CA1275424C - Methods of making cementitious compositions from waste products - Google Patents

Abstract

METHOD OF MAKING CEMENTITIOUS COMPOSITIONS FROM WASTE PRODUCTS ABSTRACT Methods for producing cementitious compositions from waste products, such as non-ferrous slags, or fossil fuel combustion residue, or ferrous slags, whereby the CaO and alumina contents of the waste products are adjusted as necessary to enable them to combine with a sulphate additive at elevated pH and so couple the faster reactions of the mineral Ettringite with the slower ones of the calcium silicates.

Description

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METHODS OF MAKING C~MENTITIOUS
OMPOSITIONS FROM W~STE PRODUCTS

Technlcal Field The invention relates to the use of various waste produc-ts in cementitious compositions, such as cemen-ted mine backfill, or other stabilized earths. Such waste products may include non-ferrous slags, as well as fossil fuel combustion residues.
Background Art sy-products of metallurgical processes, such as slags which result from the smelting of both ferrous and non-ferrous ores, and combustion products of coal from fossilfuel powered generating stations, such as fly ash or clinker, all represent the product of a significant investment of energy which is normally lost upon the subsequent disposal of these materials, heretofore considered as waste.

The term 'slag' as used in this application refers to the vitreous mass which remains after the smelting of a metallic ore, a process which entails the reduction of the metallic constituents in the ore to a molten state.

The terms 'ferrous slag' or 'blast furnace slag' refer to that slag which remains after the smelting of iron ore.
Alternately, 'non-ferrous slag~ is that slag which remains after the smelting of a non-ferrous ore such as copper, 75'~

nickel, lead, or zinc, whether it be done in a blast furnaceor otherwise. Therefore, a slag considered non-ferrous in the metallurgical sense may contain appreciable amounts of iron due t~ the presence of this compound as an impurity within the ore.

Fly ash is a combustion product resulting from the burning of coal which has been ground to a relatively fine particle size. Coal which is not as finely ground produces both fly ash and a coarse, incombustible residue known as clinker.
Many countries, including the United States, ~anada, Chile, South Africa, Australia and the Scandinavian countries, produce or export a great deal of both ferrous and non-ferrous metals. This results in the production of significant quantities of slag, produced as a by-product of the required smelting operations. Blast furnace slags are currently used as additives in some low strength concretes whereas, except for railway ballast and granular fill type applications, the feasibility of potential utilizations of non-ferrous slags and fly ashes has been comparatively disregarded, leading to the disposal of substantial quantities of these commodities with resulting large accumulations in areas surrounding the smelters and power stations.

The economic feasibility of sub-surface mining techniquçs depends upon an ability to fill the cavities created by the removal of the ore in order to establish and retain safe ~Jorking conditions. One accepted technique for performing this function involves the addition of Portland ~ ~ 7'~

cement to the fill to act as a bincler in crea~lng a hardened cementitious composition.

The Portland cements used in this manner are specially formula-ted to primarily comprise specific compounds, such as tri-calcium silicates, di-calcium silicates and tri-calcium aluminates which, on hydration, provide the desired cementing or binding action. The principal constituents of - these Portland cements, i.e. CaO and Sio2, are present in a high ratio of about 3 : l to strongly promote the calcium silicate reactions.

- 15 The difficulty and expense involved in transporting large quantities of Portland cement to often isolated mining locations has prompted a search for cheaper additives or substitutes which can reproduce the cementitious effect of Portland cement at a reduced cost. Thus, cemented fills ~ introduce a broad new flexibility into mine planning and design; however, cost considerations limit potential applications. Any means of reducing cemented fill costs for a given fill duty, therefore, broadens the potential application for the material.

In general, if a lower cost binder which allows the formation of a slurry with mine tailings and/or sand at the same viscosity as that of a Portland cement slurry and which develops adequate compressive strength in adequate times to prevent collapse was available, lower grade orebodies could be mined economically. Applicants~ invention serves ~ust such a function.

The class of materials described under the broad term ~'7~

of 'pozzolans' offers potential cost savings in cemented fill practice. A pozzolan is any materlal which can provide silica to react with calcium hydroxide in the presence of water to form stable, insoluble cementitious hydrated calcium siLicates, or related, more complex silicates. The silicates formed by pozzolanic action are closely related to some ol those formed by the hydration of Portland cement.

Iron blast furnace slag, fly ash and various 'natural~
slags and ashes have been known for some time to have pozzolanic properties. Waste industrial slags, however, do not contain the correct quantities of essential ingredients of Portland cements. Iron blast furnace slag comes closest with a CaO/SiO2 ratio of approximately l. To acquire such pozzolanic properties, however, such slags must be cooled to an amorphous (or highly vitreous) state by rapid quenching, such as by immerslon in a large quantity of high pressure water. It is well known for example, that granulated blast-furnace slag obtained in the production of pig iron can be mixed with Portland cement clinker and the mixture finely ground to bring out the inherent hydraulic properties of the slag.
~5 In most current applications wherein ferrous slag or fly ash is used in backfilling, one finds a combination of a small quantity of Portland cement providing some initial set and strength, together with the slag or fly ash. The slag or fly ash reacts with residual CaO from the cement reactions to form a 'high-grade' pozzolanic material having calcium silicates which provide the balance of the strength required over a period of time.

The p~operties of such ferrous slag-based pozzolanic materials have been set forth ln great detail in varlous reference works well known by those working in the field, including, for example, Turriz:iani, R., "Aspects of the Chemistry of Poz~olanas", Chapter 14, The Chemistry of Cenents, H.F.W. Taylor, Ed. Vol. 2, Academic Press, 1964;
Nurse, R.W., "Slag Cements", Chapter 13, The Chemistry of 1 ements, H.F.W. Taylor, Ed., Vol. 2, Academic Press, 1964;
- Kramer, w., "Blast-Furnace Slags and Slag Cements", Paper VII-2, Fourth International Symposium on the Chemistry of Cement, Washington, D.C., pp. 957-981, 1960 and Biczok, I., "Portland Blast-Furnace Cements (Slag Cement)", pp. 50-58, in Concrete Corrosion and Concr~te Protection", Chemical Publishing Co., Inc., New York, N.Y. 1967.

Additionally, the general physical requirements for S'acceptable" pozzolanic activity are set forth in the ASTM
Standard Specification for "Blended Hydraulic Cements", no.
C595. These requirements are reproduced below:

POZZOLAN
Fineness: Amount retained when wet sieved on 45 um ,No. 325) sieve, max. % 20.0 Pozzolanic Activity 30 Test: With lime (8.16), strength, minimum psi, (MPa) 800 (5.5) or with portland cement, (8.17), index, min. % 75 ~7~ J~

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Slag Activi-ty Test: With lime (8.16), streng-th, minimum psi (MPa) 800 (5.5) or with portland cement ~8.19), index, min. % 75 A pozzolan would therefore have acceptab]e pozzolanic activity under these specifications if it meets either of the two alternative limits.
The chemical composition of the non-ferrous slags, however, is sufficiently different from that of the ferrous slags to require modification as described below in order to convert such non-ferrous slags from a 'low-grade pozzolan' to a 'high-grade pozzolan'. That is to say, that, to enable the use of non-ferrous slags as cement, their chemical composition must generally be modified to produce a product capable of competing with Portland cement, i.e., one capable of achieving high early strength as well as a high ultimate strength within an acceptable time frame.

Appli~ants have determined that a higher quality, less expensive cemented backfill may be produced, without the use of Portland cement, by adjusting the proportions of both CaO
and A1203 in non-ferrous slag. This adjustment then converts the slag from a 'low-grade' pozzolan to a 'high-grade' pozzolan wherein the necessary aluminate reaction can be harnessed by adjusting the sulphate ion and-calcium hydroxide concentrations. Further, the methods for making ~ ~ 7~t~L~

cement from non-ferrous slag may also be extra~olated and used to prepare improved cements utilizing ferrous slags or fossil fuel combustion residues.

Summary of the lnvention The invention relates to a method for making cementitious compositions from a residue of waste industrial products such as non-ferrous slags, fossil fuel combustion residue or ferrous slags. This method includes the steps of grinding the vitreous waste residue whose composition may or may not have been altered by the addition of Cao and/or Al203, to a predetermined particle size, and adding calcium hydroxide or CaO, and a compound containing a sulphate anion to form a mixture with water, which is then allowed to cure to the final cementitious compositions.
The Ca(OH)2 or CaO added after the waste residue has been ground is to raise the pH, in the presence of the water, to an alkaline value to activate the alumina component and provide a hlgh early strength.
A preferr~d particle size is between about 2,500 and 5,000 Blaine, although larger or smaller particles will work in this invention. A preferred pH range is between about lO
and 14 and this range i-s achieved by the addition of an alkaline compound.

The curing of samples must be done under enclosed conditions at saturated humidity.

The application of heat during mixing and curing of 3~

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samples greatly enhances the strength/time relationship.
Tempe~ature is thus a very impor~ant parameter;in the successful application of the invention.

In these methods, a predetermined amount of Portland cement, aggregate, fillers, tailings, or other inert material can be added to the mixture prior to adding -the w~ter.

The compound containing CaO or Al203 may be added to a furnace during the generation of the slag, or it may be added to said slag after the slag has been formed and before it is granulated. A preferred CaO containing compound is lime for both composition modification and pH adjustment. A
preferred Al203 containing compound is fly ash. Also, preferred compounds containing a sulphate anion include ¦ sodium sulphate or gypsum.

Finally, the invention relates to the cementitious compositions produced by the previously described methods.

Detailed Description of the Preferred Embodiments As one skilled in the art would realize, the chemical analysis of various slags from either ferrous or non-ferrous ore smelting operations as well as that of the fly ash or clinker which results from fossil fuel combustion, can vary over a wide range. Average typical analyses for such materials are set forth in Table I. This table includes the major components of the slags, but a minor amount of additional components such as metal oxides, sulphides, etc.
may also be present.

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. g TABLE I
~OMPOSII'ION OF TYPI~AL SLAGS

Weight Percent _.______________.________ ____ 10 Ni,ckel Reverbe~atory Slag 2-10 32-36 2-10 4~-56 Copper Reverberatory Slag 1-8 33-40 2-10 47-50 Iron Blast Furnace Slag 35-50 28-38 10-20 3-5 Non-Ferrous Blast Furnace Slag 15-20 32-38 2-10 30-40 Fossil Fuel Combustion Residue ~Fly Ash) 2-15 38-67 15-38 3-13 20 The present invention relates to a composition and a method for obtaining useful cementitious products comprised of such waste residues by adjusting and balancing various important components to control the cementitious reactions in the final compositions. As shown in Table I, non-ferrous slags typically have relatively low calcium oxide and alumina contents. Such amounts of calcium oxide and alumina are often insufficient to provide for the required calcium sulpho-aluminate and calcium silicate reactions and thus, such slags are not suitable for use on their own as cements unless their chemistry is appropriately modified.

A minimum amount of about 8% CaO and about 3 1/2 - 4% of A12O3 is required to be present (in a preferred ratio of 3~

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approximately 2:1 CaO:A12O3) within the waste material utilized to form the cementitious composition of the present invention. These levels are necessary in order to provide a starting material whose alumina component may be activated upon the s~bsequent addition of a composition containing additional Ca(~l)2 or CaO to react with a sulfate--containiny composition and form a cementitious material capable of p~oviding a high early strength.

Such a modification of the calcium oxide content can be carried out using a variety of methods. During the formation oF slag in a furnace, additional lime or limestone may be added during the smelting process, with a corresponding increase in the final calcium oxide content of the slag. Similarly, a modification of the aluminium oxide content can be achieved by the addition of, for example, fly ash, during the smelting process.

Once a slag of the correct composition has been made and granulated to a high glass content, it must be ground, together with the gypsum if necessary, to a predetermine fineness, preferably between about 2,500 and 5,000 ~laine.

Thus, the addition of water and an alkaline material, preferably lime, serves to activate this composition.
Differentiation is necessary, however, between lime used as an activator and lime added to the furnace feed to increase the CaO content of the slag, this being the lime which subsequently plays a major role in the cementitious reactions. It is necessary that this CaO be incorporated into the amorphous structure of the slay to enhance its disordered chemical state and increase its reactivity.

The alkaline materlal, added in order to activate the mlxture, adjusts the p~I upwardly to about twelve and allows the formation of gels and ~l2 ions. Unless gypsum (C~S04-2H2O) or some other sulphate ion containing materials are added, however, the alumina component remains unreactive. In order for the cementitious compound to be successful, its alumina component chemistry must approach t~at of the compound Ettringite, a calcium monosulpho-aluminate compound with the approximate formulaCa6Al2(S04)3(OH)l2 26H20. The traditional 'pozzolonic~
slay-lime-water system is generally deficient in sulphate radical and unless this is added from some extraneous source, the desired cementitious reactions will not occur.
It is possible that in certain ores, the sulphate radical may exist in the mill tailings in a form in which it would be available for the cementitious reactions but for most cases, additional sulphate ions must be added to the slag.
Thus, it is critical to adjust the sulphate content to a range which, when combined with the other ingredients, provides the approximate stoichiometric ratio found in the mineral ettringite. The sulphate anion can be added as either gypsum or sodium sulphate or other.

The pH of the mix may be raised to the required alkaline value by addition of an alkali metal hyroxide or other base, or by the addition of alkaline materials such as sodium carbonate, sodium bicarbonate or potash, provide they are accompanied by the addition of free lime.

By adjusting all of these components within the parameters stated above, a cementitious composition is formed, having a portion which forms ettringite-like 3~

- ].2 -structures, thus obtaining sufficient strength and stabi].ity in the final cementitious product.

With respect to ferrous slags, a similar procedure could be followed. Such slags, however, usually contain a much higher calcium oxide and alumina content than non-ferrous slags and their compositions would not need adjusting. The o~her steps described above would be followed in an - essentially identical fashion to those for non-ferrous slags in order to achieve the desired cementitious compositions.
Fly ash or other fossil fuel combustion residue would be treated in the same manner as ferrous slags.

As would be clearly understandable to one skilled in the art, the cementitious compositions of the present invention may be used alone, or they may be mixed with a wide variety of fillers, aggregate, accelerators, r.eOtarders or other additives. Also, such cementitious compositions can be substituted for all or a portion of the Portland cement component of ordinary cementitious compositions or concrete.
Such cements can also be mixed with high aluminous cements, pozzolans or other materials to form specialty cements for specific applications.

While it is apparent that the invention disclosed herein ~ is calcu~ated to provide an improved cementitious system over those described in the prior art, lt will be appreciated that alternate embodiments may be devised by those skilled in the art. It is therefore intended that the appended claims cover all modifications or embodiments as fall within the true spirit and scope of the present invention.
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Claims (34)

The embodiments of the invention in which and exclusive property or privilege is claimed are defined as follows:

1. A method for making a cementitious composition which comprises:
adding to a waste residue of a non-ferrous slag, a fossil fuel combustion residue, or a mixture thereof during its formation in a furnace or burner a compound containing CaO and a compound containing Al2O3 to form a first mixture having a sufficient CaO and AL2O3 content to enable said first mixture to react with a composition comprising a sulphate anion, added thereto during a subsequent treatment step, to form a composition having pozzolanic qualities attainable with ettringite;
increasing the pH of the first mixture to a sufficiently alkaline value to activate the alumina component of said first mixture;
treating said first mixture by the addition thereto of a compound containing a sulphate anion and an amount of water sufficient to hydrate said treated mixture so as to form a second mixture, the proportional relationship among the CaO, Al2O3 and sulphate components in said second mixture being such that the ratio therealong sufficiently approaches the stoichiometric relation of the components of the mineral ettringite so as to form a high-grade pozzolanic material therefrom; and allowing said second mixture to cure so as to form a cementitious composition.

2. The method of claim 1 wherein said first mixture comprises at least about 8% of said CaO and at least about 3.5% of said Al2O3.

3. The method of claim 2 wherein the ratio of said CaO to said Al2O3 is about 2:1.

4. The method of claim 1, 2 or 3 wherein the pH of said first mixture is adjusted to between about 10 and 14 by addition of an alkaline compound in order to activate the alumina component of said first mixture and provide said first mixture with a high early strength.

5. The method of claim 1, 2 or 3 wherein additional CaO is added to said furnace or said burner during the formation of the waste residue.

6. The method of claim 1, 2 or 3 wherein additional CaO is added to said slag after said slag is ground.

7. The method of claim 1, 2 or 3 wherein said compound containing CaO is lime.

8. The method of claim 1, 2 or 3 wherein said compound containing a sulphate anion is an alkali metal sulphate or gypsum.

9. The method of claim 1, 2 or 3 which further comprises grinding said first mixture to a particle size of between about 2,500 and 5,000 Blaine, prior to increasing the pH thereof.

10. The method of claim 1, 2 or 3 which further comprises adding an amount of Portland cement to the first mixture sufficient to impart additional strength to the cementitious composition formed therefrom.

11. The method of claim 1, 2 or 3 which further comprises adding aggregate, fillers, tailings, or mixtures thereof to said first mixture prior to adding said water thereto.

12. The method of claim 1, 2 or 3 which further comprises curing the second mixture to obtain a cementitious composition having increased strength obtainable within the shortest curing time.

13. A method for making a cementitious composition which comprises:
adding to a waste residue of a non-ferrous slag, a fossil fuel combustion residue or a mixture thereof during its formation in a furnace or burner a compound containing CaO and a compound containing Al2O3 to form a first mix-ture having a sufficient CaO and Al2O3 content to enable said first mixture to react with a composition comprising a sulphate anion, added thereto during a subsequent treat-ment step, to form a composition having pozzolanic quali-ties attainable with ettringite;
increasing the pH of the first mixture to a suffic-iently alkaline value to activate the alumina component of said first mixture; and treating said first mixture by the additive thereto of a compound containing a sulphate anion so as to form a second mixture, the proportional relationship among the CaO, Al2O3 and sulphate components in said second mixture being such that the ratio thereamong approaches the stoi-chiometric relation of the components of the mineral et-tringite so as to obtain the pozzolanic qualities of et-tringite, thus forming a cementitious composition.

14. The method of claim 12 which further comprises grinding said first mixture to a particle size of between about 2,500 and 5,000 Blaine, prior to increasing the pH
thereof.

15. The method of claim 13 wherein the pH of said first mixture is adjusted to between about 10 and 14 by addition of an alkaline compound.

16. The method of claim 13 which further comprises adding an amount of Portland cement to the first mixture sufficient to impart additional strength to the cementi-tious composition formed therefrom.

17. The method of claim 13 which further comprises adding aggregate, filler or tailings to said first mix-ture.

18. The method of claim 13 wherein said compound containing CaO is added to furnace or said burner during the formation of the waste residue.

19. The method of claim 14 wherein additional CaO is added to said slag after said slag is ground.

20. The method of claim 13 wherein said compound containing CaO is lime.

21. The method of claim 13 wherein said compound containing a sulphate anion is an alkali metal sulphate, or gypsum.

22. The method of claim 13 which further comprises curing the second mixture to obtain a solid cementitious composition.

23. A method for making a cementitious composition which comprises:
adding to a waste residue of a non-ferrous slag, a fossil. fuel combustion residue or a mixture thereof during its formation in a furnace or burner a compound containing CaO and a compound containing Al2O3 to form a first mix-ture having a sufficient CaO and Al2O3 content to enable said first mixture to react with a composition comprising a sulphate anion, added thereto during a subsequent treat-ment step, to form a composition having pozzolanic quali-ties attainable by ettringite;
grinding said first mixture so as to reduce the particle size thereof;
increasing the pH of the first mixture to a suffic-iently alkaline value by the addition of an alkaline com-pound to activate the alumina component of said first mix-ture and thus to provide said first mixture with a high early strength;
adding to said first mixture a compound containing a sulphate anion and an additional amount of said compound containing CaO to form a second mixture;
hydrating said second mixture with a sufficient quan-tity of water such that the proportional relationship among the CaO, Al2O3 and sulphate components in said sec-ond mixture is such that the ratio thereamong approaches the stoichiometric relation of the components of the mineral ettringite; and allowing the second mixture to cure to a solid cemen-titious composition having the pozzolanic qualities of ettringite.

24. A method for making a cementitious composition which comprises:
adding to a waste residue of a non-ferrous slag, a fossil fuel combustion residue or a mixture thereof during its formation in a furnace or burner a compound containing CaO and a compound containing Al2O3 having a sufficient CaO and Al2O3 content to enable said first mixture to react with a composition comprising a sulphate anion, added thereto during subsequent treatment step, to form a composition having increased pozzolanic qualities com-pared to the untreated waste residue;
increasing the pH of the first mixture to a suffic-iently alkaline value to activate the alumina component of said first mixture; and treating said first mixture by the addition thereto of a compound containing a sulphate anion so as to form a second mixture, the proportional relationship among the CaO, Al2O3 and sulphate components in said second mixture forms a cementitious composition capable of being hydrated to a higher-grade pozzolanic material as compared to the untreated waste residue

25. The method of claim 24 wherein said slag is ground to a particle size of between about 2,500 and 5,000 Blaine.

26. The method of claim 24 wherein the pH is ad-justed to between about 10 and 14 by addition of an alka-line compound.

27. The method of claim 24 which further comprises adding an amount of Portland cement to the first mixture sufficient to impart additional strength to the cementi-tious composition formed therefrom.

28. The method of claim 24 which further comprises adding aggregate, filler or tailings to said first mix-ture.

29. The method of claim 24 wherein said compound containing CaO is added to said furnace or said burner during the formation of the waste residue.

30. The method of claim 25 wherein additional CaO is added to said slag after said slag is ground.

31. The method of claim 24 wherein said compound containing CaO is lime.

32. The method of claim 24 wherein said compound containing a sulphate anion is an alkali metal sulphate or gypsum.

33. The method of claim 24 which further comprises curing the second mixture to obtain a solid cementitious composition.

34. A method for making a cementitious composition which comprises:
adding to a waste residue of a non-ferrous slag, a fossil fuel combustion residue or a mixture thereof during its formation in a furnace or burner, a compound contain-ing CaO and a compound containing Al2O3 to form a first mixture having a sufficient CaO and Al2O3 content to enable said first mixture to react with a composition comprising a sulphate anion, added thereto during a subse-quent treatment step, to form a composition having in-creased pozzolanic qualities as compared to the untreated waste residue;
grinding said first mixture so as to reduce the par-ticle size thereof;
increasing the pH of the first mixture to a suffic-iently alkaline value by the addition of an alkaline com-pound to activate the alumina component of said first mixture and thus to provide said first mixture with a high early strength;
adding to said first mixture a compound containing a sulphate anion and an additional amount of said compound containing CaO to form a second mixture;
hydrating said second mixture with a sufficient quan-tity of water such that the proportional relationship among the CaO, Al2O3 and sulphate components in said sec-ond mixture forms a cementitious composition of a higher-grade pozzolanic material as compared to that obtainable from the untreated waste residue; and allowing said second mixture to cure so as to form a solid cementitious composition.