[0001] This application is a continuation of, and claims priority of, my prior, co-pending application, Ser. No. 09/187,471, filed Nov. 6, 1998, and which is issuing on Mar. 6, 2001 as U.S. Pat. No. 6,196,765.
[0002] 1. Field of the Invention
[0003] This invention relates generally to earth materials and the environment. More specifically, this invention relates to a process for treating rock heaps to prevent oxidized species release, including acid drainage, therefrom.
[0004] 2. Related Art
[0005] Acid drainage from closed mines and waste heaps has been an important environmental problem. Prior art methods to alleviate this problem include collecting and treating acidic water discharged from the polluting source. Also, other treatment methods have attempted to prevent the acid drainage from the source in the first place.
[0006] U.S. Pat. No. 4,861,482, issued Aug. 29, 1989, (Frankenberger et al.) discloses removing selenium from soil and water by adding nutrients, including cobalt, zinc and nickel ions, for microbes in the soil or water, resulting in the formation of volatile alkylselenides.
[0007] U.S. Pat. No. 5,387,271, issued Feb. 7, 1995, (Crawford et al.) discloses biodegrading nitroaromatics in soil and water with a first fermentation operation performed by an inoculum of aerobic and/or facultative microorganisms fed by an added carbohydrate nutrient. This first operation is followed by a second anaerobic operation performed by an inoculum of mixed anaerobic microorganisms fed by the remaining carbohydrate nutrient.
[0008] U.S. Pat. No. 5,399,048 (Walker), issued Mar. 21, 1995, discloses capping an exposed rock heap surface with an impermeable coating containing seeds and/or a coloring additive for esthetic purposes.
[0009] U.S. Pat. No. 5,616,251 (Batarseh), issued Apr. 1, 1997, discloses treating material causing acid mine drainage with a liquid containing a Lewis base group (M-) attached to a hydrophobic group (-R) for example, water-soluble alkylated phosphate. The Lewis base group component reacts with the metal in the acid-causing material.
[0010] U.S. Pat. Nos. 5,632,715 & 5,710,361 (Harrington et al), issued May 27, 1997 and Jan. 20, 1998, respectively, disclose in-situ immobilization of metals in waste heaps by injecting a nutrient into a passageway into the heap, the nutrient feeding sulfide-producing microorganisms also provided to the heap to create less-soluble metal sulfides in the heap.
[0011] Still, there exists a need to prevent acid drainage from rock heaps indefinitely in a self-sustaining manner. This invention addresses that need.
[0012] The invention is a process for treating earth materials, such as rock heaps, for example, to prevent acid drainage therefrom. According to the invention, a first step comprises displacing and/or depleting the oxygen concentration in the gas-phase of the rock heap. Preferably, the rock heap gas-phase oxygen concentration is reduced in this step enough to prevent oxidative reactions that cause acid and soluble metal formation. Preferred methods of this displacement and/or depletion include: displacement by another gas, which may be called “physical depletion”; displacement/depletion by chemical reaction(s), which may be called “chemical depletion,” in which oxygen is displaced by gas reaction products or is consumed by the reaction(s); or displacement/depletion by the reactions of microbiological activity and by the gasses produced by that activity, which may be called “biological depletion”.
[0013] Optionally, selected microbial nutrients that favor reductive reactions rather than oxidative reactions may be added to the rock heap. This way, in rock heaps containing sulfide materials, carbon oxidation is thermodynamically favored over sulfide oxidation, causing gas-phase depletion of oxygen via carbon dioxide formation. In addition, in-situ cyanide and nitrate degradation reactions are accelerated.
[0014] Another aspect of the prevent invention is the lessening or eliminating of the “chimney effect” that typically occurs in a prior art rock pile, and the consequent lessening/eliminating of oxygen infiltration (“in-flow”) into the rock pile. The “chimney effect” in a prior art rock pile is the flow of ambient air into the pile at its sides near its bottom, and then through the pile and out its top. This bottom-to-top air flow is caused by oxidative chemical/biochemical reactions occurring in the prior art rock pile, which reactions are exothermic, causing the pile to heat up. This heating effect reduces the density of the gases in the rock pile, resulting in their floating up and out of the pile. Also, because the chemical/biochemical reactions occurring in the prior art pile are oxidative, the relative composition of the gas phase changes, resulting in gases of less average density. This lighter gas composition effect also contributes to the prior art “chimney effect.”
[0015] In the present invention, formation of lower oxygen concentration conditions in the rock heap increases the density of the rock heap gas-phase, blocking the “chimney effect.” The formation of carbon dioxide gas (CO
[0016] According to an additional step of the instant invention, the gas-phase oxygen concentration in the heap is maintained at a low level. For example, additional selected nutrients are provided to the rock heap to protect against future oxygen infiltration. Preferably, to obtain this maintenance condition indefinitely, the surface of the rock heap is covered with a thin layer of soil which is planted with vegetation. The natural biological cycle of the vegetation on the surface of the rock heap provides the microbial nutrients necessary to indefinitely maintain the low oxygen concentration conditions in the heap.
[0017]
[0018]
[0019]
[0020]
[0021]
[0022]
[0023] Referring to the drawings, there is depicted in
[0024] In prior art rock piles containing sulfidic waste ore, for example, a principal chemical/biological reaction taking place includes:
[0025] wherein the product sulfate (SO
[0026] Referring to
[0027] wherein the product carbon dioxide (CO
[0028] In addition, the invention as schematically illustrated in
[0029] Referring to
[0030] Other displacing gases
[0031] Referring to
[0032] Other reagents
[0033] Referring to
[0034] In this case, the oxygen in the rock pile is consumed by the chemical reaction that is catalyzed by microbiological activity, and is displaced by the CO
[0035] If indigenous bacteria populations are not sufficient to obtain or maintain low oxygen conditions, the indigenous bacteria populations may be supplemented by adding additional indigenous bacteria or additional non-indigenous bacteria. Other nutrients and mixtures thereof may also be used. Again, these bacteria populations and nutrients may be selected to displace or consume the oxygen originally present in the rock pile gas-phase. Also, these populations and nutrients may be adjusted to account for the change in the content of the gas-phase of the rock pile as the oxygen concentration is first decreased and then maintained. For example, the following describes one approach to maintaining a decreased oxygen concentration:
[0036] Other maintenance techniques may also be used to keep the depleted oxygen concentration at a lower level suitable for the purposes of the present invention. For example, the rock pile may be capped with an impervious cover, like, for example, thick soil or other earth material, concrete or a polymer blanket. Then, optionally, additional microbiological nutrients may be supplied to the interior of the rock pile through holes or conduits in the impermeable cover. Likewise, even when the thin soil and vegetative covers are used, depending on geographical, climatological and other factors, additional microbiological nutrients may be required or desired, and, therefore, may be injected or otherwise added to the pile beneath the covers. Microbiological nutrients may be added after the rock heap is created, as discussed above. Also, these nutrients may be added as the rock heap is created, for example, by adding a carbon source from, for example, waste timber, brush or food processing waste, to each truckload or conveyor discharge load to the heap. Also, these microbiological nutrients may be added before the heap is created, by, for example, adding a carbon source to the explosive charge when the original ore pile is created (see the discussion relating to
[0037] Generally, the engineering design parameters for rock piles are functions of the surface/volume ratio of the pile. See
[0038] As stated earlier, microbiological activity that favors reductive reactions in the heap is especially beneficial. Examples of microbiological nutrients that favor these reductive reactions are sugars (dextrose, fructose, sucrose, lactose, etc.), alcohol (methanol, ethanol, ethylene glycol, glycerol), fatty acids, preferably, a mixture of dextrose and methanol/ethanol with a slow release component such as fatty acids. Typically, these nutrients are applied in the following amounts: 0.1 lb sugars, 0.2 lb alcohols and 0.05 lb fats per ton rock, depending on the moisture content of the rock and the extent of prior oxidation products contained in the rock, and the site-specific meteoric flux.
[0039] Referring to
[0040] By a “lower oxygen concentration,” suitable for the purposes of the present invention, I mean a concentration in the range of from about 0% to 18 vol %, and preferably from about 0% to 3%. At or below these ranges of oxygen concentration, oxidative reactions that cause acid and soluble metal formation are inhibited or minimized or prevented.
[0041] Practically, in the field, the oxygen concentration in the rock pile may be determined by conventional techniques, for example, by oxygen sensors in the gas or liquid phase of the heap. Alternatively, a “break-through” approach to estimating displacement of oxygen by detecting the presence or concentration of the displacing gas may be used. For example, the presence of hydrocarbon gases may be detected, and their displacement of oxygen continued to excess, to ensure an oxygen concentration below about 3%.
[0042] Alternatively, a “lower oxygen concentration” suitable for the purposes of the present invention may be inferred or deduced from a measured rock pile gas-phase density greater than about 0.00125 g/ml, or the mean ambient gas phase density. In this case, a rock pile gas-phase density greater than this amount will result in a blocking of the rock pile “chimney effect.” Rock pile gas phase density may be measured by conventional techniques, for example, a thermocouple gauge may be used as described in Levine, 1995 (
[0043] Compared to the process disclosed in the Harrington patents '715 and '361 discussed above, the instant invention is applicable to waste heaps which are not oxidized to the extent that a significant fraction of metals are already mobile by dissolution in drainage water. For example, this invention is applicable to waste heaps containing substantially more sulfidic wastes than oxidized wastes. With sulfidic waste ore, or gaugue, from a gold mining operation, for example, when the waste heap is first created, it contains mostly sulfidic materials, and few oxidized materials. Then, as the “chimney effect” is created and continues for the heap, gradually, as time passes, more and more of the sulfidic materials in the heap are oxidized to become sulfates, which sulfates are water soluble and may be leached from the heap and appear as acid drainage. If this condition is allowed to continue for a long time, eventually the heap contains mostly oxidized materials, and the possibly toxic oxidized metals are considered to be “mobile”, that is, subject to dissolution in the heap drainage and appearing as contaminants in it. For this advanced stage of waste heap deterioration, the process of the Harrington patents '715 and '361 is particularly applicable. That is, the treatment liquid of these patents, containing the microbe nutrients for producing microbial sulfides and ultimately metal sulfides, inhibits the migration of already “mobile” oxidized metals.
[0044] The instant invention, on the other hand, is applicable to waste heaps in which the possibly toxic metals are not yet “mobile” due to oxidation. In effect, the instant invention prevents the subject metals from becoming oxidized or “mobile” in the first place. This is a very positive advantage because, if the instant invention is applied to a waste heap early enough, the risk of any possibly toxic metal mobilization is minimized. Plus, with the process of the instant invention, after the depleted oxygen condition is obtained, it can be easily, inexpensively and indefinitely maintained, for example, by simply covering the surface of the waste heap with a thin layer of soil and establishing and maintaining a vegetative population thereupon.
[0045] Many of the embodiments of the invented methods feature both oxygen depletion/displacement and gas-phase density increase, and the categories of invented steps may be described by similar language. For example, while the oxygen concentration may be “physically depleted,” “chemically depleted,” or “biologically depleted,” for example, the gas-phase density may be said to be increased by similar types of steps, that is, by being “physically increased,” “chemically increased,” or “biologically increased”.
[0046] Treatment of an exemplary rock heap is performed. Initial values of the rock heap are:
[0047] 1 million ton heap of rock waste material
[0048] permeability of 10
[0049] 2% sulfur (total)
[0050] 1.8% sulfide sulfur (90% sulfide, 10% oxidized)
[0051] Treatment Phase:
[0052] a) 70,000 lbs. of a sugar syrup is injected into the heap, followed by 140,000 lbs. of an alcohol such as methanol.
[0053] b) After allowing for sufficient reaction time and the addition of water suitable to force the reagents into the heap (at least enough water is used to solubilize the alcohol) the surface of the heap is covered with a fine layer of soil and planted with native seed mixes. This soil will cause a reduction in the permeability of the heap to below 10 darcy, such that the gases contained and being produced are not able to leak out except by plant uptake through roots, and by diffusion through the heap surface.
[0054] Maintenance Phase:
[0055] If the soil and climate characteristics are not sufficient and oxygen content rises within the heap, then an injection of 2,000-10,000 lbs. of a sugar/alcohol mixture may be added annually, or less frequently, to maintain reducing conditions. This additional dosage should be applied, taking into consideration the climate, the geographic orientation, and other factors affecting vegetative success.
[0056] Although this invention has been described above with reference to particular means, materials and embodiments, it is to be understood that the invention is not limited to these disclosed particulars, but extends instead to all equivalents within the scope of the following claims.