ENHANCED BINDERS FOR IRON ORE PELLETING AND CEMENT ADHESIVE MATERIALS

Abstract

The present invention is directed to composition and methods for iron ore pelleting and cement binders. More particularly, the binders are bio compatible crosslinked levan and crosslinked polysaccharides or groups or salts thereof.

Claims

1. A binder composition comprising: a cross-linked polysaccharide; and bentonite.

2. The composition of claim 1, wherein the polysaccharide comprises.

3. The composition of claim 1, wherein the cross link of the cross-linked polysaccharide contains from 1 to 10 carbons.

4. The composition of claim 1, wherein the cross linked polysaccharide comprises levan cross linked with epichlorohydrin.

5. The composition of claim 1, wherein the polysaccharide contains substitutions along from one or more of the saccharide unites of the polysaccharide.

6. The composition of claim 1, wherein the polysaccharide contains substitutions along each of the saccharide unites of the polysaccharide.

7. A method of pelletizing a mineral ore comprising: providing mineral ore as boulders or fines, wherein boulders are reduced to approximately 5-30 mm in size; adding the binder composition of claim 1 to the mineral ore and forming agglomerates; and pelletizing the agglomerates forming mineral bore pellets.

8. The method of claim 7, wherein the mineral ore comprises iron ore.

9. The method of claim 8, wherein the iron ore pellets have a dry compressive strength that is comparable to or greater than iron ore pellets manufactured with conventional binder compositions.

10. The method of claim 8, wherein the iron ore pellets have a ball drop strength that is comparable to or greater than iron ore pellets manufactured with conventional binder compositions.

11. The method of claim 8, wherein the iron ore pellets have a pellet friability that is comparable to or greater than iron ore pellets manufactured with conventional binder compositions.

12. The method of claim 8, wherein the iron ore pellets have a tensile strength that is comparable to or greater than iron ore pellets manufactured with conventional binder compositions.

13. A method for manufacturing concrete or mortar comprising: providing a mix of cement, an amount of water and aggregate material; adding the binder of claim 1 to the mix to form a binder mix; allowing the binder mix to harden over a period of time forming concrete or mortar.

14. The method of claim 13, wherein the cement is Portland cement.

15. The method of claim 13, wherein the aggregate material comprises sand or rock.

16. The method of claim 13, wherein the period of time comprises a greater amount of time than would be necessary to form concrete or mortar without binder.

17. The method of claim 13, wherein the amount of water is from 5%-20% less than would be necessary to form concrete or mortar without binder as measured by ASTM certified slump test.

18. The method of claim 13, wherein the concrete or mortar has a decreased degree of structural deformation as compared to concrete or mortar manufactured without binder.

19. The method of claim 13, wherein the concrete or mortar has an increased dry compression strength as compared to concrete or mortar manufactured without binder.

20. The method of claim 13, wherein the concrete or mortar has an increased tensile strength as compared to concrete or mortar manufactured without binder.

21. A composition comprising a cross-linked polysaccharide, wherein the polysaccharide comprises levan, dextran, guar gum, and/or derivatives, salts and combinations thereof, and the polysaccharide comprises a carbon linker (C1-C8) and/or long chain hydroxy aliphatic groups or salts as side chains which may also contain a carbon linker (C1-C8).

22. The composition of claim 21, wherein the polysaccharide is cross-linked by epichlorohydrin (EPCH).

Description

DESCRIPTION OF THE FIGURES

[0020] FIG. 1 Chemical process for the preparation of crosslinked Levan.

DESCRIPTION OF THE INVENTION

[0021] Existing methods for the production of iron pellets and cement adhesives utilize binders that require high-grade compounds and are thus expensive and difficult to commercially produce. Bentonite is the traditional binder with different types of bentonite named after the respective dominant element, such as potassium (K), sodium (Na), calcium (Ca), and aluminum (Al). However, this bentonite, regardless of the dominant element, does not improve either the homogeneity of the metallurgical process or the quality of the resulting pellets, yet considerable increases cost.

[0022] It has been surprisingly discovered minerals, such as iron ore, can be pelletized by combining the mineral with a binder that comprises a crosslinked polysaccharide. Mineral ore is generally ground or a finely divided ore concentrate obtained by flotation or the like. Polysaccharides include, but are not limited to levan, dextran, guar gum, scleroglucan, welan, xanthan gum, schizophyllan, cellulose and/or combinations thereof. Linking compounds include linkers that create cross-linked polysaccharides with, preferably, from 1 to 10 carbons linkers. The polysaccharide may also include one or more substitutions of one or more saccharide units of the polysaccharide compound. Preferably the polysaccharide comprises levan and preferably the cross-linker comprises EPCH.

[0023] Binder composition of the invention are added to mineral ore during palletization as a main/primary binder or as a single component binder. The cross-linked polysaccharides to be employed in the present invention can vary broadly in type and is preferably sufficiently stable to be effective under the process conditions actually used such as, for example, high temperatures and strong caustic conditions (e.g., about 85 C.-107 C. {about 185 F.-225 F.}). This resulting mineral pellets increases the relative purity of ore pellets by decreasing the non-ore binder, improve the mixing and handling of the pellet which, in turn, lowers operational costs while uniformly reacting pellets of high structural strength and tensile strength.

[0024] One embodiment of the invention is directed to a binder composition containing a cross-linked polysaccharide and bentonite. Binder compositions of the invention are preferably aqueous and contain from 4-85% (by weight) cross-linked polysaccharide and a percentage (by weight) of bentonite. Preferably binder compositions of the invention contain from 10% to 50% less bentonite (by weight) than conventional binder compositions while maintaining or increasing dry compressive strength, ball drop strength, and improving pellet friability as compared to binder compositions without cross-linked polysaccharides of the invention. Conventional amounts of bentonite in binders are from 30-80% of the binder composition (by weight), whereas bentonite concentrations in binders of the invention contain from less than 30%, preferably less than 25%, preferably less than 20%, preferably less than 15%, preferably less than 10%, preferably less than 5%, and preferably less than 2% (by weight), Cross-linked polysaccharides of the invention, which may contain chemical moieties substitutions of one or more saccharides, preferably comprise from 10-80% (by weight) of the binder composition, preferably from 20-70%, preferably from 25-60%, preferably from 15-75%, preferably from 10-80%, preferably from 40-50%, and preferably from 25-50% (by weight)

[0025] Binder compositions of the invention may also contain molasses; polyacrylamide, starch, chlorides, iron sulfate, lime and/or calcium hydroxide. The composition may also comprise a synthetic polymer derived from natural polysaccharides such as carboxymethyl cellulose (CMC) or modified starches present in an amount of up to 10%, preferably from 4% to 8%, by weight based on the total weight of the binding mixture. Carbonates and bicarbonates of alkaline metals or soluble hydroxides from alkaline metals such as carbonates, bicarbonates or hydroxides of sodium, lithium or potassium may be present in a percentage of up to 20%, preferably from 7% to 20%, by weight of the binder composition. Preferably these additional components each comprise from 0.5 and 20% by weight of the composition. Preferably binder compositions of the invention do not increase or substantially increase the silica concentration of the pellet and/or do not reduce or substantially the mineral concentration of the mineral ore in the resulting pellet as compared to pellets made with conventional binder compositions.

[0026] Another embodiment of the invention is directed to the manufacture of concrete or mortar. Preferably, cement, water and an aggregate material are mixed with a binder composition of the invention and allowed to set over a period of time, optionally, in a form, to harden. Concrete or mortar manufactured using binder composition of the invention has increased tensile strength and increased dry compression strength as compared to concrete or mortar made without such binder. Also, water consumption is reduced during concrete production. Another advantage of this invention comprises providing bio compatible cement plasticizers for cement and concrete products. For example, the levan biopolymer is characterized by significantly higher reactivity and adhesion properties as compared to other known biopolymers such as guar and xanthan gums. Additionally, the intrinsic viscosity of levan in water is vanishingly low as compared to other polysaccharides.

[0027] An important additive in cement is called a plasticizer. Plasticizers are admixtures to a concrete or cement mix that improves the flow properties of a mix prior to hardening without negatively impacting the other properties after it sets. They are characterized by such properties as how much water is required or saved to maintain the flow properties, otherwise known as workability, the delay or acceleration of hardening (set time), and the impact it has on the final compressive strength of the cement with it in the mix. The most advanced category of plasticizers is called superplasticizers. These additives reduce water requirement by greater than or equal to 5% by weight of the cement, and are known as high range water reducer. These additives are used where well-dispersed cement particle suspension is required. These additives are used to minimized gravel, coarse and fine sands segregation, and enhance the flow properties workability. Superplasticizers to a concrete mix allow the water to cement ratio to be reduced. This increases the strength of the cement while maintaining the workability of the mixture. Strength of concrete increases as the water to cement ratio decreases.

[0028] Exemplary of the polymers which may be crosslinked for use in process of the present invention are acrylic, methacrylic, crotonic, etc., acid ester polymers such as polymers produced from the polymerization of methyl acrylate, ethyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, dimethyl aminoethyl methacrylate, dimethyl aminoethyl acrylate, methyl crotonate, etc., polymers of maleic anhydride and esters thereof, and the like; nitrile polymers such as those produced from acrylonitrile etc; amide polymers such as those produced from acrylamide, methacrylamide and the like.

[0029] Generally, these crosslinked polymers produced by reacting the containing the pendant reactive group, in solution, with a epichlorohydrin (EPCH) or its salt at a temperature ranging from about 50 C. to 100 C. for several hours. From about 1-90 percent of the available pendant reactive groups of the polymer may be replaced by epcichlorohydrin in accordance with said procedures.

[0030] The molecular weight of the polymers useful in the process of the present invention range from about 1 million to 50 million Daltons.

[0031] The polymers used in the present invention are employed by adding them, usually in the form of a dilute aqueous solution, to the iron ore and cement. Generally, for best results, at least about 0.5 gram, of the crosslinked Levan, per liter of the process stream should be employed. More preferably, at least one gram of the crosslinked Levan is added.

[0032] One or ordinary skill in the art will understand that higher amount may be employed without departing from the scope of the invention, although generally a point is reached in which additional amounts of crosslinked Levan do not improve the separation rate over already achieved maximum rates. Thus, it is uneconomical to use excessive amounts when this point is reached.

[0033] The following examples illustrate embodiments of the invention, but should not be viewed as limiting the scope of the invention.

Examples

Example 1 Preparation of Crosslinked Levan

[0034] As shown in FIG. 1 and Tables 1 and 2, Levan polysaccharide was reacted with cross linker epichlorohydrin (EPCH) in water and base (NaOH) at elevated reaction temperatures to yield crosslinked Levan (TacBond, Spectre 82x, Spectre 825x and Spectre 8255x). Product produced comprises pellets containing cross-linked Levan of approximately 1-3 cms.

TABLE-US-00001 TABLE 1 Mix Slump (in.) 3-day compressive Strength (psi) Control 2.5 4210 Spectre 8255x 6.25 4250

Data:

TacBond IOP Features

[0035] High water retention. [0036] Much higher green tensile strength. [0037] Much higher hydroxyl number (high adhesive strength). [0038] Low viscosity (ease of handling).

TABLE-US-00002 TABLE 2 Property Spectre (82X) Guar Xanthan CMC Tensile Strength (psi) 991 63 33 193 Hydroxyl No. (mg KOH/g) 89 27-29 20-30 NA Intrinsic Viscosity (dl/g) 0.14 15 150 10-100 Plate Water Absorption 775 1030 4890 1270 (PWA) *Bentonite: Biopolymer ratios: TacBond 90:10; Guar, Xanthan, CMC 50:50

[0039] Additional crosslinked polysaccharides may be utilized in accordance with the process of the disclosure herein.

Example 2 Preparation of Ore Fines with Crosslinked Polysaccharides

[0040] Iron ore fines in the form of hardened pellets are formed from taconite ground very fine prior to beneficiation to increase the percentage content of iron oxide. Beneficiated iron ore fines are mixed with a binder composition and tumbled in a drum to produce pellets. The binder composition contains bentonite and a cross-linked polysaccharide. The presence of bentonite increases the structural strength of iron-ore pellets and aids in the formation of rounded structures. By adding Levan cross-linked with EPCH, the amount of bentonite of the binder composition is reduced.

[0041] Other embodiments and uses of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. All references cited herein, including all publications, and all U.S. and foreign patents and patent applications are specifically and entirely incorporated by reference. The term comprising, where ever used, is intended to include the terms consisting and consisting essentially of. Furthermore, the terms comprising, including, and containing are not intended to be limiting. It is intended that the specification and examples be considered exemplary only with the true scope and spirit of the invention indicated by the following claims.