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Process for Preparing a Stabilized Chromium \III\ Propionate Solution

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Process for Preparing a Stabilized Chromium \III\ Propionate Solution Europaisches Patentamt European Patent Office © Publication number: 0 194 596 Office europeen des brevets A2 © EUROPEAN PATENT APPLICATION C 07 C 53/122 © Application number: 86103020.3 ©intci.": C 07 C 51/41, C 08 L 5/00 © Date of filing: 07.03.86 C 08 L 33/26, E 21 B 47/00 © Priority: 11.03.85 US 710754 © Applicant: PHILLIPS PETROLEUM COMPANY 5th and Keeler Bartlesville Oklahoma 74004(US) © Date of publication of application: 17.09.86 Bulletin 86/38 © Inventor: Mumallah, Nairn Abdul-Kader 4519 E. Tuxedo Blvd © Designated Contracting States: Bartlesville, OK 74006IUS) AT DE FR GB IT NL SE © Inventor: Shtoyama.TodKay 5620 East Circle Bartlesville, OK 74006(US) © Representative: Dost, Wolfgang, Dr.rer.nat, Dipl.-Chem. et al. Patent- und Rechtsanwalte Bardehle-Pagenberg-Dost-Altenburg & Partner Postfach 86 0620 D-8000 Munchen 86IDE) © Process for preparing a stabilized chromium (III) propionate solution and formation treatment with a so prepared solution. © A A sulfate-free clear green solution of chromium (III) propionate is prepared by mixing aqueous propionic acid containing up to 55 weight percent propionic acid with a chromium (Vf) oxidant, such as a dichromate or chromate, and a sulfur-containing reductant, such as a bisulfite, which on reacting yields two phases: a lower sulfate-containing phase for discard or recycle and an upper phase solution of sulfate-free clear green propionate-sequestered chromium (III), the latter phase being stabilized with additional acid. The upper phase solution is useful for crosslinking polymeric viscosifiers such as partially hydrolyzed acrylamide-based polymers and the like in permeability contrast corrections in enhanced oil recovery operations. < (0 0) in 0) Q. Ul Croydon Printing Company Ltd. Field of the Invention The invention pertains to methods of preparing stable aqueous sulfate-free propionate-sequestered chromium(III) solutions. In a particular aspect, the invention pertains to the use of inorganic sulfur compound/chromium(VI) redox system to prepare aqueous sulfate-free propionate-sequestered chromium(III) solutions. The invention further pertains to methods for correcting the water permeability contrast of heterogeneous subterranean formations. Background of the Invention In oil-producing fields employing waterflooding, the water tends to channel through zones of high permeability and to by-pass a large amount of oil-in-place. Since waterflooding fluids usually contain chemicals, and even relatively small amounts of chemicals in the hundreds of millions of gallons of water employed become expensive, an efficient sweep by the waterflood is important. I Water channeling can be reduced by injecting a solution of a polymer and a polyvalent metal cation crosslinking agent under conditions which gel the polymer, plugging off the more permeable zones, and diverting the subsequently injected water into the formerly less permeable but now relatively more permeable oil-bearing strata. The use of such as aluminum citrate and related polyvalent metal cations as crosslinking agents has been known for some time. However, citrate-sequestered aluminum type of agents has not been entirely satisfactory in some of the more hostile environments, such as formation temperatures of greater than about 170°F and/or hardness cation values in the formation water of greater than about 500 ppm. Chromium(III) propionate solution is an effective agent for crosslinking polymers such as the partially hydrolyzed acrylamide-based polymers to form a gel in high permeability zones of an oil bearing reservoir, in either near-well treatments or indepth applications. Not only is chromium(III) propionate solution effective for such permeability correction processes, and is useful in hard brines, but that, surprisingly, the propionate component is biocidal against the pestiferous sulfate-reducing bacteria usually present in the formation water. Thus, both the crosslinking benefits can be obtained, plus the biocidal benefits. However, preparation of useful chromium propionate solutions has proven difficult. The chromium(III) propionate solution must be discretely prepared. Sulfate by-products in the product solution, are undesirable because of the potential formation damage caused by precipitation of CaS04 and/or BaS04, and in addition can be metabolized by sulfate-reducing bacteria to produce corrosive "souring" gas H2S. Some methods of preparation have resulted in sludges, objectionable due to potential clogging of the oil-bearing strata. Aqueous solutions of sulfate-free propionate-sequestered chromium(III) of good clarity, easily and readily prepared in a reproducible manner have been a goal, or perhaps an obstacle, in the path of the use of this highly important material in oil field processes. Brief Description of the Invention We have discovered a unique process in which the use of an inorganic sulfur compound reducing agent such as bisulfite and a chromium(VI) oxidant such as a chromate or dichromate in admixture with a propionic acid source, and water, employing particular proportions and separatory steps, results consistently in a two liquid phase system of which one is an easily separable essentially sulfate-free clean clear green chromium(III) propionate solution, a propionate-sequestered chromium(III). Our method of producing a clear clean green propionate-sequestered chromium(III) solution involves two basic steps: Cr+6@Cr+3 a) reduction of by, e.g., bisulfite in aqueous propionic acid, b) separation of the by-product sulfate-containing phase. The above steps optionally can be followed by: c) dilution and/or neutralization of the Cr(III) propionate solution. The steps in more detail are as follows: (a) Reduction of chromium(VI) to chromium(III) is effected by an inorganic sulfur-based compound as reducing agent, such as bisulfite, in aqueous propionic acid containing a sufficient complexing amount of propionic acid, but not more than 55 weight percent. This reductive step at controlled temperature results in two readily separable liquid phases. The lower aqueous phase contains the undesirable sulfate. The upper aqueous phase is sulfate-free and consists of an aqueous acidic solution of propionate-sequestered chromium(III). (b) Separation of the two-liquid phases is carried out by any convenient means. The sulfate-containing phase is discarded, or otherwise treated for recovery. The clean essentially sulfate-free (upper) phase solution of aqueous acidic propionate-sequestered chromium(III) solution is retained as product for use in down-hole treatment. Subsequently, to the aqueous acidic propionate-sequestered chromium(III) solution, can be added a further acid, other than propionic acid, if desired, or where needed as discussed hereinafter. The aqueous acidic propionate-sequestered chromium(III) solution, with the additional acid where employed, can be diluted with water to a convenient metering volume, or partially neutrolyzed with an alkaline agent, or both, in any order. At least about a 4:1 molar ratio of propionate:chromium is required to ensure a proper chromium(III) propionate solution and further that an excess of acid (ligand) is necessary to form a stable solution so as to have a total ligand:chromium molar ratio on the order of at least about 11:1. This needed excess ligand acidity can be provided by a less expensive acid than propionic acid, such as acetic acid or muriatic acid, if such other acid is added after the chromium(III) propionate complex solution itself is first formed, and thus achieve a stable solution at lesser cost. It is an object of our invention to prepare propionate-sequestered chromium(III) solutions of effective character, uniform, clear, essentially sulfate-free, and without sludge or polymer content. It is a further object of our invention to prepare chromium(III) propionate solutions useful for gelling water-soluble polymeric viscosifiers. It is also an object of our invention to provide improved methods of permeability contrast correction in high permeability streaks both for indepth crosslinking applications and for near-well applications. An additional object of our invention is to provide a method to produce propionate-sequestered chromium(III) solutions in a stable as well as an economical form. It is also an object of our invention to provide a method for treating underground formations employing a gelable injectable liquid composition employing our propionate-sequestered chromium(III) solutions. Brief Description of the Drawing FIG. 1 illustrates a preferred method of mixing the preparative ingredients to form the solution of the chromium(III) propionate-sequestered complex. Chromium(VI) compound 1, sulfite-type reducing agent 2, acid 3, and water 4, are added 5 through opening 6 to mixing vessel 7 to form admixture 8, with fill or level line shown as 9. Heating/cooling 11 controls mixture temperature. Loop circulating pump 12 provides mixing by taking admixture out 13 and returning 14. A free-board 15 is maintained to avoid overfilling and splash-out. After desired mixing, the mixture can be allowed to separate, or can be transferred to a separatory means. FIG. 2 presents the spectra of solutions of material resulting from several different preparative routes for the attempted preparation of active chromium(III) propionate solutions. The spectra are shown in the visible range of 390 to 600 nm wavelength numbers. Active chromium(III) propionate solutions exhibit absorbance maxima at about 435 nm and 580 nm. Spectrum (1) is that of a solution prepared with
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