CA2536428A1 - Converting spent potliners into a glass frit - Google Patents

Abstract

A pyrometallurgical process and apparatus for converting spent potliners from aluminium manufacturing or other hazardous materials into an amorphous sodium and calcium fluroaluminosilicate glass frit and a high carbon material.
Spent potliners, silica or siliceous material, and a calcium oxide source are fed into vessel such as an electric melting furnace. The material is heated and melted to destroy cyanides, convert fluoride salts to calcium fluoride and form a homogeneous liquid material. Carbon is then physically separated from the material. The material is then vitrified to produce a valuable glass frit and a high carbon material. Optionally, prior to melting, the material is heated in a rotary kiln.

Description

CONVERTING PENT POTLINERS INTO A GLASS FRIT
FIELD OF THE INVENTION
The present invention relates generally to processing spent potliners from aluminium manufacturing or other hazardous materia~s, In particular, the invention relates to a pyrometallurgical process and apparatus for converting potliners into a glass frit, and to products obtained by the prpcess.
BACK .C'aRlaUNf3 OF THE INVEN'~'IC3N
In the process of aluminum production, alumina is dissolved in cryolite in electrolytic cells, or pots, which are stee# shells protected by refractory material and lined with carbon. A number of pots, usually more than 10fl, are arranged in series to form a potline. The pots contain a molten electrolyte consisting primarily of cryolite (Nay4lF~} and operate at approximately ~J30° to 1000'C, Other materials ace added to the electrolyte to improve the efficiency of the operation or to reduce power ConSGlllptidn, SUCK aS alur»ina, aluminium f~uor9de, sodium fluoride, Soda ash, Calcium fluoride, #ithium carbonate and magnesium oxide.
The hearkh or lining of the cell is composed of carbon, which is backed by insulation and Contained within a steel container called a potshell. The carbon portion of the lining serves as the cathode and contains the molten electrolyte. The carbon lining is composed of preFabrivated carbon blacks joined together by a carbon paste, which is hydraulically rammed in the seams between the carbon blocks. The sidewalls of the lining are typica!!y formed with carbon paste, but may contain prefabricated carbon blocks.
Over the life of the Gathvda and its cell lining, the Carbon and insulating materials become impregnated with fluoride~containing salts- Failure can occur by cracking or excessive heaving of the lining. When these faitures occur. the cell is taken ofi-line and the cathode fining material is removed from the potshell by mechanized digging equipment. This spent cathodic material is referred to as spent pott#ner (SPt-).
The electrolysis of a#umina in sme#ting pots is cause for the production of residual material in the form of SPL amounting to same 20 fcg per ton pf aluminium produced.
nround the world, one estii»ate is that around 15Q,000 tons of new and old SPt_ is available on a yearly basis.

in addition to containing fluoride salts, as mentioned above, SPL cpntains cyanides that are fprmed by the: ingress of air through openings in the potshell and subsequent reaction of nitrogen with the carbon lining.
Spent potliner was listtd by the Environmental Protection Agency (EPA) on Sap. 13, 1588 (53 Fed. Reg. 35412} as a hazardous waste (K088~ under 4d C.i'.R., Part 269, Subpart D, because it may contain significant amounts of Iran cyanide complexes and free cyanide. Thus, there is a need in the aluminium industry far an economical process for detoxifying spent patliner such that the treated residue is npt a hazardous waste, This is important because of the need fnr alternatives to Land disposal of hazardous waste, established as national policy in the RCRA
Hazardous and Solid Waste Amendments (HSWA) of '1984, 2nd the anticipated lack of hazardous waste treatment capacity.
The composition of SPL is highly variable, One range of analyses is given in Table t. A process for the treatment of SPL should be versatile enough to treat SPA.
generated while using different ceEl designs, electrolyte compositions, and insufation packages, and any residues generated should meet anticipated EPA-defined limits far all constituents of concern (e.g., cyanide, fluoride, organics and metals}.
The components of SPt_ of greatest concern environmentally era cyanide and soluble fluoride salts. Of environmental and safety concern is the presence of waist reactive materials (carbides) created during the pot life and resulting in explosive gases (hydrogen, methane and ammonia) upon exposure to water or oven moisture of the air.
Table 1. Chemical Composition of Spent Pottiners The aluminum industry has Iong recognized the environmental liability of SPL
and has pursued many options for treatment andlor disposal. These options include landfilling, recycling as a feedstock in other industries, such as the steel, cement, aluminum, ar mineral wOpl industries. fluidized bed combustion, cryalite recovery, pyrohydrolysis, pyrasulfolysis, and others. Landfilling is an option that is presently available but will became inGreasingiy expansive, and eventually may be prohibited,

-2-since hazardous waste landfills are required. In certain prior processes, the residuals produced require landiilling, sometimes in an amount greater than the SPL
troated_ SPL is considered a hazardous residual material because of its:
Toxicity due to its content of highly soluble fluorine and reactive cyanhydric salts.
2. Reactivity with water either liquid or from moisture contained in the atmospheric air due to carbides and nitrides formed during the active life of the liner.

3. t3eryllium salts andlor oxides present that are recognized to sometimes induce berylliosis which is an allergic response of the human immune system to the presence of dust containing minute amounts of beryllium in the lungs.
SPL has traditionally been a difficult material to recycle du>~ to its fluorine content and because it is highly variable in its chemical composition.
Previous efforts to rECycle SPL by pyrometallurgical processes have encountered difficulties presented by the fluorine salts, namely the sodium fluoride has a tendency to vaporize and escape from the solids t~in9 treated during the process.
The salts clog the gas handling system when cooling down andlor chemically attack the refractory and mete! it encounters. This action is augmented fohowing the reaction:
2NaF * H20 * E --~i Na~O * 2NF (whore E is energy). Such actions are cause for very high maintenance costs. Furthermore, they render such process difficult to control thus increasing operating time.
certain existing treatment processes are described below, and are grouped into two categories based an the amount of carbon combusted in the described process.
The first throe processes operate under Conditions in which little, if any, carbon is combusted. In these three processes, the carbon remains in the final product.
U. S. Patent No. 5, i 64,174 (Reynolds Metals Company) describes a method for detoxifying SPL by thermal treatment in a counter-current rotary kiln.
Limestone and metal silicates are added to destroy cyanides by oxidation, and convert the soluble fluoride salts to relatively insoluble calcium fluoride and fluoride-bearing minerals. Air emissions contain very Tittle fluorine and cyanide because of the law kiln operating temperature. Ash and particulate matter are removed and recycled or land-filled. The discharge material is air cooled and contains the carbon. Wowever, because of the relatively low processing temperatures, the conversion of NaF to CaF2 is inefficient.

U.S. Patent No. 4,497,464 (Ogden Environmental Services) describes a process for the treatment of ground SPL to reduce cyanide content to environmentally non-hazardous levels. Ground SPt, is roasted in a stream of air or nitrogen at a temperature between about 260° and 760°C (500° and 1400°F), Cyanide levels are reduced without combustion of a major portion of carbonaceous material, resulting in an end product rich in carbon and fluorine. Because no calcium oxide source is added the following chemical reactions do not occur:
CaGOa -7 Ca0 + COz;
2NaF + Ca0 -~ CaF; * Na~O; and 2AIF;~ + 3CaO -> 3CaF,, + AIZOa.
Therefore, the fluoride salts are not converted to a stable, calcium fluoride.
The Ogden discharge is essentia4y a land5fl material.
il.S. Patent No. 4,993,329 (Tabery et ail.) describes a method for thermal destruction of SPt. by 1=luidized Bed Cocnbustian (t°8C) in a mixture of lignite and limestone, Fluoride salts are Converted to calcium fluoride. Significant carbon would remain in the final product.
The following processes for processing SPL result in the combustion of large amounts of carbon.
U.S. Patent No. 4,763,585 (Ogden Environmental SQrvices) describes a process for the combustion of ground SEaL using about 'E to about 20 weight percent of a powdered inert anti-agglomeration additive. The SPL is burned at between '1400°F to about 2200° F (760° to 't204°C). The contaminated components are bound or encapsulated into a solid glassy slag, described as a glassy sodium metal (AI) silicate matrix encapsulating fluorine residues. Silica is added to the feed.
Conditions are adjusted to produce hydrogen fluoride, which is scrubbEd with water to produce a hydrogen fluoride solution. The high combustion temperatures cause much of the carbon to be combusted. Since no calcium oxide source is added, the following chemical reactions do not occur:
GaGO~ -> CaU + C02;
2NaF + Ca0 -> CaF~ + Na~O; and 2Ali=3 + 3CaO -> 3CaF2 + A12O3.
_4_ In fact, aluminium f#uoride and hydrogen fluoride are produced. AEsp, this process is not be able to convert substantially all of the fluorides salts to calcium fluoride. tn fact, much sodium fluoride would be evaporated, and fluorine merely encapsulated as a calcium salt.
U.S. Patent Na. 5,711,018 (A#coa) describes an industrial wash management facility (fWMF) for disposing of SPL using a co-current gas-fired rotary kiln.
The iWM!=
recovers and recycles fluorides from discharge gases to the molten bath and collects and withdraws glass frit residue. The operating temperature is between 115(1°C and 1250°C, and cannot exceed 125t?°G to avoid generating fluoride gas. A solid oxygenating and gasifying agerst (e.g, limestone) is added to form COZ which reacts with C to farm CO. The CO is burned above the molten bath, Siliceous material is added to the bath. Fluorides are fixed in the frit. Carbon is burned, as it is not desired in the frit because of its deleterious effect on porosity and leachability.
Silicon oxide is added to help convert the fluorides to a stable form, Due to poor kinetics, conversion of the fluorides salts to calcium fluoride is poor.
U,S. Patent No. 5,280,274 (Elkem Technology) descrsbes a method for treatment of SPL for use as a filler, ar as a raw material. Crushed SPt. is supplied optionally with an SiO~ source, to a closed electrothermic smelting furnace.
The SPL is melted at a temperature between 1300°C and 17501°G. Art oxidation agent is supp#ied to the furnace to oxidize carbon and other oxidizable components, such as metets, carbides and nitrides. Further, a source of calcium oxide is supplied to the smelting furnace in an amount nECessary to react with all fluoride present to form CaF7 and to farm a calcium aluminate or calcium aluminate silicate stag containing CaFr.
The slag is liquid at the bath temperature in the furnace, and it, and optionally a metal phase, era tapped from the furnace and cooled to blocks ar granules. Cyanide is oxidized, and the conversion of the fluoride sails to calcium fluoride is poor.
U.S. Patent No. 5,245,915 (Aluminium Pechiney) describes a thermal shock treatment of ground SPL mixed with a miners! additive (selected from the grpup consisting of anhydrous CaSO~, CaO and mixtures thereat. The minera# additive combines, with or without melting or fusion, with fluorine-containing compounds to form CaF:, hinary, ternary or quaternary compounds of NaF, CaF2, SiO;, AhO:,, CaSOn, Nay SO.,, of the nephelite, hauynite ar similar type. T'he conversion of the fluorides salts to calcium fluoride is poor.
_g_ U,S. Patent No. 4,113,832 (Kaiser A#uminum & Chemical Corporation) describes a treatment process far waste rrEaterials, such as SPL, channel and trench cleanings, floor sweepings and spent alumina from offgas purifying dry scrubbers. The waste material is pyrohydrafyzed at elevated temperature. Fluorides, such as NaF and HF can be recovered from the affgas generated by pyrohydrolysls, white alumina and Na;.O, or if desired, sodium aluminate, can be reclaimed from the solid residue of pyrohydrolysis. Na+ and f#uorine are volatized in this process.
U.S, Patent No. 4,735,784 (Morrison-Knudsen Company, Inc,) describes a process for treating solid substantially non-volatile waste contaminated with a heat sensitive contaminant. At least a portion of the contaminating components (i.e. fluorine) are either decomposed or evotve from the melt as a gas. The slag is cooled and any remaining contaminating compounds are bound or encapsulated into a solid glassy slag. The residue from the s#agging reaction Is a glassy solid sodium metal silicate matrix. Substantially alt of the fluorine is volatized and captured as HF.
U.S. Patent No, 6,074,823 (Vick et at.) describes a process of converting SPL
by gas#fication technology to produce an inert vitreous frit and useful gases including hydrogen fluoride, hydrogen and carbon monoxide. Substantially a#I of the fluorine is volatized and captured.
The first processes, described in U.S. Patents Nos. 5,164,17~t (Reynolds);

4,497,464 (Ogden) and 4,893,323 (No Assignee), relate to processes in which little, if any, carbon is combusted. In alt instances, the carbon remains in the final product.
Therefore, the described processes fail to provide a process where the carbon is removed, Likewise, these processes fail to provide a product from which carbon has been removed.
The next processes, described in U.S, Patents Nos. 4,763,585 (Ogden);

5,711,018 (Alcoa); 5,286,274 (Flkem) and 5,245,195 (Aluminum Pechiney); and 4,113,832 (Kaiser), relate to prpcesses in which a large portion of the carbon is combusted and an attempt is made to capture fluorine in the final product.
These processes do not permit recycling of carbon and have poor conversion of the fluoride salts to calcium fluoride.
The final three processes, described ire U,S. Patents Nos. 4,113,x32 (Kaiser);
4,735,784 (Marrison-Knudson) and 6,074,823 (Na Assignee), describe processes in which a large amount of fluorine is volatized and a large amount of carbon is _g_ Combusted. These patents fail to provide processes in which fluorine is efficiently captured in the frit and carbon is separated by physical means.
In the Applicant's PCT Application Na. CA 20051000199, another process is described. In an embodiment of that process, spent potliner, a calcium oxide source and a silica source are combined and heated to destroy cyanides, convert fluoride salts to calcium fluoride and form a generally homogeneous amorphous liquid material.
Carbon is then physically separated from the material and the material is vitrified. The process optionally includes, after the combining and heating step, a glass finishing step in which the material is held at a temperature sufficient to enhance matrix formation and to facilitate separation of carbon from the material. In one embodiment, the material is heated to between 800'C and about 1204°C. In an embodiment of an apparatus of CA 20051040199, the apparatus comprises a first vessel for heating the mixture and a second vessel for physically Separating the carbon from the material and a third vessel for vitrifying the material. The first vessel may be a rotary kiln for heating in counter-current fashion. The second vessel mey be a glass finishing furnace for holding the material at a temperature sufficient to enhance matrix formation and to facilitate separation of carbon from khe material. ThE third vessel may tae a quench basin.
It is, therefore, desirable to provide a process for converting SPL into a glass frit which obviates or mitigates at least one of the disadvantages of the prior art.
SUMMARY OF THS tNVENT10N
It is an object of the present invention to obviate or mitigate at least one disadvantage of previous processes, apparatuses or products.
According to an aspect of the present invention there is provided a process comprising the stops af: combining spent potliner, a calcium oxide source and a silica source and melting the combination to achieve a material temperature of between 900'C and 1250°C to destroy cyanides, convert fluoride salts to calcium fluoride and form a generally homogeneous amorphous liquid materiaE; physically separating carbon from the material; and vitrifying the material. The combination may be melted to achieve a material temperature of between 1025°C and 1 i 50°C.
The process may further comprise, prior to the melting step. heating the combination to between 450"C
and 850°C in a rotary kiln. The combination may be heated to between 700°C and _ 7 ,.

850°C in the rotary kiln. The material may be in a solid sfate in the rotary kiln. About 9 to about 18% by weight of a total feed may be aluminium. The heating in the rotary kiln may be effected in counter-current fashion, The process may further comprise, after the melting step, a glass finishing step in which the material is held at a temperature sufficient to enhance matrix formation and to facilitate separation of carbon from the material. The spent potliner may be crushed to less than 10 mm. Vtrifying the material may be effected by quenching. In one embodiment, a sufficient amount of calcium oxide is used to result in a substantially complete conversion of: GaCO~ and NaF to CaF2, Na?O and COz, according to: CaCO~, + 2 NaF ~ CaFz + NazO + COz. In one embodiment, an amount of calcium oxide is added to achieve a CaO to vitrifced material ratio of between about p.p.4:1 and about 0.10:1 by weight, In one embodiment, an amount of silica is added to achieve a Na~OISit?z ratio in the vitrified material of between about 0,2'1:1 and about x.36:1 by weight. The melting may be at a temperature that retains fluorine and carbon. tn one embodiment, glass is added to a molten portion of the material to increase production and to improve cementitious properties of the vitrified material. The material, after vitrification, may be ground to between about 4000 and about 8000 m'~kg. The melting may occur in an an electric melting furnace.
hccarding to an aspect of the present invention there is provided an apparatus comprising; (a) a first vessel for heating and melting a mixture of spent potliner, silica source and a calcium oxide source, to achieve a material temperature of between 900'C and 1250°C, for destroying cyanides, converting fluoride sails to calcium fluoride, forming a homogeneous liquid material, and fvr physically separating carbon from the material; and fib) a second vessel for vitrifying the material. The material temperature may be between 1025°C and '1154°C. The apparatus may further comprise a third vessel for heating, prior to heating and melting in the first vessel, the spent potliner, silica source and calcium oxide source to a material temperature of between 450°C and 850°C. The third vessel may a rotary kiln for heating in a counter-current fashion. The material temperature in the rotary kiln may be between 700°C
and 850°C. The first vessel may be an electric melting furnace. The electric melting furnace may also be for holding the material at a temperature sufficient to enhance matrix formation and to facilitate separation of carbon from the material. The second vessel may be a quench basin.
_g_ According to an aspect of the present invention there is provided a vitrified material made by the process described herein. Jn one embodiment, there is provided a composition comprising Por#land cement, blast furnace slag, silica fume, quartz, and the vitrified material described herein. In one embodiment, there is provided a composition comprising by weight, 30-50% Portland cement, 0-10% blast furnace slag, 5-15% silica fume, 0-10% quartz, and 35-65% vitrified material described herein.
According to an aspect of the present invention there is provided a use of a generally amorphous solid matrix of calcium and sodium fluoro-aluminosilicate with a carbon content of less than about 9 weight percent and a calcium #luoride content of between about 5 and about 35 weight percent having cementitious properties when finety ground that is produced from spent potliners together with Portland cement, blast furnace slag, silica fume, and quartz as a cementitious composition.
Other aspects and features of the present invention will become appac~ent to those ordinarily skilled in the art upon review of the following description of speci#ic embodiments of the invention in conjunction with the accompanying figures.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the present invention will now be described, by way of example only, with reference to the attached Figures, wherein;
Fig. 1 is a schematic of an apparatus according to an embodiment of the present invention;
Fig. 2 is a bloc diagram of a process according to an emt~odiment of the present invention;
Fig. 3 is a flow chart illustrating a process according to an embodiment of the present invention;
Fig. 4 is a schematic at a gas ci~CUit of a process according to an embodiment of the: present invention;
Fig. 5 is a schematic at a solid circuit of a process according to an embodiment of the present invention;
Fig. 6 is a schematic of a water circuit of a process according to an embodiment of the present invcntian;
Fig. 7 is a diffractogram of a product according to an embodiment of F'CT Application No, CA z4Q5naa199.
_g_ Fig. 8 is a graph showing chloride ion-permeability of blended concretes, some of which contain a product according to an embodiment of t'CT Applieatian No. CA 20051fl00199; and Fig. 9 is a graph showing the expansion obtained on aoncretes, some of which contain a product according to an embodiment of PCT Application No. CA 20g5lpg0199.
DETAILED DESCRIPTIpN
Generally, the present invention provides a pyrometallurgical process and apparatus for converting spent potliners (SPL) from aluminium manufacturing, or other hazardous materials, into commercially saleable amorphous calcium and sodium fluoroaluminosilicate glass frit (an example of which currently carries the trade mark CAISiFrit~') and a high carbon material (an example of which currently carries the trade mark CAISiCoke°~), Spent potliners, a calcium oxide source, and a silicate source are fed into a vessel such as an electric melting furnace. The material is heated and melted to destroy cyanides, convErt tluoride salts to calcium fluoride and form a homogeneous liquid material. Carbon is then physically separated from the matEarial in the electric melting furnace and the material is thin vitrified. dptionally, prior to melting, the material is heated in a rotary kiln. Goth the rotary kiln (if present) and the electric melting furnace are linked to a flue gas treatment system. It is to be understood that whsle the following description discusses a rotary kiln, this kiln is optional.
The process consists mainly of physical and timely $eparativn of the different phases necessary to accomplish the desired goal, which is to transform SPL
into an amorphous and non-toxic materiaE. This resultant material in tum may be ground and used as an Alternate Supplementary Cementitious Material (ASCM) being a partial substitute for Portland typo cement, enhancing the desired properties of the concrete.
Alternatively, the resultant material may be used to produce a new mineral binder with properties and a composition different than Portland cemEnt generally in use.
The term "spent potliners" is known in the art. The word "spent" is not intended to limit the expression "spent potliners" to patliners which are completely spent as manufacturers may determine when a potliner should be replaced according to different criteria. Potliners are replaced well before their useful life ends in certain instances, according to plant operations. Other hazardous materials, especially those containing aluminium, calcium, or silicon can be treated according to the present process, such as catalysts from petroleum refineries, polycyclic aromatic hydrocarbons, contaminated refractories, water purifying mulls, and carbon anodes from aluminium smelters.
The term "electric melting furnace" means a furnace in which an electric current is applied to the material via electrodes by using the electrical resistivity of the material, to melt the material.
The apparatus according to the present invention will now be described with reference to Figure 1. SPt_, energy and additives are fed into a long body rotary kiln (101 ) at a non-burner end thereof (i.e. at the right hand side in Figure 1 }
(or directly into an electric melting furnace). The material passes through the kiln to an electric melting furnace {103) and to a quench basin (105). Gas and water treatment systems are integrated with the apparatus as detailed below.
Referring to Figure 2 far a generat description of the process, SPL (201), energy (203), and additives (205) are added to the Tong body rotary kiln (207) or directly into the electric melting furnace where heating occurs. Gases are treated by a gas treatment system (208) and treated gases are discharged through a chimney (211 ), At the exit of the kiln, the material falls into an electric melting furance {209) where the high carbon material (217) is separated and the remaining material passes to a quench basin (213) where it is vitrified info a glass frit (218). Where the kiln is not used, the material is both heated and melted in the electric meking furnace. A
portion of the water from the quench basin (213) is fed to the gas treatment system (208) and the balance is fed to the cooling Circuit (214) and water treatment system (215), where it is cooled and returned to the quench basin (213). Since the process consumes water, make-up water (216) is added.
A process flow chart is provided in Figure 3. The feed comprising SPL and additives is combined and heated (301). The feed is further heated, melted and optionally retained at a high temperature to enhance matrix formation (302}.
Carbon is physically separated from the material (303). The material is vitrified to produce a glass frit (305). The process is described in greater detail below.
A) Crushing and preparation of the mixture: (i) The SILL is crushed to a dimension of 1p mm or less or, on average, 6 mm, and continuously sampled during stockpiling. 9n an integrated system. sampling takes place during silo filling so that a computer has the information at all times of which material corresponds to which analysis, As an example, eight silos can simultaneously be used to correctly homogenize the SPL destined to feed the furnace. Stockpiling inside a specially designed silo comprising Sir Intake and filtering ventilation is presently preferred over large reclaiming stockpiles due to the reactivity of the material with moisture in the air.
Homogenizing in vented silos allows for the explosive gases to be vented without unduly exposing the material to water or moisture-laden atmosphere. Sampling and chemically analyzing the SPL permits controlled preparation of the feed. (it) The crushed SPL is quarantined awaiting analysis. (iii) After receipt of the chemical composition data of the SPL, additives and reagents are added during its feeding accordingly to the analysis. The quantities of additives and reagents are determined by a software program to provide a consistent feedstock. Alumina bearing material such as recycled material may optionally be added tn the SpL to present a totat A!
content of about 9 to 19% of the total feed, 93.5% if such an end product chemistry is desired. tn one embodiment, alumina is not added. Alternatively, SPt_ is crushed after been mixed to form the recipe. Enough calcium (such as in the form of calcium hydroxide, GaCO~.
limestone, calcium oxide (or quicklime), hydrated lime, possibly dolomite, and calcium containing waste) is added to complete the following simplified reaction:
CaGO, + 2 Nat= -~ CaFZ + Na,O + COz Additional Calcium is added over the above stochiometric reaction amount for a ratio CaO/gfass frit of between about 0.0? to 0,12, preferably about 0.07.
Sufficient silica is added according to the sodium of the SPL to offer a final Na20ISiO;
ratio of about A.1~ to 0.36, preferably about of 0.26 in the glass frit.
!n one embodiment, the recipe contains at feast sufficient calcium oxide, hydroxide or carbonate to allow for the stolchiometric transposition of the fluorine from a sodium attachment to a stable calcium attachment. The rECipe may else contain sufficient silica to form a sitioa matrix comprising the components of SPL
other than the carbon, which wilt be separated and recuperated during the process. Other additional elements such as alumina can be part of ths3 feed recipe in order to attain a particular end product chemistry. Alumina may be added to satiate the melted material about its chemical balance therefore preventing it from looking for this material and finding it in the refractories, A different refractory material could alternatively or additionally be _12_ used if resistant to such attack and having the physical resistance to endure the kinetics experienced in the rotary kiln. The process and the chemical balance of the recipe are used to ensure that fluorine will stay tightly bound into the new material composition.
It is possible to use as such additional elements and materials already considered residuals, either hazardous or not, because of the oxidation that will occur at high temperatures at a later stage during the process.
B) Feeding the furnace: Such feeding may be continuous. The furnace may be a long body rotary furnace (t.BRF) or kiln. The furnace may be lined with refractory material, The material progresses from upstream to downstream and is heated.
~'he feedstock i5 fed to the furnace by rate controlled conveyors andlor a chute.
When the kiln is not present, the feed is fed into the electric melting furnace, Feed is dispersed continuously aver a feeding portion of the melted bath arid dissolution of the solids into the silica matrix promotes the chemical reactions necessary to the integration of alt the different materials at the exception of the carbonaceous portion into the silica matrix. Thickness of the unmetted feed may be kept below 300 mm and in one embodiment, between 75 and 200 mm, in order to prevent crusting of the feEd which behaviour would cause separation of the unmelted feed from the molten surface and therefore reduce the dissolution rate of the feed material whilst requiring a higher operating temperature of the bath, This unmolten layer of solid feed particles acts as a filter condensing the evaporated fluorides, The solids have a tendency to agglomerate together and float. The molten bath is gradually mixed and leached by the hat liquid bath due to the action of gases introduced at the bdttam of the basin. Oxygen is a preferred gas for use in these bubblers as it heats the floating mass consecutively to the combustion of a portion of the contained carbon. The decarbonatian of the limestone contained into the feed recipe also helps the dislocation of the floating mass and therefore its dissolution. Air or other gases may be used although thtese are lass effective in the combustion of the carbonaceous top layer.
A second method used to improve dissolution of the solid feed in the hat bath consists of a modified fend system wham the solid feed material is pushed or rammed over the molten bath with the help of a piston or a screw feeder. Adding new matErial -'I3-results into pushing and tumbling previous#y fed material deeper in the furnace. Gas bubblers will help in promote a good mixing Of the solids into the molten bath.
C) Operation of the long body rotating furnace {LBRF}, if present, the electric melting furnace and the quench basin: (i) The LBtaF has a diameter of between 2.5 and 4.5 meters (3.0 in one embodiment) and a length of at least 20 m. It should be understood that while specific dimensions or shapes may be described or shown titrOUghput this description, these are intended to be illustrative and not limiting.
tnirared temperature detectors are disposed along its entire length to measure the exterior temperature of the furnace and, consequently, the temperature variations in the furnace. Once control is established, it may be sufficient to monitor the cold end temperature of the process gases and the temperature of the exiting material.
{ii) The material is progressively heated, starting from ambient, as it moves within the kiln. The heat source is downstream, making the process counter-current. Figure i shows the various phases through which the material passes. zone 9 (~t009) is the cold zone where material enters the kiln. Zone 2 ('1002) is where the material is heated to between 450°C and 850°C, in one embodiment 700°G to 850°C, The L~RF may be etluipped with appropriate dams to promote a retention time of between one and two and a half hours in order to permit sufl5clent chemical transfer of the fluorine to the calcium based material.
The length of the kitn shoutd be sufficient to allow a proper inner shell temperature profile in order to condensate or attach the fluorine arid fluorides, either in their gaseous or particulate forms, to the refractory and to the advancing material. The kiln should have a diameter 8u~cient to allow for a reduced er,trainment of the lighter partiGes outside the kiln area. A slope limited to 3.5% may allow far sufficient retention time.
The rotary action of the kiln causes a tumbling and rolling action of the feed recipe material as it advances down the kiln. This promotes a desired close contact between the fluorine corEtaining material with the calcium containing material thus favorizing the desired chemical reaction. This action also erodes build-up of sticky fluorides into the rotary kiln as some of the fluorine comes from evaporation in the secondfurnace.
The hot but still solid unmelted material is discharged from the rotary kiln, following the continual advance induced by the rotation of the inclined kiln, into the electric molting furnace. Initial loading of the electric melting furnace may require the use of flame burners to liquify a load of broken glass or a load of previous production material until sufficient conductivity is reached to permit electrical heating through inner resistivity to elmctric current. Leaving the LBRF, the still solid and granular material enters the electric melting furnace where it is heated and melted and to at least 900°C
and not aver 1250°C, in one embodiment 1p25°C to 1150"C before being discharged and quenched. The aforementioned temperature ranges represent a large portion of the material and, in practice, certain portions of the material may achieve temperatures outside these ranges, fn Zone 3 (1003), solid material slowly melts while undergoing chemical reactions. The material becomes liquid and final chemical liaison are taking place. Gas bubblers may be used to cause advancement of the materialralong the electric melting furnace as otherwise floating carbon mixed with unmelted material may bfock the operation of the furnace. In one embodiment, oxygen bubbling is used as it not only induces the advancement of material but also burns same of the floating carbon and therefore prevents the carbon from insulating a frozen crust above the liquid bath. The liquid silica matrix carrying over itself a layer of floating Carbon granules slowly advances towards the exiting spouts where the carbon Is blown into cooling recovery conveyors by jet burners or removed with mechanical screws at a dam station, The liquid is then free to flow under the dam and be directed to a quench basin where, under quick cooling action, the molten silica matrix retains Its energy level into an amorphous state. The feed material, in the LBRF, is generally kept from melting ar becoming tea sticky which would hinder the operation of the kiln.
Separation of carbon also takes place in this electric melting furnace. The electric melting furnace should effectively separate carbon from the matrix, Carbon separation from the molten siliceous matrix may be effected by gravity and may be enhanced by properly positioned gas bubblers, Also, gravity carbon separators may be present consisting mainly of channels equipped with floating material retaining dams and raised spouts ensuring the glass molten level is kept at ail time over the retaining dams tower level.
The retaining dams are located in such places as to permit the timely removal of the retained floating material being the carbon separated by gravity from the liquid bath.
Removal of the floating rt'~ateriat may be effected, for instance, by blowing it down exiting chutes with the help of hat gases or by mechanical devices such as piston rams ar retrieving screws. The first method is preferred as it does not necessitate mechanical moving parts to be exposed to high temperatures during any Length of time, The mo#ten siliceous matrix flowing under the retaining dams wilt exit the furnace at the spouts when its #evet in the furnace permits, In place of a rotary ki#n, another vessel could be used for heating the solid material. In pace of the Qlectric melting furnace, another vessel could be used, especially a vessel that permits the use of fragile refractories. done 4 (1p04) represents the quench basin. {iii) #ncreasing temperature favours the breaking of certain existing Chemical bonds, and the creation of the bands which define new compositions. Thls causes the destruction of cyanides by oxidation, and the capture of fluorides which pass from a sodium bond to a calcium bond. The primary reactions are as fotlpws:
2CN + 20z -~ 2CQ, ~ N.
CaCO~ -> Ga0 * COz 2NaF * Ca0 -~ CaFz * Na2Q
2A#F~ + 3Ca0 -~ 3CaFz + AI,Oa (iv) The material, which at the entrance of the LBRF was composed heterogeneously of solid materials, becomes a homogeneous #Iquid composition in done 3 (1003) and the matrix is farmed. The following reactions occur:
wCaF: + xSiOz * yNazO + zAizO;, * --~ matrix of fluoraluminv silicate of calcium and sodium, where x, y and a rnay be 0.7 to i.46 and where x may be 1.5 to 3.6; and C + Oz -~ COz D) Vitrification of siliceous matrix: {i) The use of the electric melting furnace prolongs the time of retention at high temperature, thereby ensuring the complete formation of ~ complex matrix of fturoatum#nosilicate of sodium and calcium.
The electric melting furnace also permits the gravitational separation of carbon, and, by raking it or blowing it out, the production of a matrix with very little carbon. The carbon floating on the matrix is recovered instead of being burnt as in certain other processes, This high carbon material witl have a carbon content as high as most metallurgical cakes sound on the market. Chemically, it will consist of a pyrametallurgical coke containing greater than 80 percent carbon. In the #ess than 20 percent of ashes, 2 to 4 percent will be G2tcium fluoride, a level which presents a marked advantage with respect to the fluidization and the lowering of eutectic points of c#inkers and of metallurgical stags. The recovery of residual carbon in this process will increase the global co-efficient of recycling of the spent pottiners and wilt reduce as much the greenhouse gas effect by tonne of spent patliners used. (iii) The glass liquid thus extracted is quickly immersed in water to rapidly reduce the temperature and to conserve its amorphous character. (iv) The resulting glass frit is dried and ground. -the glass frit is preferably ground to a Stains value of from about 2040 to 8000cm21g and more preferably about 4p00 to 6000 cm'!g. The glass frit in matrix form wilt be composed of (CaF2 5-35°l° or preferably 10-25°/a), SEOZ
{30-60% or preferably 35-45%), NaZO (5-2 or preferably 10-15°~) and AfZO~ (10-25%). Smaller amounts of Ca0 (3-12%) and Fe~Oa (1-3°!°) wits atso be present. Less than 1°~ carbon will be present. The ratio of glass frit to SPt- is about 1.4 or 1,55.
E) Treatment of gases: t-'figure 4 illustrates the gas circuit. (t) In order to capture all the gases generated during the production of the glass frit the LBRF (403) and the electric melting furnace (401 ) are connected by a mobile head of high temperature type. The mobile head may have an estimated temperature of approximately 600°C.
The LBRF burner is shown as (402) white the burner of the electric melting furnace is spawn as (41.2)_ This assures a seated system, which, under negative pressure, directs all the gases of combustion and gases of production (decomposition of carbonates and ferrocyanides, etc,) to an after-burner and purging system (404), before their emission to the chimney {410). {ii) A first purging takes place in the relaxation chamber (4U3a) of the furnace, through the vertical exit of gases to a high temperature cyclone (not spawn). This avoids massive entrainment of dust downstream. The cyclone is not necessary. Once separated from the flux gas, the dust is re-fed to the LBRF
via a solid feed circuit (discussed below with respect to Figure 5)_ {iii) The temperature #n the after-burner system is raised to about 775-950"C, preferably 875°C to Combust CO, and eliminate hazardous air pollutants such as polycyclic aromatic hydrocarbons, {iv) The gases are then Coated to a temperature compatible with the filter bags (407). This also neutralizes acid gases to be further polished in a dry reactor {406). (v) The dry reactor (406) Eliminates, by injection of calcium hydroxide, HF and other acids, which may be found in the gas stemming from the after-burner (411), if the detection system signals the presence of fluorine gases to the chimney, the dry reactor (40G) automatically increases the inJectian of calcium hydroxide in order to assure the quality _17_ of the emissions into the atmosphere. (vi) The filter bags (407) capture the solid dust coming from the dry reactor (40G}. The presence of an adequate cake on the filtering sleeves helps to assure that the acidic molecules are absorbed by the Ga(OH)~
and, therefore, plays a role similar of that of the dry reactor (~iOG). A further burner (412) is present far the fixed-bed furnace (401 ). Combustion of natural gas andlvr other combustibles occurs at (A13), Continuous natural gas measurement occurs at (414).
Other combustibles, liquid or solid, can be used with the kiln burner. Natural gas is preferred at the after-burner to ensure complete burning of all elements which is the purpose of the after-burner. A post combustion chamber (405} is also provided.
F) Verification of atmospheric emissions: Figure 4 illustrates the gas circuit. (i) After littering, the gases are directed to the chimney (a10). Continuous measurement of the atmospheric emissions: HF. C4, Ct~~, O~. SO~, NQX and opacity are pertormed in the analysis and sampling atmospheric station (409).
G) Treatment of dust and returns: Figure 5 illustrates the solid circuit. {ij Att dust coming tram the gas treatment is returned into the solid feed and re-injected into the furnace. Feed debris, quench-water treatment mud and the like such as spent kiln refractories are also recycled back into the process. The crushed SPL comes from SPL
container (50i) via a hopper {502) and conveyor (503j although conveyors are not necessary. Alternatively and more presently preferred is to crush the SPL and homogenize it into the bank of silos. Additive silos (504) hold the additives.
Recipe hopper (505) and furnace hopper (508) are used for feeding. Feed debris (507), post combustion and conditioning recycles (508), and recycles Pram filter bags (609) are re-fed into the furnace hopper (508). Also shown are the LBRF (510), LBRF burner (511}, electric melting furnace {512), high carbon material container (513), glass frit quench basin (51~4), automatic glass frit sampler (515}, and the glass frit {516).
H) Water treatment: Figure 5 illustrates the watQr circuit, (i) Lime is added to the treatment water to prevent its acidification. The water is then cooled before being recycled back to the quench basin. (ii) A portion of the water feeds the conditioning tower of the after-burner. Water cooling is done through evaporation. Overall, the process consumes water and, therefore, there is no waste water expelled.
Referring to Figure 6, glass frit (fi09) is shown coming from quench basin (601}. Water from quench basin (601 ) fIpWS through holding basin (603) and pump basin (ti04) and thert~fore a portion is added to the conditioning arid post-combustion tower (605) and the balance _-ig_ is fed to cold water treatment basin (608) from which water evaporates (606).
Additional water (607) is added to the water basin (60s). Waste water is collected in catch basin (602) and using eonection basin pump (610) is pumped to holding basin (603). Water basin pump (619 ) is used to pump water to the quench basin (601 ).
Temperature orafile in the kiln ~'he material temperature at the feed end is approximately ambient. It is estimated that at 8 meters inside the hot kiln zone, the material temperature wilt be approximately 7d0°G. The material exit temperature will depend on the length of the kiln, kiln shape, retention time and ether factors. it is estimated that the temperature of the exiting gases wilt be approximately 225°C. The material temperature along the kiln can be controlled by increasing or decreasing the amount of fuel used by the front burner. Additional correction involving the varying of the flame type from axial to radial is done after observing the location and state art the annulus at approximately ten to twelve meters from the burner end.
In relation to the feed rate, the gas temperature at the burner end of the kiln and the flow rate at the feed end of the kiln will indicate whether the profile is being raised or tooted. This would be confirmed by the shell temperatures being measured continuously at, far instance, 20 sections, which trends will indicate in which direction the process i5 proceeding. These shell readings would be affected by the external temperature, wind, rain etc. and therefore would be useful In a relative way to indicate a trend not absolute values, The shell temperature readings would also be affected by the thickness and state of the refractory lining augmented by the thickness of present accretions, As discussed above, measurement along the shell can help but is not necessary.
If the profile is not controlled, the accretions inside the kiln will get rapidly to a paint where you cannot feed more material. To remove these accretions, the operation is stopped to enter the kiln to physically break away the accretion with jack-hammers.
Radial CQ~ blasting, axial gun shooting and superheating have proved themselves quite ineff~ctive ways to removeleontrol the accretions.
KinetiC9 _ ~[ ~ _ Gounter current kiln favors preheating of feed material and cooling of gas.
The temperature inside the kiln is contrnlied by adjusting the ventilator (408) (see Figure 4) situated before the escape chimney and the energy input by the primary burner.
The use of a LBRF (long body rotary kith) in a coup#er-current set-up permits operators to properly, dynamically and relatively Slowly raise the temperature of the material as it ntoves down the kiln towards the hot zone. The rotation of the kiln ensures an intimate contact between the different materiais. The rotation also promotes rubbing of the different compositions one against the other in an eroding action.
Thermodynamic simulations have shown the necessity to minimize the amount of H,Ca vapor inside the furnaces to prevent the reaction 2 NaF + W?t~ ~ NazO + ~ HF
The simulalians also showed the desireabitity to finalize the process at less than 1200°C to reduce the vapor pressure of NaF and therefore the creation of NF due to the water vapor created by the combustion of natural gas.
CHa * 02 -~ COr + 2Hz0 The pros~ss of the present invention employs these thermodynamic features.
The process of the present invention thus differs from the others which heat rapidly the SPk. and provoke the creation of MF.
Auxiliary Feed Mat rial tn one embodiment, an auxiliary feed material is used to increase the produc#ion of the kiln and to improve cement proper#ies. The counter-current t.RRF has its cold zone at the feed section (upper section). Material is added in the hoi zone right into the molten basin in the lower section of the kiln. This material is injected into the kiln at 6(t feeilsec to reach 4 to 6 metres into the kiln. The added material then has time to melt and partially or totally mix with the glass matrix. Up to about 7 tans per hour is expected to be able to be added in this manner therefore greatly increasing the kiln output.
The injection info the hot zone of the kiln is also done because the material being injected is broken glass (culiet) which would negatively affec# the melting (and chemical reactions) of the recipe if it was fed intp the kiln in the cold upper zone, Culiet is presently preferred but others materials could be used.
These additions modify the structural liaison between the different components of the glass matrix which in turn affect the reactivity of the amorphous produced glass and thus, its cementitious properties. Lowering the ratios of Ca:glass frit and Al:glass frit reduces its susceptibility to sulfate and carbonate attacks rendering the concretes made out of the glass frit more durable, These additions resort in a product offering some of the praperties actually brought to concretes by silica fumes.
The glass frit can make conGretes at high temperatures without reactions creating deleterious ettringite, High temperature reduces strengthening time required by concretes therefore increasing the turn-over capability of concrete pre-lab plants. An activator is used to turn the glass frit into a high performance binder for the manufacture of resistant and durable cements (an example of which currently carries the trade mark CAISiBinderHP°~, data from the following three sections (Mass Balance, The Class Frit, and The High Carbon Material) relate to an embodiment described in CA 2005/000199. It is estimated that; the Carbon consumption of the process described herein would ba of the order of 15 to 30%; the quantity of glass frit will be about the same; and about 70 to 85°!0 of carbon wiA be recovered in the form of the high carbon material.
Mass Balance A study of the mass balance of this process during the recycling of 1000 metric tonnes of spent potliners revealed the following: a #luorine mass balance of 99.26°I°
(the loss of fluorine by atmospheric emission represents only 0.003°~6 of the total mass of fluorine fed in the form of potliner, a Ct7Z mass balance of 99.02% (or 100°/o taking into account the admissible tolerance of the various instruments of measurement), a solid mass bal2nce of 99.4/0 (or i 00°/, taking into account the admissible tolerance of the various instruments of measurement). The fluorine mass balance confirms that fluorine is not lost somewhere in the process. The quantity of carbon feed as pottiner was measured as 324,99 : 2.03 metric tonnes and the carbon found in the glass frit and high carbon material respectively was 126.30 ~ 0.51 and 102.12 ~~$.i7 metric tonnes indicating that the quantity of carbon consumed during the process in the kiln and found as carbon dioxide gas in the chimney is 96,573 8.43 metric tonnes.
Only 0.84 tonnes of C02 are produced per tonne of potliner which favourably compares to 1.19 tonnes in another known process, The Glass Frit The glass frit is an amorphous sifiaea~s material forming a calcium and sodium fluoraaluminosilicate matrix, This homogenous solid substance possesses a high reactivity potential and shows superior cementitious properties when finely ground. The glass frii once quenched Is finely ground into a powder, of, for instance 410 m~lkg.
f=igure 7 is an X-ray diffraction analysis of the glass frit shows that the amorphous character of character of the glass frit, Although a J6% amorphous character is desired, at least 98%, is preferrEd, and at least 99°/° more preferred. Table 3 stows a chemical composition of the glass frit using one specific measurement. The values shown under the "normal" heading are the limits over which the material is dEClared a "Hazardous Material". TCLh is the standard practice defining the method to analyse lixiviation using an acidic madium.
ParameteE Normal Result Total Analysis AI, % , 12.0 Ca, jo "~""""~.~"'._-..._.__._................~2.1...~

., - Mg; __.__..._.g.~ ._.
~o ...

.~.....__._._...' ,.
._..__.._ ~e, 1.6 .o! .._~

K, / 1.55 -. .

F total, ... . 6.2......_.
ojo ~.......
~

...............__..........."w.,,",~
Na, % ,~~10.2 ixiviatfCn TCLP

As c 5 ~ a.(71 mgll ~3a < 100 0.38 mgll .___.._~~____~ app ~.~9 _..... m911 _..

Cd ~ c 0.5 mgll, t),3a _....__. Cr_........~_...~ 5.0 mgl! ~~~....Ø02 ~ p.~...~~1~_ ._ ~ 0.000 ,.. ...-._.P~ .. y 5_0 mg/f ..,_..._3.3 _..
~......Se .~ 1 1.Oryt~gll .-~t 0.01 .._..._.__.._ ~ ....._...... .~ ~ ~.0 mgll ..... .. ~ 0.00'.
< 150 mgll f 14.
< 100 ma/~< ~Lln The glass frit is useful a5 a cementitious addition and hydraulic binder. When used as a cement enhancer, it has been demonstrated by a report prepared by the University of Sherbrooke that the glass frit improvEs the flawabifity of the blended concretes. This rheoiogy allows for a reduction of the water to binder (WIB) ratio.
Besides reducing the chemical admixture dosage requirements (especially in water reducer and superptaticizers), this improved rheotogy permits a reduction of the binder content without sacrificing either the workability or the physical properties of the concretes. The glass trit is a chloride-ion permeability reducer that enhances the durability of concrete. Figure 8 shows the results of chlorine ion permeability tests carried out after 91 days of curing in 100% RM and at a temperature of 23fi2°C, water to binder ratio (V11/B) of 0.35, according to AS'f'M 01202 standard. The cements of Figure 8 are defined as fotlows~ Control is 10D% Portland cement. Binary is 75%
Portland cement and 25°~ blast furnace slag. 8insry CF is 7590 porttand cement and 25°k glass frit. Ternary is 'T5% Portland cement, 20°/0 of the glass flit, and 5°!° silica fume. Quatlf=A is 50% Portland cement, 25°Io of the glass frit, 5°~ silica fume, and 20%
fiyash. Quatlsfag is 40% Portland cement, 25% of the glass frit, 5% silica fume, and 30°/a SEag.
t=figure 8 shows that the permeability of concrete to chloride-ion decreases by more than 50°!° when using 25% of the glass frit as a F~ortiand cement substitute. 20%-30% is presently preferred. Figure 8 shawl that using the glass frif is a quaternary mixture resulted in a permeability reduction to 1115'" the level of a control concrEte using a cement made of 100°/o Portland Type 10. Concrete's resistance to chlorine-ion attack is one of the most important factors to consider when determining its durability.

This is precisely wherQ The glass frit excels as an additive. Due to its discontinuous pore network, it ensures better resistance to salt, acid and water attack.
figure 9 shows the expansion obtained on Concrete prisms of 75 x 75 x 300 mm cured for longer than two years in 100% RH and at a temperature of 38°C, aCCording to CSA A23.2-14A standard. Replacing 25% of the cement with the glass frit reduced expansion. Following standardized curing for 853 days, the expansion noted in concrete using 100°!o Portland Cement was 0.23°!0; while it was 0.13°i6 with cement containing 25% of the glass frit. To evaluate a material's effectiveness in controlling alkali-aggregate reaction, article 6 of CSA standard A23,2~29A stipulates a limit to the expansion of concrete containing additives to 0.04% after two years of toting.
The analysis of the graph allows us to conclude that although The glass hit did not meet the standard, its expansion is still far less than that caused by commercial Portland Type cement. However, even though the glass frit has a significant alkali content, when used in concentrations above 90%, it meets CAS norm A23, 2-28A article 8.
The glass frit, being more than 99.f3% amorphous, boasts strong binding potential a:; a cement. When ground to 4001) Elaine and when combined with an alkaline activator at hydration, it becomes an effective hydraulic binder enabling its use in RPC-type concretes. As shvwri by American laboratory F.L, Smidth, pulverization of the glass frit to 4000 Bla;ne rectuired less energy than that of clinker or slag.
Resistance and other mechanical characteristics of concrete are improved when the glass frit is used. All tests performed to date by the University of Sherbrooke and St. Lawrence Cement corroborate this_ More specifically, compressive, tensile and flexile strengths of blended concrete are improved, as is durability. By substituting, as the principle durability agent. 209'° of the glass frit for Portland cement used in the preparation of general use concretes. not only are the tensile, flexite and compressive strengths increased, their permeability is also greatly reduced. 'their workability is improved whilE smaller quantities of Theology enhancing agents are needed_ The paleness of finely ground glass frit is another quality. 'this is especially true when the aesthetics of a finished product is perceived as a component of its quality and durability. The glass frit also shows potential as an element in the formulation of reactive powder concrete.
The glass frit allows for the reduction of greenhouse gas emissions (GHG).
When used as a substitute of clinker in the manufacture of cement, it generates a credit equivalent to 450 kgslmt of replaced Portland. This GHG credit reaches kglmt of substituted Portland when cullet is added to the silica matrix. Thus is a more environmentally friendly and valuablQ material within a sustainable development framework. On an environmental and sustainable development level, the addition of The glass frit to cement is particularly beneficial. It eliminates an environmental risk for the aluminium smelters by transforming a haxardaus waste into a commercially viable product. There will no longer be a need to landfill spent pot-liners, thus the major environmen#al benefit of this process. There are mayor socia-ecological benefits in the reclamation of restdua# hazardous materials into commercial products by the use of a clean, residue-less recycling process.
Another use of the glass frit is fn a composition with Potland cement, blast furnace slag, silica fume and quartz. In one embodiment, the tampositian comprises, by weight, 30-50°r6 Portland cement, 0-10% blast furnace slag, 5-95%
Silica fume, 0-10°!° quartz, and 35-65°/o vitrified material. Such a composition may be used as a cementitious composition to providE a high strength material, and may provide a material with a strength pf about of at least 200 MPa.
The high carbon material In one such composition, the weight percentages are as fvl#ows:
Another product of the glass frit process is a high carbon material or cake (an example of which currently carries the trade mark CAISiCoke~'. The high carbon material has a carlavn content as high as most pyromQtallurgical cokes found on the market. Minor metal oxides contained give the material additional metallurgical properties sought by cement and metallurgical industries. Primary users of the high carbon material may be cement and sleet makers, who require coke to supply energy, ar as a means of reducing oxides and recarbonising steel. Alurnina may be added to satiate the melted material about its chemical balance therefore preventing it from looking for this material and finding it in the refractories. A different refractory material could alternatively ar additions#ly be used if resistant to such attack and having the physical resistance to endure the kinetics experienced in the rotary kiln.
Table 4 shows the chemical composition of the high carbon materia#, ~~ -Parameter Units Results ..._. _., ......._............. . ..__.._.__..._ .. ...

....._._.Ca~n~ g0.1 .,_._.~~..u~~hur.....% _ ~
~
"

. l0 1.5 Ca tuts) ... Gd % ...._.....~,~.01......_ total P total .... ~N ...~~~~....._.__~.3 totaj ...._ _-..
..._ .

F % 2.9 'uorine ~
total Pb total % 0.01 ~

Fe tots! %",. ._......_0.4 ,.

.._...~g ~ % -i0.05 total -Na total -.~/~ ~4 -..._._ -VV ...
$i tats! %w 1.5 ~~ AI total% ~ 3.3T~~

I_IX1VIATiON

TC(_P

As mgll ~p, ~

____._ .- -...
_~_........_.___mg~l 19.2 -;

.-._ ... ,..
...._.....__....._, Ba ~~~i ~
~.~

.._._~ --~9'~-0.01 ~d ~._.._..

......................Cr_-...__.__ ma/t..._._....~.04 _....

_.....__._._mgll ._.,c H~ . O.b03 .....

...........__.....mg/I74.6 Pb ....-~~~~....~...~.02 ... _ ..._.__ ~~~~.:_...~
Se ...._.__... 0,1 Possible advantages of embodiments of the present invention especially those embodiments in which the kiln is present include;
(a) Reduced refractar~~ wear in the rotary kiln The explanation lies in the energy level of the aggressive elements or compounds, mainly Na and F, found in the recipe. The higher the temperature, the higher the energy level and therefore the higher the chemical activity of such an element or compaurtd over a neighbouring one, albeit refractory material.

(b) f~educed operational control difficylku~~ of the kiln temperature arid re UCEd C!(X7qinc~
This is explained by the tact that the components are kept in a solid state instead of a mushy or even a liquid state. It is much simpler to operate a long body rotary kiln in a dry solid state than trying to keep the equilibrium among;
(i) too hot a molten basin (overheating the molten glass and refractories so that the former is more prone to cnemlcally attack the latter);
(ii) too Tong a molten basin (letting the molten bath limit rEach way up the kiln towards the cold zone) generally due to more induced draft than necessary and therefore a displaced tEmperature profile along the kiln. This would result in an upstream ring damming tf~e flew of material and reducing the effective slope of the kiln.
The slope and rotating speed along with the diameter of the kiln is a governing parameter of the kiln capacity. Such a build-up can be very difficult to dislodge, melt or break away when located far up in the kiln; and (iii) too cold (felting the discharging material become mushy and sticky) resulting in a massive build-up of sticky material aver the kiln lip, thus obligating the manual removal of it.
c) Redt.~,ced oneratinc~ temraerature of the kiln mobile head AS the discharging material is kept dry and solid, the lip of the rotary kiln does not need to be heated to prevent the build-up of an excessive rang from sticky cooling glass. This affects the temperature of the mobile hood which, in a rotary kiln, is always critical due to distortion and false air intake. If the malaria! is kept solid in the kiln, there is na need to over-heat the gas kiln outlet in the mobile head;
d) Prevgnted build-ups and related rxoblem at kiln lip (exit), As explained in b).
e) R~,duced flue,- aas pr,.aduction an,~ therefore entrainment of fines in aas stream eguinment Feed material {granular and f<nes) must traverse kiln exiling gases when entering the kiln. The higher the velocity of the exiting gases, the higher the quantity of fines that will be entrained wish them.
t -27~

f) Reduced oas speed inside kiln therefore promoting chemical reaction The reduced speed is caused by the reduced amount of gas needing to be burnt in the kiln- The energy needed is the multiplication of the quantity of material by the energy rise needed, Rurthermore, the temperature of the process gases being lower, the actual volume of the gas is smaller according to the law PV=nRT.
g) Reduced flue~c ases volume decreasing enerc~V cost for environmental prpteCtidn As explained in f), h) Possibility to completelXautomati~,~",he oraeratiQn a), b) and d): the modified process removes the difficulties of passing frpm the solid to the liquid state which difficulties (rings, length of liquid basin, sticking to the lip etc.) prevent the operation from being automized, The above-described embodiments of the present invention are intended to be examples only. Alterations, modifications and variations may be effected to the particular embodiments by those of skill in the art without departing frorn the scope of the invention, which is defined solely by the claims appended hereto.
-2$-

Claims (29)

CLAIMS:

1. A process comprising the steps of:
combining spent potliner, a calcium oxide source and a silica source and matting the combination to achieve a material temperature of between 900°C and 1250°C to destroy cyanides, convert fluoride salts to calcium fluoride and form a generally homogeneous amorphous liquid material;
physically separating carbon from the material; and vitrifying the material.

2. The process of claim 1, wherein the combination is melted to achieve a material temperature of between 1025°C and 1150°C.

3. The process according to claim 1 or 2, further comprising, prior to the melting step, heating the combination to between 450°C and 850°C
in a rotary kiln.

4. The process according to claim 3, wherein the combination is heated to between 700°C and 850°C in the rotary kiln.

5. The process according to Claim 3 or 4, wherein the material is in a solid state in the rotary kiln.

6. The process according to any one of claims 1 to 5, wherein about $ to about 19% by weight of a total feed is aluminium.

7. The process according to any one of claims 3 to 5, wherein the heating is effected in counter-current fashion.

8. The process according to any one of claims 1 to 7, further comprising, after the melting step, a glass finishing step in which the material is held at a temperature sufficient to enhance matrix formation and to facilitate separation of carbon from the material.

9. The process according to any one of claims 1 to $, wherein the spent potliner is crushed to less than 10 mm.

10. The process according to any one of claims 1 to 9, wherein vitrifying the material is effected by quenching.

11. The process according to any one of claims 1 to 10, wherein a sufficient amount of calcium oxide is used to result in a substantially complete conversion of: GaCO3 and NaF to CaF2, Na2O and CO2, according to:
CaCO3 + 2 NaF .fwdarw. CaF2 + Na2O + CO2.

12. The process according to any one of claims 1 to 11, wherein an amount of calcium oxide is added to achieve a CaO to vitrified material ratio of between about 0.04:1 and about 0.10:1 by weight.

13. The process according to any one of claims 1 to 12, wherein an amount of silica is added to achieve a Na2O;SiO2 ratio in the vitrified material of between about 0.21:1 and about 0.36:1 by weight.

14. The process according to any one of claims 1 to 13, wherein the melting is at a temperature that retains fluorine and carbon.

15. The process according t4 any one of claims 1 to 14, wherein glass is added to a molten portion of the material to increase production and to improve cementitious properties of the vitrified material.

16. The process according to any one of claims 1 to 15, wherein the material, after vitrification, is ground to between about 4000 and about 8000 m3/kg.

17. The process according to any one of claims 1 to 16, wherein the melting occurs in an electric melting furnace.

18. An apparatus comprising: (a) a first vessel for heating and melting a mixture of spent potlinar, silica source and a calcium oxide source, to achieve a material temperature of between 900°C and 1250°C, for destroying cyanides, converting fluoride salts to calcium fluoride, forming a homogeneous liquid material, and for physically separating carbon from the material; and (b) a second vessel for vitrifying the material.

19. The apparatus according to claim 18, wherein the material temperature is between 1025°C and 1150°C.

20. The apparatus according to claim 18 or 19, further comprising a third vessel for heating, prior to heating and melting in the first vessel, the spent potliner, silica source and calcium oxide source to a material temperature of b9tween 450°C and 850°C.

29. The apparatus according to claim 20, wherein the third vessel is a rotary kiln for heating in a counter-current fashion.

22. The apparatus according to claim 21, wherein the material temperature in the rotary kiln is between 700°C and 850°C.

23. The apparatus according to any one of claims 18 to 22, wherein the first vessel is an electric melting furnace.

24. The apparatus according to claim 23, wherein the electric melting furnace is also for holding the material at a temperature sufficient to enhance matrix formation and to facilitate separation of carbon from the material.

25. The apparatus according to any one of claims 18 to 24, wherein the second vessel is a quench basin.

26. A vitrified material made by the process according to any one of claims 1 to 17.

27. A composition comprising:
Portland cement, blast furnace slag, silica fume, quartz, and the vitrified material of claim 26.

28. A composition comprising, by weight, 30-50% Portland cement, 0-10%
blast furnace slag, 5-15% silica fume, 0-10% quartz, and 35-65% vitrified material of claim 26.

29. Use of a generally amorphous solid matrix of calcium and sodium fluoro-aluminosilicate with a carbon content of less than about 1 weight percent and a calcium fluoride content of between about 5 and about 35 weight percent having cementitious properties when finely ground that is produced from spent potliners together with Portland cement, blast furnace slag, silica fume, and quartz as a cementitious composition.