# Patent

## Title
Binder composition for waste materials

## Abstract

An inorganic binder composition has a first constituent which is a poly(sialate) or a poly(sialate-siloxo) admixed with a second constituent which has one or more of: fly ash F, fly ash C, fumed silica, Al2O3, pozzolan, ground slag, nepheline syenite, anhydrous aluminum silicate, hydrous aluminum silicate, hydrous sodium hydroxide, silicic acid, potassium salt, and sodium salt. The binder is used to recycle and reuse revert materials from metal smelting operations.

## Background
FIELD
The invention relates to an inorganic binder composition and the production of such binder composition and the uses of such binder composition. In particular, this invention relates to an inorganic binder composition which is particularly useful in treating waste materials for recycling and safe and secure disposal.
BACKGROUND
The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
Inorganic binder compositions have been proposed to solidify and dispose harmful wastes. In Davidovits et al. U.S. Pat. Nos. 5,352,427; 5,349,118; 5,342,595; 4,859,367; 4,349,386; 4,472,199; and 4,509,985; in Neuschaeffer et al. U.S. Pat. Nos. 4,522,652; 4,533,393; and 4,608,795; and in Heitzmann et al. U.S. Pat. Nos. 4,640,715 and 4,642,137; a geopolymer comprising alumino-silicate oxide is described. These geopolymers were developed for inclusion in masonry tiles but were found to be useful for solidifying wastes for long term disposal.
Alumino-silicate binders are comprised of two components: a fine dry powder and a syrupy, highly alkaline liquid. The powder is a soluble alkali polysilicate which can be activated by the alkaline liquid to form tetrahedra of SiO4 and AlO4. The tetrahedra are cross-linked by shared oxygen molecules to form inorganic polymeric networks. A mildly exothermic reaction in the alkali activated mixture is accompanied by hardening and polycondensation.
Inorganic binders are characterized by several distinct properties, including thermal stability, high surface smoothness, precise mobility and hard surfaces. As a result, inorganic binders are particularly useful in specialty construction applications, such as saline or aqueous environments.
Further, the inorganic binder compositions of the prior art have been found to provide long term solutions for hazardous and harmful wastes. Various organic and inorganic wastes can be mixed with the inorganic compounds displacing the normal volume of aggregates in forming a monolithic solid. As the crystal structure grows and the solution solidifies, the waste components are co-bound into a lattice, rendering the waste chemically inert, suitable for landfilling, recycling into construction media or reintroduction into a production process. The most significant properties of a waste treated with an inorganic binder is the ability to resist chemical attack from acidic conditions and to transform soft, disaggregated or sludge-like waste into hard, cohesive solids in a relatively short period of time.
Unfortunately, the cost of the raw materials has prevented the inorganic binder compositions of the prior art from being commercially competitive with other existing technologies for long term disposal or recycling of wastes or even with conventional Portland cement.
SUMMARY
According to one aspect, there is provided a first constituent of an inorganic binder composition. In a non-limiting embodiment, the first constituent comprises about 20% silicon dioxide; about 60% tri-calcium silicate; about 10% di-calcium silicate; about 6% tri-calcium aluminate; about 1% aluminum oxide; about 1% ferric oxide; about 1% magnesium oxide; and about 1% sulfur tri-oxide.
According to another aspect, there is provided an inorganic binder composition comprising about 5-20% fumed silica; between 40-60% anhydrous aluminum silicate; between 1-10% silicic acid; and between 1-10% either potassium or sodium salt.
According to another aspect, there is provided an inorganic binder composition has as a first constituent a poly(sialate) or a poly(sialate-siloxo) admixed with one or more of: fly ash F, fly ash C, fumed silica, Al2O3, pozzolan, ground slag, nepheline syenite, anhydrous aluminum silicate, hydrous aluminum silicate, hydrous sodium hydroxide, silicic acid, potassium salt, and sodium salt. The admixture has a molar ratio of SiO2 to Al2O3 of between about 5.2 to about 14.3.
According to another aspect, there is provided an inorganic binder composition comprising a first constituent comprising silicon dioxide, tri-calcium silicate, di-calcium silicate, tri-calcium aluminate, aluminum oxide, ferric oxide, magnesium oxide, and sulfur tri-oxide, admixed with a second constituent selected from one or more of the following: fly ash F; fly ash C; fumed silica; Al2O3; pozzolan; ground slag; nepheline syenite; anhydrous aluminum silicate; hydrous aluminum silicate; hydrous sodium hydroxide; silicic acid; potassium salt; and sodium salt. In various embodiments, the second constituent comprises fly ash F and at least one of Al2O3, pozzolan, nepheline syenite, aluminum silicate, sodium hydroxide, silicic acid, potassium salt, and sodium salt.
According to another aspect, there is provided a method of recycling waste materials from a smelting furnace comprising the steps of: admixing revert materials of a metal smelting furnace with an inorganic binder composition, and compacting the admixture into a briquette for recycling in said furnace.
According to another aspect, there is provided a method of recycling waste materials from a smelting furnace, including coke breeze, furnace sludge, mill scale and flue dust. The method comprises the steps of: admixing the revert materials of a metal smelting furnace with 131⁄2% to about 171⁄2% by weight of an inorganic binder composition, and compacting the admixture into a briquette for recycling in said furnace.
Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.


DETAILED DESCRIPTION
The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses.
First Embodiment
The invention relates to a binder composition as a replacement for or additive to cement. The inorganic binder composition of the first embodiment of the present invention includes a first constituent comprising by weight:

    
    
        20% silicon dioxide;
        60% tri-calcium silicate;
        10% di-calcium silicate;
        6% tri-calcium aluminate;
        1% aluminum oxide;
        1% ferric oxide;
        1% magnesium oxide;
        1% sulfur tri-oxide.
    
    


The first constituent is a poly(sialate) or a poly(sialate-siloxo). However, the composition of the first constituent of the present invention has molar ratios of components which differ from the poly(sialate) or a poly(sialate-siloxo) of the prior art.
EXAMPLE 1
Between 62 and 90%, by weight, of the first constituent of the first embodiment of the binder composition can be admixed with:

    
    
        5-20% fly ash F;
        4-10% fumed silica;
        1-8% Al2O3.
    
    


The resulting composition has a molar ratio of SiO2 to Al2O3 in the range of about 5.2 to about 7.6.
The composition of this example is useful as a construction material, either in partial substitution for or in conjunction with Portland cement. The fly ash F in combination with fumed silica acts as a Portland cement-type material when combined with Al2O3.
EXAMPLE 2
Between 60 and 85%, by weight, of the first constituent of the first embodiment of the binder composition can be admixed with:

    
    
        4-10% pozzolan;
        4-10% ground slag (calcium oxide);
        5-10% anhydrous aluminum silicate;
        1-5% silicic acid;
        1-5% potassium salt.
    
    


The resulting composition has a molar ratio of SiO2 to Al2O3 in the range of about 5.2 to about 8.9, of M2O to SiO2 in the range of about 0.07 to about 0.11, of H2O to M2O in the range of about 5.0 to about 10.0 and of M2O to Al2O3 in the range of about 0.30 to about 0.45, where M2O is selected from the group comprising of Na2O, K2O and a mixture of Na2O and K2O.
The composition of this example is particularly useful for hazardous waste applications. The anhydrous aluminum silicate provides the building block for the zeolite structure when it combines with the silicic acid and potassium salt. Additional crystal structure is provided by the calcium silicate bonds. The bonding effectively encapsulates the molecules of the hazardous materials.
EXAMPLE 3
Between 60 and 85%, by weight of the first constituent of the first embodiment of the binder composition can be admixed with:

    
    
        4-10% pozzolan;
        4-10% ground slag;
        5-10% anhydrous aluminum silicate;
        1-5% silicic acid;
        1-5% sodium salt.
    
    


The resulting composition has a molar ratio of SiO2 to Al2O3 in the range of about 5.2 to about 8.9, of M2O to SiO2 in the range of about 0.07 to about 0.11, of H2O to M2O in the range of about 5.0 to about 10.0 and of M2O to Al2O3 in the range of about 0.30 to about 0.45.
The composition of this example is also useful for hazardous waste applications.
EXAMPLE 4
Between 60 and 89%, by weight, of the first constituent of the first embodiment of the binder composition can be admixed with:

    
    
        5-20% fly ash C;
        4-10% pozzolan;
        1-5% silicic acid;
        1-5% potassium or sodium salt,
        preferably potassium.
    
    


The resulting composition has a molar ratio of SiO2 to Al2O3 in the range of about 7.4 to about 14.3, of M2O to SiO2 in the range of about 0.05 to about 0.10, of H2O to M2O in the range of about 5.0 to about 9.0 and of M2O to Al2O3 in the range of about 0.25 to about 0.45.
The composition of this example is useful as a construction material, either in substitution for or in conjunction with Portland cement.
The composition of this example is relatively more expensive than the previous examples. Fly ash C currently is more expensive than flay ash F, however, fly ash C has better quality.
The pozzolan replaces anhydrous aluminum silicate as a source of Al2O3.
EXAMPLE 5
Between 88% and 60%, by weight, of the first embodiment of the binder composition can be mixed with:

    
    
        4-10% pozzolan;
        4-10% nepheline syenite;
        1-5% hydrous aluminum silicate;
        1-5% hydrous sodium hydroxide;
        1-5% silicic acid;
        1-5% potassium or sodium salt, either separately or in combination.
    
    


The resulting composition has a molar ratio of SiO2 to Al2O3 in the range of about 5.2 to about 9.0, of M2O to SiO2 in the range of about 0.50 to about 2.00, of H2O to M2O in the range of about 5.0 to about 9.0 and of M2O to Al2O3 in the range of about 1.75 to about 3.50.
In this example, the nepheline syenite and hydrous aluminum silicate may be replaced by 5-10% anhydrous aluminum silicate. However, nepheline syenite and hydrous aluminum silicate are preferred since it is a waste material and therefore relatively inexpensive.
The binder composition of this example is particularly useful in the steel industry. Industrial waste, such as coke breeze, mill scale, flue dust and other revert materials can be briquetted for reuse in the steel manufacturing process. Reclamation of the revert materials reduces the need to landfill the industrial waste, as well as recovering valuable iron units.
In the past, the revert material has been mixed with binders such as starch, lime, tar, cement, or molasses. The agglomerated material is then briquetted for recycling. However, incineration of the organic binders generates toxins such as phenols (carbolic acid). The Environmental Protection Agency in the United States has recently banned the use of organic binders for use in recycling revert materials.
The binder composition of this example is mixed with the revert waste material. In various embodiments, the binder composition content of the binder-waste material is about 131⁄2% to about 171⁄2%, for example when feeding cold binder stock. If the binder stock is heated, less binder may be used to achieve satisfactory results. As the binder content increases, for example if the binder content is greater than about 14%, it can become desirable to dry the binder-waste material before compressing into a briquette.
In various embodiments, the waste material comprises by weight up to about 55% coke breeze and furnace sludge, about 10% flue dust and about 20% recycled mill scale.
The binder-waste material is then compressed into a briquette using a conventional briquetting machine. In a non-limiting example, the briquette is compressed at a pressure of between 1800 and 2600 psi, preferably between 2100 and 2600 psi, using a wheel speed of between 4-6 RPM. The briquette is then re-introduced into the furnace for incineration.
Using iron ore pellets of virgin materials in a blast furnace, the recovery of iron content is about 85%. Using the recycling techniques of the prior art, the recovery is about 40%. Using the briquettes of the present invention, recovery of iron may be as high as 78%.
It can be readily understood that the process described herein is also applicable to other processing of base metals, including smelting of lead, nickel and zinc.
Second Embodiment
The binder composition of a second embodiment includes a composition by weight of:

    
    
        5-20% fumed silica;
        40-60% anhydrous aluminum silicate;
        1-10% silicic acid;
        1- 10% either potassium or sodium salt, or combinations thereof.
    
    


When using potassium salt, the resulting composition has a molar ratio of SiO2 to Al2O3 in the range of about 0.24 to about 2.2 of M2O to SiO2 in the range of about 0.04 to about 0.10, of H2O to M2O in the range of about 5.0 to about 12.5 and of M2O to Al2O3 in the range of about 0.12 to about 0.30.
When using sodium salt, the resulting composition has a molar ratio of SiO2 to Al2O3 in the range of about 2.5 to about 3.4, of M2O to SiO2 in the range of about 0.04 to about 0.15, of H2O to M2O in the range of about 5.0 to about 9.0 and of M2O to Al2O3 in the range of about 0.10 to about 0.40.
Third Embodiment
The binder composition of a third embodiment includes a composition by weight of:

    
    
        10-20% fumed silica;
        40-50% anhydrous aluminum silicate; and
        equal parts of 15-25% silicic acid; and
        15-25% either potassium or sodium salt, or combinations thereof.
    
    


The binder composition of this embodiment is particularly useful in the steel industry.
It is readily understood that each of the examples described herein have applications in recycling, construction and hazardous waste disposal. However, each has been found to have particular applications as a result of the costs and/or the specific characteristics which are required. In general, the inorganic binder of the present invention has been found to be non-shrinking on setting, to have high early strength, high surface hardness (>6 on moh scale) and high compressive strength in comparison to Portland cement and even other inorganic binder compositions.
It is now apparent to a person skilled in the art that numerous combinations of binders may be manufactured using the present invention. However, since many other modifications and purposes of this invention become readily apparent to those skilled in the art upon perusal of the foregoing description, it is to be understood that certain changes in style, amounts and components may be effective without a departure from the spirit of the invention and within the scope of the appended claims.

## Claims

1. An inorganic binder composition comprising an admixture of:
(i) a first constituent comprising silicon dioxide, tri-calcium silicate, di-calcium silicate, tri-calcium aluminate, aluminum oxide, ferric oxide, magnesium oxide, and sulfur tri-oxide; and
(ii) a second constituent different from the first constituent and comprising fly ash F and at least one member other than fly ash F, selected from the group consisting of nepheline syenite, aluminum silicate, sodium hydroxide, silicic acid, potassium salt, sodium salt and mixtures thereof;

wherein said admixture has a molar ratio of SiO2 to Al2O3 in the range of from about 5.2 to about 14.3.

2. The inorganic binder composition defined in claim 1, wherein said composition comprises from 40 to 90% by weight of the first constituent.

3. The inorganic binder composition defined in claim 1, wherein said molar ratio of SiO2 to Al2O3 is in the range of from about 5.2 to about 7.6.

4. The inorganic binder composition defined in claim 1, wherein the first constituent is present in an amount of from 62 to 90% by weight, and the second constituent comprises 5-20% by weight fly ash F, 4-10% by weight fumed silica and 1-8% by weight Al2O3.

5. The inorganic binder composition defined in claim 1, wherein said admixture has a molar ratio of SiO2 to Al2O3 in the range of from about 5.2 to about 8.9, a molar ratio of M2O to SiO2 in the range of from about 0.07 to about 0.11, a molar ratio of H2O to M2O in the range of from about 5.0 to about 10.0 and a molar ratio of M2O to Al2O3 in the range of from about 0.30 to about 0.45, where M2O is selected from the group consisting of Na2O, K2O and a mixture of Na2O and K2O.

6. The inorganic binder composition defined in claim 1, wherein said admixture has a molar ratio; of SiO2 to Al2O3 in the range of about from 7.4 to about 14.3, of M2O to SiO2 in the range of from about 0.05 to about 0.10, of H2O to M2O in the range of from about 5.0 to about 9.0 and of M2O to Al2O3 in the range of from about 0.25 to about 0.45, where M2O is selected from the group consisting of Na2O, K2O and a mixture of Na2O and K2O.

7. The inorganic binder composition defined in claim 1, wherein said admixture has a molar ratio of SiO2 to Al2O3 in the range of from about 5.2 to about 9.0, of M2O to SiO2 in the range of from about 0.50 to about 2.00, of H2O to M2O in the range of from about 5.0 to about 9.0 and of M2O to Al2O3 in the range of from about 1.75 to about 3.50, where M2O is selected from the group consisting of Na2O, K2O and a mixture of Na2O and K2O.

8. The inorganic binder composition defined in claim 1, wherein the pozzolan comprises fly ash C.

9. The inorganic binder composition defined in claim 1, wherein the pozzolan comprises fumed silica.

10. The inorganic binder composition defined in claim 1, wherein the pozzolan comprises slag.

11. A method of recycling waste materials from a smelting furnace, comprising:
admixing revert materials of a metal smelting furnace with an inorganic binder composition; and
compacting the admixture into a briquette;

wherein the inorganic binder composition comprises
(i) a first constituent comprising silicon dioxide, tri-calcium silicate, di-calcium silicate, tri-calcium aluminate, aluminum oxide, ferric oxide, magnesium oxide, and sulfur tri-oxide; and
(ii) a second constituent different from the first constituent and comprising fly ash F and at least one member other than fly ash F, selected from the group consisting of nepheline syenite, aluminum silicate, sodium hydroxide, silicic acid, potassium salt, sodium salt and mixtures thereof.

12. A method according to claim 9, wherein said admixture has a molar ratio of SiO2 to Al2O3 in the range of from about 5.2 to about 14.3.

13. A method according to claim 11, wherein the molar ratio of SiO2 to Al2O3 is from about 5.2 to about 7.6.

14. A method according to claim 11, wherein the admixture comprises 131⁄2- 171⁄2% by weight of the binder composition.

15. A method according to claim 11, comprising feeding cold finder stock.

16. A method according to claim 11, comprising the inorganic binder composition.

17. A method according to claim 11, comprising drying the admixture before compressing it into a briquette.

18. A method according to claim 11, wherein the revert materials comprise coke breeze, mill scale, flue dust, or furnace sludge.

19. A method of operating a blast furnace comprising
smelting a metal ore in a blast furnace;
admixing revert materials from the smelting with an inorganic binder composition;
compacting the admixture into a briquette; and
reintroducing the briquette into the furnace, wherein the binder composition comprises
(i) a first constituent comprising silicon dioxide, tri-calcium silicate, di-calcium silicate, tri-calcium aluminate, aluminum oxide, ferric oxide, magnesium oxide, and sulfur tri-oxide; and
(ii) a second constituent comprising fly ash F and at least one member other than fly ash F, selected from the group consisting of Al2O3, pozzolan, nepheline syenite, aluminum silicate, sodium hydroxide, silicic acid, potassium salt, sodium salt and mixtures thereof.

20. A method according to claim 19, wherein the metal ore comprises iron, lead, nickel, or zinc.

21. A method according to claim 19, wherein the metal ore comprises iron.

22. A method according to claim 19, wherein said admixture has a molar ratio of SiO2 to Al2O3 in the range of from about 5.2 to about 14.3.

23. A method according to claim 19, wherein the molar ratio of SiO2 to Al2O3 is from about 5.2 to about 7.6.

24. A method according to claim 19, wherein the admixture comprises 131⁄2- 171⁄2% by weight of the binder composition.