Priority Statement

[0001] This application claims priority from U.S. Provisional Patent Appl. No. 61/433,553, which was filed on January 18, 2011, the entire contents of which are hereby incorporated by reference.

Background

[0002] The Bayer process, invented in 1887 by Karl Bayer, is used throughout the world to produce aluminum from bauxite. A by-product of the process is the production of undissolved bauxite residue which is red in color and is commonly called Red Mud. More than 80 aluminum refinery plants around the world produce approximately 1.5 tons of tailings for each 4 tons of bauxite processed in the manufacture of 1 ton of aluminum. The global industry generates over 80 million dry metric tons of tailings each year which are stored in bauxite residue ponds and behind dams.

[0003] Red Mud is highly caustic with a pH value of about 13. The high pH is due to the use of sodium hydroxide to extract aluminum oxide from the bauxite. Despite a longstanding recognition by the aluminum industry of the disadvantages associated with residue storage, it has nevertheless continued to be the preferred solution considering economic, environmental, and social factors. As of 2007, stored bauxite residue totaled 2.7 billion tons with residues projected to reach 4 billion tons by 2015. [0004] A number of potential options for re -use of bauxite residues have been suggested. Some of these are:

• agricultural amendment for improvement of sandy soils

• neutralizing treatment material for acidic mining wastes

• material for construction purposes (e.g., road fill, brick making)

• source of raw materials for ceramics

• feedstock for mineral production (e.g., pig iron).

[0005] None of these is widely used as evidenced by the estimated 3 billion tons of bauxite residue currently in storage. No viable process for the use of bauxite residue as a feedstock for the production of mineral and metal values has ever been implemented to date.

[0006] As noted above, Red Mud is characterized by an alkaline pH of 12-13. Red Mud particle sizes tend to be very small, the particle size distribution being such that about 20 to 40% of the particles will have a diameter of less than 1 micrometer, and about 60% will have a diameter between 1 and 10 micrometers. Although the solids content of Red Mud varies depending on how long and under what conditions it has been stored, the solids content generally ranges from 60 to 70%, with the principal chemical compounds in Red Mud being:

• 20 to 45 % Fe ₂ 0 ₃

• 6 to 12% Ti0 ₂

• 7 to 20% Si0 ₂ • 5 to 12 % Na ₂ 0

• 7 to 8% CaO

[0007] The majority of the solid material in Red Mud is a mixture of Fe ₂ C>3 and AI2O ₃ . Both of these compounds have similar crystalline structures which are described as rhombohedral, that is, the structures are a parallelepiped whose faces are rhombuses. The similarity in crystalline structure of these two compounds results in interactions which make it difficult to separate the two minerals economically.

Brief Summary

[0008] The presently disclosed methods utilize both physical and chemical processes by which the Fe ₂ C>3 (iron oxide) contained in Red Mud is converted to synthetic Fe ₃ 0 ₄ (magnetite), and thereafter separated for recovery and reuse. The methods, when executed in accord with the disclosed steps, are capable of extracting 80 to 90% of the iron (Fe) in the Red Mud. The form of the iron, synthetic magnetite, is a black powder-like material that is widely used as a pigment in industrial manufacturing applications including high-temperature composite materials, coatings, acrylic and oil-based paints, plastics and other polymer resins, as well as being used in adding color to various types of metallic surfaces. At the present time, synthetic Fe ₃ 0 ₄ sells on the open market in the range of $800 to $1,200 per ton.

[0009] Disclosed herein and discussed in more detail below are methods of recovering magnetite from bauxite residue including reducing the pH of the bauxite residue to form a treated bauxite residue, drying the treated bauxite residue, heating the treated bauxite residue to a reduction temperature while applying a reducing fluid to produce a reduced bauxite residue in which a major portion of Fe ₂ C>3 present in the treated bauxite residue has been converted to Fe ₃ 0 ₄ ; and separating the reduced bauxite residue into an iron-enriched portion containing Fe ₃ 0 ₄ and/or Fe and an iron- depleted portion.

[0010] As will be appreciated by those skilled in the art, the basic the methods of recovering magnetite from bauxite residue may include other steps and sub-steps depending on the

composition of the starting material, the equipment and feed streams available. For example, some embodiments of the disclosed methods may include cooling the reduced bauxite residue under a non-oxidizing environment before separating the Fe ₃ 0 ₄ , combining a quantity of coke with the treated bauxite residue and generating at least a portion of the reducing fluid by decomposing a portion of the coke to form carbon monoxide.

[0011] Other embodiments of the disclosed methods may include combining a volume of carbon dioxide with the carbon monoxide to form a reducing fluid having a CO/CO ₂ ratio of, for example, 1: 1 to 2:1. Again, depending on the particular process conditions, other CO/CO ₂ ratios may be sufficient for suppressing further reduction of the Fe ₃ 0 ₄ in the reduced bauxite residue, thereby increasing the yield of magnetite in preference to elemental iron. As will be appreciated by those skilled in the art, the reduction reaction can be conducted under a variety of conditions, again depending on the equipment and feed streams available, but a reduction temperature of 700° C to 1100° C, and preferably at least 800° C, are expected to provide satisfactory results.

[0012] In addition to forming and recovering magnetite from bauxite residue, i.e. , Red Mud, the residual portion of the Red Mud after the magnetite has been removed can be subjected to additional processing to recover other metals and/or metallic compounds including, for example, aluminum, aluminum compounds, titanium and titanium compounds. And, despite a preference for a CO/CO ₂ reducing atmosphere, other reduction agents may be used with or instead of the preferred composition including, for example, NO _x , N ₂ , NH ₃ , H ₂ and mixtures thereof. [0013] With respect to the drying operation, the goal is to produce a treated bauxite residue that comprises predominately particulates through which the reducing fluid can pass readily in order to contact and interact with the Fe ₂ 0 ₃ within the Red Mud. As will be appreciated by those skilled in the art, a variety of drying techniques and equipment may be utilized to achieve this goal of reducing the moisture content of the treated bauxite residue to something on the order of 3% to 6%. Other unit operations including, for example, milling, screening and agitating, in order to obtain an appropriate particle size distribution within the treated bauxite residue.

[0014] Again, although it is expected that in most instances magnetite will be the target iron-rich product, in some cases there may be a need or a preference for elemental iron. In such instances, the composition of the reducing fluid(s) and the reduction temperature may be adjusted to promote more complete reduction of the Fe ₂ 0 ₃ and/or Fe ₃ 0 ₄ . Such modifications may include, for example, increasing the duration of the reduction processing, using a more aggressive reducing agent and/or reducing the content of reduction reaction suppressing components including, for example, C0 ₂ , to increase the reduction rate and/or completion percentage.

Brief Description of the Drawings

[0001] FIG. 1 illustrates a process flow comprising a first embodiment of the disclosed method;

[0002] FIG. 2 illustrates a process flow comprising a second embodiment of the disclosed method; and

[0003] FIG. 3 illustrates a process flow comprising a third embodiment of the disclosed method.

[0004] It should be noted that these Figures are intended to illustrate general characteristics of the disclosed methods and to supplement the written description provided below. As will be appreciated by those skilled in the art, therefore, these drawings do not reflect the structural or logical arrangement of the unit operations and equipment that could used to practice the disclosed methods and, accordingly, should not be interpreted as unduly defining or limiting the following claims. Indeed, it is well within the skill of one of ordinary skill in the art guided by this disclosure to design a plant, with all of the necessary auxiliary equipment and materials, for practicing the disclosed methods. Similarly, it is well within the skill of one of ordinary skill in the art to modify and/or adjust the parameters of the disclosed methods in order to compensate for variations in materials, equipment and/or process goals.

Detailed Summary

[0005] The present invention takes advantage of the very fine particles of Fe ₂ 0 ₃ in the Red Mud by using CO as a reducing agent, the CO being supplied either directly as a gas or, in another embodiment, generated from low VOC coke, while heating the mixture in the presence of C0 ₂ to temperature sufficient to reduce the Fe ₂ 0 ₃ . Typically, a reducing temperature greater than 800°C will be sufficient to initiate and achieve substantial completion of the reduction process that changes the Fe ₂ 0 ₃ to Fe ₃ 0 ₄ . The primary chemical reaction to be utilized is represent in Reaction [1] :

3 Fe ₂ 0 ₃ + CO => 2 Fe ₃ 0 ₄ + C0 ₂ [1] although one or more additional reduction reactions can be utilized at the operator's discretion including, for example, those reactions illustrated in Reactions [2] - [4]:

Fe ₂ 0 ₃ + 3 H ₂ => 2 Fe + 3 H ₂ 0 [2]

Fe ₃ 0 ₄ + 4 CO => 3 Fe + 4 C0 ₂ [3]

3 Fe ₂ 0 ₃ + H ₂ => 2 Fe ₃ 0 ₄ + H ₂ 0 [4]

[0006] As will be appreciated by those skilled in the art, other reducing agents such as NH ₃ or H ₂ , either singly or in combination (e.g. , forming gas) with or without one or more nitrogen compounds could accomplish the reduction. Carbon monoxide is preferred over these reducing agents, however, for providing improved control of the reaction and/or increased safety. Using hydrogen and/or ammonia, for example, tends to introduce additional safety considerations and increases the likelihood that these reducing agents would also tend to reduce at least a portion of the desired magnetite, Fe ₃ 0 ₄ , to elemental iron.

[0007] Of particular interest, at the reducing temperature the crystalline form of Fe ₂ 0 ₃ , which is rhombohedral, is converted to the crystalline form of Fe ₃ 0 ₄ , which is cubic. It is believed that this morphological change from rhombohedral to cubic that makes possible the physical separation of Fe ₃ 0 ₄ from A1 ₂ 0 ₃ . Reducing temperatures below 800°C are generally less preferred both because the reduction reaction will tend to be incomplete and because the severing of the bonds between the Fe ₃ 0 ₄ and A10 ₂ components of the Red Mud will not tend to be as complete. [0008] Depending on factors including, for example, the particular goals for the treatment, the composition of the Red Mud being treated and the market for the various products that can be recovered from the Red Mud, the basic production processes, as illustrated in the FIGURE, may be modified through the addition or adjustment of a number of major steps, each of which may, in turn, consist of several sub steps.

[0009] The process will typically begin by using an acidic neutralizing solution, for example, a concentrated aqueous phosphoric acid solution (54% P2O5) to treat the Red Mud.

Although other mineral acids such as HC1 could accomplish the buffering, such use would, for example, release chlorine which could cause a dangerous condition, and are, consequently, less preferred. Organic acids could also be used. The neutralizing solution is used to reduce the pH of the Red Mud from its typical range of 12-13 into a range of about 4-9, preferably about 7.

[0010] The neutralized Red Mud is then dried to a moisture content range of 3 to 6 %. The drying operation may use, for example, a preheated column operating at a temperature of, for example, 100 to 200° C, with the heat supplied by any combination of off gases, onsite cogenerated electricity or heat, or other recovered sources of heat and/or energy. The drying operation may also be conducted under a partial vacuum to increase the drying rate.

[0011] At this point in the process, if CO is to be the reducing agent of choice, the means of delivering the CO to the treated bauxite residue may be selected from a number of options. In a preferred method, CO gas is injected as discussed infra. Alternatively, coke, preferably low VOC coke (< 10% VOC and <5% ash), may be used to supply CO. If coke is selected as the CO source, a sufficient volume of coke is added to and mixed into the Red Mud such that the coke comprises 30 to 60% by weight of the resulting Red Mud/coke mixture. The Red Mud/coke mixture is then pulverized using, for example, one or more mechanical grinders to ensure a homogeneous mixture and a achieve a target particle size range within the mixture. It is preferred, for example, that the maximum particle size of the pulverized Red Mud/coke mixture be around 150 μιη. Although smaller particle sizes could certainly be acceptable, and would be expected improve the yield and/or rate of the reduction reaction, achieving the smaller particle size range would also tend to increase the processing costs significantly. Accordingly, the preparation of particle size ranges substantially less than 150 μιη is feasible, it is expected that in most instances such additional processing would not be deemed cost effective.

[0012] The treated and dried Red Mud mixture or, alternatively, the pulverized Red Mud/Coke mixture, may be fed into a reducing reactor comprising, for example, a rotary kiln, operating at a reduction temperature of 700 to 1100°C. In a preferred embodiment, as the treated and dryed Red Mud material flows through the kiln, a sufficient volume of a CO/CO2 mixture is injected in a counter flow direction such that atmospheric oxygen in the kiln is purged so that a less oxidizing atmosphere, and preferably a substantially non-oxidizing atmosphere is established and maintained within the reducing reactor during the reduction operation.

[0013] In the CO/CO2 mixture, the C0 ₂ acts as an "inert" gas to suppress or reduce the oxidation rate of the Fe ₂ C>3 contained in the material while the CO acts as the primary reducing agent. Other "inert" gasses could be considered including, for example, N ₂ , Ne, He or Ar.

However, these alternative gases are less preferred than CO2 because, for example, under the conditions within the reducing reactor N2 can be oxidized to NO _x , a corrosive and a pollutant while Ar and other noble gases are generally considered to be too expensive for cost-effective use. It is also believed that the addition of CO2 also acts to slow down the interaction of CO to reduce the Fe ₂ 0 ₃ and form Fe ₃ 0 ₄ while suppressing further reduction of the Fe ₃ 0 ₄ , thereby increasing the yield

[0014] It is believed that a CO/CO2 ratio of between 1 : 1 and 2:1 will generally achieve acceptable reduction results, but factors including, for example, the Red Mud composition, the reactor design and the reducing temperature may dictate use of CO/CO ₂ ratios outside the preferred range in order to achieve better results. If coke is being used to supply CO for the reduction, it is preferred that a sufficient volume of C0 ₂ be injected into the reducing reactor to achieve both the oxidation suppression and reduction tempering functions.

[0015] As the reduced Red Mud composition exits the reducing reactor, it will typically be cooled in preparation for further processing. A preferred method of cooling is to pass the reduced Red Mud material through a heat exchanger that will allow for recovery of some of the excess heat added in the kiln. At least during the initial period of cooling, it is also preferred that the reduced Red Mud material be maintained under a substantially non-oxidizing atmosphere to suppress reversion of the Fe ₃ 0 ₄ . The heat removed in this step may be utilized either in the drying step or alternatively used to cogenerate electricity that may be used to power the kiln and/or other equipment and thereby reduce the overall operating cost of the plant. Alternatively, the cooling may be achieved by simply holding the mixture at ambient temperature for a sufficient period of time.

[0016] After cooling, the synthetic Fe ₃ 0 ₄ magnetite may be separated from the mixture using a magnetic separator to separate an iron-rich product stream. The synthetic Fe ₃ 0 ₄ magnetite flow stream exiting the magnetic separator may then be directed to an air classifier or other particle separator device(s). Classification may be performed because particles smaller than 100 nm, nano- scale magnetite, typically comprise about 10 to 15% of the total Fe ₃ 0 ₄ and there are separate, higher value markets for this nano-scale magnetite. Indeed, the market price for the smaller particles tends to be several times greater than the market price for those particles that are larger than 100 nanometers so effective separation can improve the economics of the overall process. Those particles larger than 100 nanometers, typically comprising about 85 to 90% of the Fe ₃ 0 ₄ generated, are collected for sale and use as pigment. In the event that there is no particular interest in selling the smaller particles separately, or if the classification process is uneconomical, this additional separation may be eliminated and the smaller particles can remain in a mixture with the large particles.

[0017] The non- magnetic particle flow stream exiting from the magnetic separator can be subjected to additional processing as well. For example, the non-magnetic particle flow stream may be combined with water or other carrier liquid or composition to form a slurry that is, in turn, processed through multiple gravity separation steps that separate the particles according to their densities. It is estimated, for example, that titanium dioxide can be separated with a purity of 70- 80%, followed by aluminum oxide with a purity of 50-60%.

[0018] A wide range of separation equipment suitable for use in this step is well known to those of ordinary skill in the art and may include, for example, spiral concentrators, centrifuges, or a combination of the two as well as other equipment depending on the physical composition of the feed stream. The recovered titanium dioxide and aluminum oxide are sold for reuse. The remaining residue may be further processed for the recovery of other valuable metals, or optionally segregated and disposed as a waste.

[0019] Currently, undissolved bauxite residue, Red Mud, is stored indefinitely in holding ponds or behind dams at aluminum refineries throughout the world. Despite ongoing efforts by the aluminum industry and researchers to develop uses for the residue, no use has been found that is feasible, scalable to accommodate large volumes, economic, and acceptable to the public. The method detailed herein provides the following advantages: [0020] It applies chemical reduction theory well-known in the art to a problematic waste product, Red Mud, to produce a high value product, synthetic Fe ₃ 0 ₄ pigment and it utilizes existing industrial equipment to derive further value from the non-magnetic component of the processed Red Mud to produce/separate other high value products. The methods are easily scalable for accommodating the high volumes of bauxite residue currently being generated. Further, because the disclosed methods utilize processes based on proven chemical theory, can be achieved using conventional equipment and can be achieved without generating any particularly problematic waste products, it is expected that plants operating in accord with the disclosed processes should be acceptable to both the public and governmental regulators and not present any significant environmental or other regulatory concerns.

[0021] While the present invention has been described with reference to preferred embodiments, various changes or substitutions may be made on these methods by those ordinarily skilled in the art without departing from the scope of the present invention. Therefore, the scope of the present invention encompasses not only those embodiments described above, but all those that fall within the scope of the claims provided below.