferrous iron to ferric iron, optionally increasing the pH to form solid iron oxide, and separating the solid iron oxide from the solution in a filter. The process is particularly useful for removing iron from oilfield completion, drilling, and workover fluids
- Iron dissolved in various kinds of aqueous solutions has caused many undesirable effects, and its removal has long been a vexing problem. As applied to workover and completion fluids used in hydrocarbon recovery, sometimes called clear completion brines, used in oil recovery, the background of the problem has been well described by Qu et al in U.S. Pat. No. 7,144,512:
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- “High density brines (completion brines) have been widely used in well completion and workover operations in oilfields in the past several decades. The completion brines are salt solutions typically having fluid densities ranging from about 8.4 ppg (pounds per gallon) to about 20 ppg. Depending on the density desired, a completion brine can be a one salt solution (e.g. NaCl, NaBr, CaCl2, CaBr2, ZnBr2 or formate salt in water), a two salt solution (e.g. CaCl2/CaBr2 or ZnBr2/CaBr2), or a three salt solution (e.g. ZnBr2/CaBr2/CaCl2). The composition of the brines determines the fluid properties such as pH, density, etc.
- Depending on the economics, a fluid can be used in a well and then purchased back to be cleaned and reused later.
- At the conclusion of any completion or workover project, a substantial volume of ‘contaminated’ or unneeded completion/workover fluid typically remains. Such fluids may be contaminated with any or all of the following: water, drilling mud, formation materials, rust, scale, pipe dope, and viscosifiers and bridging agents used for fluid-loss-control pills. Depending on their composition and level of contamination, these fluids may or may not have further practical or economic value. If it is deemed that the fluids have future use potential, they may be reclaimed. Conversely, if they are determined to have no further use, they must be disposed of in an environmentally responsible way.
- The benefits derived from the use of solids-free fluids, and especially high-density brines, for completion and workover operations have been extensively documented in the literature. Unfortunately, the costs associated with the initial purchase and subsequent disposal of such brines has been a hindrance to their universal acceptance especially since the “use once and dispose” means of disposal is neither prudent nor economically sound.
- Because of the relatively high cost and limited worldwide natural mineral resources available for producing medium- and high-density completion/workover fluids, it is essential that their used fluids be reclaimed. The reconditioned fluids must meet the same specifications as those of ‘new’ or ‘clean’ fluids. With respect to completion/workover fluids, the term ‘clean’ denotes not only the absence of suspended solids but also the absence of undesirable colloidal or soluble species which are capable of undergoing adverse reactions with formation, formation fluids or other completion fluids to produce formation-damaging insoluble substances.
- There are many known methods for removing contaminates from a brine solution. One approach is to remove suspended solids by filtration. Simple filtration processes, wherein the brine is filtered through a plate and frame type filter press with the use of a filter aid such as diatomaceous earth and then through a cartridge polishing filter, are effective to remove solid contamination but they have no effect on removing other types of contamination such as colloidal or soluble species. This is the case since colloidally dispersed and soluble contaminants cannot be removed by filtration without first treating the fluid to change the chemical and/or physical properties of the contaminants. The treatments required to salvage the fluid depend on the nature of the contaminants incorporated and their chemical and physical properties.”
- Almost all used clear completion fluids, and also many drilling fluids, contain iron, which has historically been extremely difficult to remove in the process of cleaning and preserving the fluids for reuse. Iron is generally in the form of FeO, which is soluble in the low pH common in completion fluids. Dissolved iron in the form of FeO cannot be filtered unless it is oxidized to a higher oxidative state. Simply raising the pH means the useful zinc and calcium bromide salts will also precipitate. The fluid incorporates dissolved oxygen from the air with normal pumping and handling, which converts the iron to Fe2O3 in the form of a 0.5 micron colloidal suspension, but the quantity of oxygen dissolved in this manner is seldom enough. Such small colloidal suspensions are very difficult to filter. Leaving 0.5 micron solids downhole is a problem since the formation is essentially a porous medium that cannot be backwashed. Everyone knows about iron, but until now no one has developed a practical solution for iron removal. One can add oxygen scavengers to try to keep the iron in solution, but that masks the problem and is never a permanent solution. One cannot add enough oxygen scavenger to prevent the iron from precipitating in the formation. There is simply too much oxygen. In addition, iron oxidation is a relatively slow process. One can filter a fluid today and it will be crystal clear, but tomorrow one will start seeing rust or Fe2O3 dropping out of solution. Thus, the problem has been that the ubiquitous iron is usually in solution in a used clear completion fluid, but it will damage the formation if it is not removed; removal without diminishing the other components of the fluid, or undertaking an enormous expense, has been elusive.
- Various methods of oxidizing iron in water are reviewed by Schlafer et al in U.S. Pat. No. 5,725,759. See also Maree, U.S. Pat. No. 6,419,834. Hydrogen peroxide is one of several oxidizing agents proposed to oxidize iron in well servicing fluids to a higher oxidation state; the oxide is stabilized at a higher pH, and the fluid is then filtered, in Darlington et al U.S. Pat. No. 4,465,598. Particles as small as 0.1 micrometer are said to be filtered from oil and gas well fluids by Abrams et al in U.S. Pat. No. 4,436,635.
- As none of these processes has achieved commercial success, there is a need in the industry for a practical way to prepare used completion, workover, and drilling fluids for reuse, including removing iron from them.
- The invention involves passing the iron-containing completion, drilling, or workover solution, in the presence of added oxidizing agent, through a cavitation device, followed by filtration using a filter capable of removing particles as small as 0.5 micrometers. Concentration of dissolved oxygen or other oxidizing agent is maintained within the cavitation device at levels of at least 2 mg./L, and the temperature within the cavitation device is maintained at least at 60° C. The elevated temperature promotes iron oxidation. The pH is beneficially increased by any convenient means, such as the addition of lime or alkali metal hydroxides, to at least 2.5.
- The cavitation device is operated so that oxygen or other oxidizing agent is thoroughly mixed and/or dissolved in the fluid and the temperature of the fluid is increased to the point at which the ferrous iron is converted to ferric iron, forming a colloidal-size precipitate of Fe2O3, which may be in hydroxide form—Fe2O3.xH2O. Colloidal iron is typically about 1 micron in size. Residence time in the cavitation device may be enhanced by recycling. The solution, now containing colloidal solids, is removed from the cavitation device and the solids are separated by a filter, preferably capable of removing particles as small as 0.5 micrometers.
- The solution may be monitored for iron content before entering the cavitation device, and the introduction of oxygen controlled to supply the amount required to oxidize the iron or slightly more. The oxygen may be introduced in the form of air, oxygen, ozone, or a chemical oxidizing agent such as hydrogen peroxide, chlorine-containing bleaches, various carbamates, or any other suitable oxidizing agent. Generally also it may be expected that air may enter the system through seals and/or the ordinary action of centrifugal or other pumps that move the fluid into the cavitation device and elsewhere in the system; the pumps may introduce air into the fluid in amounts approaching or even in excess of the 2 milligrams per liter usually sufficient to oxidize the iron present.
- When processing used completion and workover fluids, we do not require filtration before passing the fluid into the cavitation device, since its operation is unaffected by undissolved solids which may be found in used workover or completion fluids After passing through the cavitation device, a coarse filter may be used to remove larger particles before iron is removed in a microfilter. In processing used drilling fluids it may also be desirable to filter or screen the fluid before passing the fluid into the cavitation device.
- The cavitation device has a distinct advantage in the common situation where polymeric viscosifiers, or other polymers, are present in the fluid to be treated for iron removal. Water-soluble polymers of almost all varieties are notorious for their tendency to plug filters, and this is especially true where the pore size of the filter is small. Subjecting the viscosity-enhancing polymers to the cavitation process and its accompanying temperature increase, however, will physically destroy the polymer molecules and render their remnants filterable without plugging the filters. The heat generated within the cavitation device during its normal operation also assists in reducing the detrimental effects of polymers via breakdown and/or viscosity reduction.
- Our invention benefits from the additional use of certain types of activated carbon which have been found to rapidly decompose peroxides or otherwise catalytically enhance the oxidation rate of the iron species in the liquid. The liquid is beneficially contacted with the activated carbon immediately downstream from the cavitation device, but may be used anywhere in the system to enhance the reaction of a peroxide with the iron species in the liquid.
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FIGS. 1 a and 1 b are views of slightly different cavitation devices useful in our invention. -
FIG. 2 is a flow sheet showing the use of a cavitation device for treatment of a used oilfield fluid to remove iron. -
FIG. 3 is a flow sheet which includes an activated carbon unit. - We use a cavitation device to increase the temperature of the completion, drilling, or workover fluid while also mixing it with an oxidizing agent to oxidize the iron. A cavitation device heats a solution within it by generating shock waves within the solution and also by friction within the device. The term “cavitation” derives from pockets or cavities which are filled by shock waves of fluid.
- We use the term “cavitation device” or to mean and include any device which will impart thermal energy to flowing liquid by causing bubbles or pockets of partial vacuum to form within the liquid it processes, the bubbles or pockets of partial vacuum being quickly imploded and filled by the flowing liquid. The bubbles or pockets of partial vacuum have also been described as areas within the liquid which have reached the vapor pressure of the liquid. The turbulence and/or impact, which may be called a shock wave, caused by the implosion imparts thermal energy to the liquid, which, in the case of water, may readily reach boiling temperatures. The bubbles or pockets of partial vacuum are typically created by flowing the liquid through narrow passages which present side depressions, cavities, pockets, apertures, or dead-end holes to the flowing liquid; hence the term “cavitation effect” is frequently applied. Steam or vapor generated in the cavitation device can be separated from the remaining, now concentrated, water and/or other liquid which frequently will include significant quantities of solids small enough to pass through the reactor. We prefer to use cavitation devices made by Hydro Dynamics, Inc., of Rome, Ga., most preferably the device described in U.S. Pat. Nos. 5,385,298, 5,957,122 6,627,784 and particularly U.S. Pat. No. 5,188,090, all of which are incorporated herein by reference in their entireties. In recent years, Hydro Dynamics, Inc. has adopted the trademark “Shockwave Power Reactor” for its cavitation devices, and we use the term SPR herein to describe the products of this company and other cavitation devices that can be used in our invention. The term “cavitation device” includes not only all the devices described in the above itemized patents U.S. Pat. Nos. 5,385,298, 5,957,122 6,627,784 and 5,188,090 but also any of the devices described by Sajewski in U.S. Pat. Nos. 5,183,513, 5,184,576, and 5,239,948, Wyszomirski in U.S. Pat. No. 3,198,191, Selivanov in U.S. Pat. No. 6,016,798, Thoma in U.S. Pat. Nos. 7,089,886, 6,976,486, 6,959,669, 6,910,448, and 6,823,820, Crosta et al in U.S. Pat. No. 6,595,759, Giebeler et al in U.S. Pat. Nos. 5,931,153 and 6,164,274, Huffman in U.S. Pat. No. 5,419,306, Archibald et al in U.S. Pat. No. 6,596,178 and other similar devices which employ a shearing effect between two close surfaces, at least one of which is moving, such as a rotor, and/or at least one of which has cavities of various designs in its surface as explained above. The cavitation process also causes intimate mixing of the fluid constituents as they pass through the device, and additional heating is provided as a result of friction generated as the fluid and the rotor move within the housing.
-
FIGS. 1 a and 1 b show two slightly different variations, and views, of a cavitation devices sometimes known as a cavitation pump, or a cavitation regenerator, and sometimes referred to herein as an SPR, which we use in our invention to regenerate solutions comprising heavy brine components. -
FIGS. 1 a and 1 b are adapted fromFIGS. 1 and 2 of Griggs U.S. Pat. No. 5,188,090, which is incorporated herein by reference along with related U.S. Pat. Nos. 5,385,298, 5,957,122, and 6,627,784. As explained in the U.S. Pat. No. 5,188,090 patent and elsewhere in the referenced patents, liquid is heated and mixed in the device without the use of a heat transfer surface, thus avoiding the usual scaling problems common to boilers and distillation apparatus. - A
housing 10 inFIGS. 1 a and 1 b enclosescylindrical rotor 11 leaving only asmall clearance 12 around its curved surface andclearance 13 at the ends. Therotor 11 is mounted on ashaft 14 turned bymotor 15.Cavities 17 are drilled or otherwise cut into the surface ofrotor 11. As explained in the Griggs patents, other irregularities, such as shallow lips around thecavities 17, may be placed on the surface of therotor 11. Some of thecavities 17 may be drilled at an angle other than perpendicular to the surface ofrotor 11—for example, at a 15 degree angle. Liquid (fluid)—in the case of the present invention, a used workover, drilling, or completion fluid containing iron,—is introduced throughport 16 under pressure and entersclearances port 16 toclearance 13 toclearance 12 and outexit 18, areas of vacuum are generated and heat is generated within the fluid from its own turbulence, expansion and compression (shock waves). As explained at column 2 lines 61 et seq in the U.S. Pat. No. 5,188,090 patent, “(T)he depth, diameter and orientation of (the cavities) may be adjusted in dimension to optimize efficiency and effectiveness of (the cavitation device) for heating various fluids, and to optimize operation, efficiency, and effectiveness . . . with respect to particular fluid temperatures, pressures and flow rates, as they relate to rotational speed of (the rotor 11).” Smaller or larger clearances may be provided (col. 3, lines 9-14). Also the interior surface of thehousing 10 may be smooth with no irregularities or may be serrated, feature holes or bores or other irregularities as desired to increase efficiency and effectiveness for particular fluids, flow rates and rotational speeds of therotor 11. (col. 3, lines 23-29) Rotational velocity may be on the order of 5000 rpm (col 4 line 13). The diameter of theexhaust ports 18 may be varied also depending on the fluid treated. Pressure atentrance port 16 may be 75 psi, for example, and the temperature atexit port 18 may be as high as 300° F. Thus the heavy brine components containing solution may be flashed or otherwise treated in and/or following the cavitation device to remove excess water as steam or water vapor. Note that the position ofexit port 18 is somewhat different inFIGS. 1 a and 1 b; likewise the position ofentrance port 16 differs in the two versions and may also be varied to achieve different effects in the flow pattern within the SPR. - Another variation which can lend versatility to the SPR is to design the opposing surfaces of
housing 10 androtor 11 to be somewhat conical, and to provide a means for adjusting the position of the rotor within the housing so as to increase or decrease the width of theclearance 12. This can allow for different sizes of solids present in the fluid, to reduce the shearing effect if desired (by increasing the width of clearance 12), to vary the velocity of the rotor as a function of the fluid's viscosity, or for any other reason. - Operation of the SPR (cavitation device) is as follows. A shearing stress is created in the solution as it passes into the
narrow clearance 12 between therotor 11 and thehousing 10. This shearing stress causes an increase in temperature. The solution quickly encounters thecavities 17 in therotor 11, and tends to fill the cavities, but the centrifugal force of the rotation tends to throw the fluid back out of the cavity, which creates a vacuum. The vacuum in thecavities 17 draws fluid back into them, and accordingly “shock waves” are formed as the cavities are constantly filled, emptied and filled again. Small bubbles, some of them microscopic, are formed and imploded. All of this stress on the fluid mixes the constituents of the fluid and generates heat which increases the temperature of the fluid dramatically. The design of the SPR ensures that, since the bubble collapse and most of the other stress takes place in the cavities, little or no erosion of the working surfaces of therotor 11 takes place, and virtually all of the heat generated remains within the fluid. - Temperatures within the cavitation device—of the
rotor 11, thehousing 10, and the fluid within theclearance spaces 12 between the rotor and the housing—remain substantially constant after the process is begun and while the feed rate and other variables are maintained at the desired values. There is no outside heat source; it is the mechanical energy of the spinning rotor—to some extent friction, as well as the above described cavitation effect—that is converted to heat taken up by the solution and soon removed along with the solution when it is passes throughexit 18. The rotor and housing indeed tend to be lower in temperature than the liquid inclearances - Any solids present in the solution, having dimensions small enough to pass through the
clearances - Hudson et al U.S. Pat. No. 6,627,784, one of the patents incorporated by reference above, describes the introduction of a gas to a fluid just prior to entering a cavitation device. Gas such as air is injected into the conduit leading to
port 16, as depicted herein inFIGS. 1 a and 1 b. There may be more than oneport 16, not all of which need necessarily contain both liquid and gas. As explained in the Hudson et al patent, the cavitation process, acting on the crude mixture of liquid and gas—for example, air—breaks down the air bubbles into a large number of very small bubbles, thus greatly increasing the surface area of the bubbles and greatly increasing the likelihood of contact by the air with a species susceptible to oxidation. The air may be dissolved in the liquid. Hudson et al describe specifically the oxidation of sodium sulfide in black liquor, a byproduct of cooking wood chips. - For the present invention, it should be understood that the oxidation of iron, and FeO, present in a used workover, drilling or completion fluid, requires not only simple contact with an oxidizing agent, but a facilitating temperature and a residence time sufficient to bring about oxidation in the practical amounts.
- Referring now to
FIG. 2 , the iron-containing used completion, drilling or workover fluid enterscavitation device 30 throughconduit 31, being propelled by a pump not shown. An oxidizing agent is introduced toconduit 31 throughline 32. The oxidizing agent may be oxygen, air, a solution of hydrogen peroxide, sodium or ammonium persulfate, or any of various carbamates known as oxidizing agents, or any other convenient oxidizing agent such as a chlorine-containing bleach. The oxidizing agent immediately begins mixing with the fluid and the mixing effect is greatly enhanced within the cavitation device as explained above, bringing about intimate contact between the oxidizing agent and the iron species in the fluid under elevated temperatures due to the cavitation effect. If the oxidizing agent is a gas, such as air or oxygen, bubbles formed in theconduit 31 will immediately be dispersed and greatly divided into microbubbles, to the point of dissolution, similar to the effect described in the above cited Hudson et al patent U.S. Pat. No. 6,627,784. The dispersion and intimate contact of the oxidizing agent with the iron species causes oxidation and formation of Fe2O3, which may be in hydroxide form—Fe2O3.xH2O. These oxides are in solid or colloidal form, generally from 0.5 to 1.5 micron in size and are filtered out by afilter 33 capable of removing such materials. Where chloride oxidizing agents are used, the precipitates may be somewhat larger. -
Line 34 passes from exhaust port 18 (FIGS. 1 a and 1 b) to filter 33.Filter 33 is desirably a nanofiber medium of Nylon 66 or materials having similar properties, and desirably such a filter medium made and sold by DuPont under the trademark HMT. The filter may be operated in the dead-end or cross-flow mode. For cross-flow, a beneficial filter medium is a sintered 904 stainless steel metallic membrane or a sintered ceramic membrane; porous plastic filters having a membrane coating of an appropriate pore size may also be used. Membrane and other filters able to remove particles of size 0.5 are readily available commercially. We may use any filter capable of removing particles as small as one micron and preferably as small as 0.5 micron. The retentate infilter 33 may be disposed of in any convenient manner; desirably the filter will be capable of convenient cleaning or backwashing for reuse, but disposable filters are also contemplated. Permeate of greatly reduced iron content passing throughfilter 33 is taken inline 29 to a holding tank for reuse or recirculation as a workover or completion fluid, or can be sent directly to such use. - Optionally, the system also utilizes
flash tank 36.Flash tank 36 is used to enhance the removal of water from the completion, drilling or workover fluid in a manner similar to that shown and described by Smith and Sloan in U.S. Pat. No. 7,201,225. As shown in the '225 patent,upper outlet 39 fromflash tank 36 contains vapor or steam which may be vented or condensed to make clean water for use elsewhere; its removal may be enhanced by an applied vacuum. Removal of water from the input solution inconduit 31 means that less fluid must be handled by the filters. This somewhatconcentrated fluid 37 is supplied through line 34 b fromflash tank 36 to filter 33. Liquid inline 34 can be sent entirely to the flash tank through line 34 a, or directly to the filters, or partially to each, within the discretion of the operator. If theflash tank 36 is used, oxygen from the air will be entrained in the somewhat concentrated fluid 37 in the bottom of the flash tank, and this fluid 37 may be recycled to the cavitation device throughline 38, thus providing more oxygen for use in oxidizing the iron in the liquid while also providing another opportunity for oxidation of any yet unoxidized iron. In some situations, the flash tank may be used as the source of all the oxygen in the system. - The system of
FIG. 2 is provided with recycle capabilities as well as pH-adjusting capabilities. The pH is generally beneficially increased by introducing a base throughline 35, so that it will be intimately mixed along with the oxidizing agent. As is known in the art, a pH higher than about 2.5 is necessary for ferrous oxide to achieve a colloidal, filterable state. Accordingly, where the pH is lower than 2.5, addition of a pH-increasing agent is recommended. - Generally, we maintain the temperatures within the cavitation device at 60° C. or higher. Maintenance of the temperature, and consequent enhancement of the oxidation reaction, is benefited by a significant percentage of recycling through the cavitation device.
Recycle line 28 accordingly returns a portion of the liquid inline 34 toconduit 31 for reintroduction tocavitation device 30. Although in some situations recycling may not be necessary, the process may benefit from recycling as little as 10% of the fluid inline 34 and as much as 90%. Specifications of the cavitation device should be reconsidered when recycling a very large volume of fluid is contemplated. -
FIG. 3 , in many respects similar toFIG. 2 , is a flow sheet illustrating the use of activated carbon to enhance the oxidation reaction. Analternate line 40 carries the output liquid from an exhaust port 18 (FIG. 1 a or 1 b) ofcavitation device 30 directly to acontainer 41 for a bed of activated carbon capable of enhancing the oxidation of the iron species present in the liquid by an oxidizing agent in the liquid. A catalytic activated carbon made by Calgon Carbon Corporation and sold under the trademark CENTAUR has been found satisfactory. See U.S. Pat. No. 5,356,849, which explains that activated carbon made in a certain way will accelerate the decomposition of hydrogen peroxide, thus making the reactive oxygen more readily available for reaction with ferrous iron. See also Hayden U.S. Pat. No. 5,637,232 and the prior art reviewed in relating to catalytic oxidation by activated carbon. It is recommended that the operator review the specifications of the activated carbon with respect to the particulars of the type of oxidizing agent used. The activatedcarbon container 41 may also be fed byline 27 from theflash tank 36, which has the advantage that less liquid must be handled by the activated carbon than otherwise would be the case, sincefluid 37 is somewhat concentrated. After passing through the activated carbon bed incontainer 41, where additional colloidal iron is created, the liquid is passed through line 43 to thefilter 33, similar to thefilter 33 inFIG. 2 . - The configuration of
FIG. 3 is not the only one in which an activated carbon unit may be used. For example, a unit such as activatedcarbon container 41 could be placed upstream ofcavitation device 30 at any point alongconduit 31. If it is placed upstream ofline 32, which introduces the oxidizing agent, it could have its own intake for oxidizing agent. An activatedcarbon container 41 could be placed inrecycle line cavitation unit 30 is not impaired by the presence of solids in the fluid it handles. - It is seen, therefore, that our invention comprises a method of treating a used oilfield fluid containing iron to remove iron therefrom comprising (a) passing the used oilfield fluid through a cavitation device in the presence of added oxygen, thereby mixing the oxygen with the oilfield fluid, elevating the temperature of the oilfield fluid and forming iron oxide solids therein, and (b) passing the used oilfield fluid through a filter capable of removing the iron oxide solids.
- It also includes a method of treating an oilfield drilling, workover or completion fluid to remove iron therefrom comprising adding an oxidizing agent to the fluid and passing the fluid through a bed of activated carbon capable of enhancing the oxidation of ferrous iron.
- In addition, our invention includes a method of removing iron from an oilfield drilling, completion or workover fluid containing iron comprising (1) passing the fluid through a cavitation device in the presence of an oxidizing agent (2) controlling the operation of the cavitation device to maintain it effective to (a) elevate the temperature, (b) dissolve and mix the oxidizing agent with the fluid, and (c) achieve the reaction of the oxidizing agent and the iron to form insoluble iron oxide, and (3) separating the insoluble iron oxide from the fluid in a filter.
Claims (20)
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US12/009,915 US20090183922A1 (en) | 2008-01-23 | 2008-01-23 | Method of removing dissolved iron in aqueous systems |
US12/321,534 US20090184056A1 (en) | 2008-01-23 | 2009-01-22 | Method of removing dissolved iron in aqueous systems |
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US12/009,915 US20090183922A1 (en) | 2008-01-23 | 2008-01-23 | Method of removing dissolved iron in aqueous systems |
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US12/321,534 Continuation-In-Part US20090184056A1 (en) | 2008-01-23 | 2009-01-22 | Method of removing dissolved iron in aqueous systems |
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