CA2176118A1 - Method for inerting waste by crystallisation - Google Patents

Abstract

A method for inerting residues from the incineration of industrial or household waste or metal hydroxide sludge, whereby the toxic metals contained therein are stabilised and thus immobilised over the long term. The method includes the steps of heating a mixture containing the waste to be processed and one or more nucleating agents containing ferrous compounds in particular. Heating is performed under conditions such that a liquid-phase mixture also known as a molten mixture or melt is obtained, wherein at least 5 % of the Fe¿2?O¿3? oxides are converted into FeO oxides. The method further comprises the steps of controllably cooling the melt to give a solid in which the heavy metals contained in the processed waste are included within crystalline structures, and recovering the resulting solid. The heating step may include a phase of stabilising the mixture at a temperature which enables the complete liquefaction of the mixture to be processed.

Description

~ Wo 95/13116 PCT / FR94 / 01322 21 ~ 6.1 18 .,.

PROCESS OF J ~ AT ~ OF DECXETS BY CRYSTALLIZATION

The present invention relates to an inerting process of waste, making it possible to immobilize in the long term by stabilization, the toxic metals contained in these waste.
By the term "waste" in the context of this request means waste incineration residues industrial or domestic or hydroxide sludge metallic.
Among the wastes likely to be treated in accordance with the process of the invention, therefore, As examples, the slag (or bottom ash) from the incineration of industrial or domestic waste, metal hydroxide sludge.
Usually incineration of waste domestic and industrial products that brutally cooled during the hydraulic quenching leaving the oven, form a polyphase material containing crystals of iron oxides and aluminosilicates embedded in a glassy matrix weakened by extreme thermal variations. The toxic heavy metals, shared between different structures, are then easily mobilized by external agents, natural or induced, and make them potentially dangerous slag from the environment.
The glasses produced during the incineration have often regarded as stable products suitable for immobilize heavy metals in a sustainable manner.
It is important to emphasize that these slag, only "pro parte" glassy and evolving over time, represent a delayed danger. Indeed the baths aluminosilicate produced in incinerators manufacturers undergo very hydraulic quenching detrimental. During this brutal cooling of a WO95 / 13116 PCT ~ 4 / Q1322 -, ~ i ~

polyphase material, generally made up of spinels embedded in a glassy material, differential contractions appear due to the important difference between the expansion coefficients isobaric thermal of the spinels and the glassy phase.
Contracting more on cooling, the glass fracture and / or accumulates stresses whose relaxation is at the origin of a micro-fracturing on the storage site. Thermodynamically unstable, the glass is also mechanically.
As the mass of metals extracted by leaching of the glassy phase is proportional to the surfaces coming into contact with the solution, we can see that these slag (also called bottom ash), can get to be percolated to heart in durations of a few years, very short durations compared to the unit of time geological: the million years.
In order to ensure both legal compliance and the long-term safety of these clinkers, a solution consists in immobilizing these harmful elements in crystal clear buildings, stable over time geological.
The crystalline phase behaves differently from behavior of the glassy phase on leaching. In effect, crystal is an organization of matter much more stable than glass of the same composition.
Also the destruction of one or more species mineral crystallized from rocks by dissolution, oxidation and hydrolysis combined is excessively slow and operated on a million-year scale. Metals harmful that they contain, released at the same rate, are therefore practically harmless to our environment.
A recourse has also been proposed vitrification. A first way is through realization a high temperature glass (4000 to 5000-C), using of a plasma torch, by modifying very little the ~ woss / 13116 PCT ~ R941Q1322 chemical composition of the original product. A second way requires the synthesis of an alkaline borosilicate glass, insoluble, in which the waste is dispersed. This process considerably changes the content of the initial product.
No other slag treatment solution from the incineration of industrial waste or household waste, does not seem to have been proposed. The bottom ash stabilization treatment by recrystallization changes the chemistry very little;
waste and in particular the slag it contains, and brings very little additional material allowing the transformation of a waste into a material neighbor of a natural material.
To provide a solution to the storage problem harmful industrial or domestic waste, inventors of the present application therefore propose to transform this waste into a material with the properties of natural rocks with regard to their crystal structure.
To this end, a process has been developed which consists, depending on the structures and compositions waste, directing the migration of metals they contain glassy material to the phases growing crystallized.
The method according to the invention for the treatment of waste is according to a first embodiment, characterized in that it comprises the following stages:
- heating a mixture comprising the waste to process and one or more nucleating agents containing in particular ferrous compounds, said heating being carried out under conditions such that it allows obtaining a liquid phase mixture also called melting mixture or "melt", of which at least 5% of the oxides Fe203 are mainly transformed into FeO oxides;
- controlled cooling of the melt to obtaining a solid material in which the metals WO95 / 13116 pcTn ~ 4lol322 -heavy content in treated waste is stabilized within crystalline structures containing crystals from the spinel family;
- recovery of the solid material obtained.
The purpose of the process thus characterized is to allow initially the complete liquefaction of waste to be treated and, secondly, the inclusion during controlled cooling, contained metals in waste, within crystal structures d ~ veloppant as the solidification of the * usion mixture during its cooling. In in other words, mastering the gradual decrease of the temperature during cooling of the "melt"
helps control the germination process of crystals formed including heavy metals contained in waste. These crystal structures contain crystals of the spinel family.
Preferably 10% to 80% or more of the oxides Fe2O3 are transformed into FeO oxides.
Advantageously, the method for processing the invention makes it possible to obtain between approximately 20% and approximately 50% or more spinels expressed by weight of the mixture to be heated.
The relative proportions of the waste to be treated and nucleating agents by weight relative to the weight of the mixture to be heated are determined with respect to the chemical composition of the waste to be treated, whether be slag or hydroxide sludge.
To this end, the composition of waste oxides of type SiO2, CaO, Fe2O3, Al2O3, TiO2, MgO is mainly taken into account. The invention may likewise be applied to waste distinguished from previous but whose chemical analysis reveals a kinship with the slag or metal hydroxide sludge for main elements.

~ WO 9S / 13116 r ~ ~ 2 1 7 6 1 1 8 PCTn ~ 94/01322 The method of processing the invention before favor the formation of spinels (AIlBllIX4) and not the unique formation of magnetite (FeO (L) + Fe2O3 (L)), it is it is necessary to favor the reduction of Fe2O3 oxides in particular by providing nucleating agents capable to react preferentially with these Fe2O3 oxides rather than with oxides such as CaO. These nucleating agents are for example iron filings or any composition containing iron in proportion to the weight of the mixture to be heated during the heat treatment, varying from approximately 0.5% to approximately 15%.
When the waste to be treated is sludge hydroxides, the nucleating agents are advantageously slag.
Preferably, inerting of the waste is achieved by complete crystallization of the material under form of structure including metals contained in waste. A crystallization allowing immobilization from 80 to 100%, preferably 90 to 100% of the metals (expressed as a percentage of the weight) contained in the waste already appears satisfactory.
The process described has the advantage of leading to immobilization of metals stably over time on a geological scale (inerting) thus ensuring the safety of the metals contained in the waste.
is called controlled cooling of the mixture of fusion or "melt", a cooling which we control decrease at least until the solidification of the melting mixture. In other words, it is a = progressive cooling, the progression of which is determined to be slow enough.
-The complete solidification of the melting mixture is normally obtained at a temperature between about 1050-C and about 1250-C, preferably between around 1100 and around 1210C.

WO95 / 13116 PCT ~ R9 ~ / 01322 -~ ls ~ ~ 17 ~

It marks the end of crystallization and is considered to have immobilized at least 80% of metals, expressed as a percentage of the weight of treated waste.
Preferably, the cooling will be carried out in such a way so the temperature drop is around from around lC to 10-C per minute at least until crystallization or even until complete solidification of the fusion mixture. Generally up to obtaining this solidification, cooling should be as slow as possible.
Different known cooling techniques can be used. We could for example proceed this cooling in the air.
Another possibility is to use the capacity heat of the melting mixture which in contact with a surface with a lower temperature will undergo a temperature decrease. We can in this hypothesis, knowing the thermal conductivity of the mixture, determine the cooling rate of this mixture and choose the surface temperature in contact with which cooling must take place, to obtain the slow cooling sought.
The heating step referred to above in the treatment method of the invention, must be r ~ made so as to obtain a mixture to'alement liquefied. To do this, we can use a temperature stabilization step when it has reaches its highest level, in order to ensure this complete liquefaction. The stabilization time varies in function of the highest temperature of the stage of heater ; it can for example be of a duration about 1 hour or be adapted according to the amount of waste treated.
According to a first embodiment of the method of the invention, the waste to be treated is slag ~ WO95 / 13116 PCTn ~ 4/01322 '' ~ 61 ~ 8 resulting from the preliminary incineration of waste industrial or domestic.
The average composition of the slag is given in the following examples based on samples of industrial waste. Generally, slag mainly contain mineral matter incombustibles combined in multiple forms oxidized. In particular, slag contains in generally a relatively large proportion of oxides of iron.
These iron oxides are for example in the form of magnetite which belongs to the spinel family, and the object of the invention is in particular to lead to the formation of additional spinels, different from magnetite.
Thus during the heating carried out within the framework of the process of the invention, magnetite and the others solid elements of the slag, are melted and their progressive cooling then leads in particular the substitution of the iron atoms contained in magnetites, by metal atoms contained in waste. The same substitution process can have place with other spinels formed from slag during the treatment according to the invention.
This phenomenon can be favored by the addition to slag from waste, nucleating agents, particular of ferrous compounds, for example iron filings.
For example, the slag to be treated can represent from 100% to 85% estimated by weight, of the mixture reaction subjected to the heating step, the nucleation representing in this case from 0% to about 15%
by weight of the reaction mixture.
According to another embodiment of the invention, the treated waste is hydroxide sludge metallic.

WO95 / 13116 PCT ~ R94 / 01322 ~

The composition of metal hydroxide sludge is also illustrated in the following examples.
In the case of the treatment of hydroxide sludge metal, the process of the invention is advantageously implemented by replacing all or part of the ferrous compounds constituting the agents of nucleation, by slag. In this case, we can have a reaction mixture comprising, expressed as a percentage relative to the weight of the waste to be treated, from 70% ~ 30%
sludge and 30% to 70% slag.
Possibly, a fraction of the slag intervening as nucleating agents promoting the formation of spinels can be replaced by ferrous compounds as described above. So the proportion of ferrous compounds can be about 5 ~ by weight of the mixture to be heated.
The treatment method according to the invention is according to a preferred embodiment, characterized in that the heating stage is carried out under conditions as it allows a) the liquefaction of the magnetite contained in the slag and the release of Fe2O3 oxides, and b) the reduction of the Fe2O3 oxide formed, into FeO oxide by addition of agents such as iron.
Advantageously, the temperature of the mixture heat treatment is increased to approximately at least 1450C preferably up to around 1500-C. This temperature can be adjusted according to the quantity of waste to be treated and its initial composition.
In a preferred embodiment of the invention, ferrous compounds used as nucleating agents are iron.
In another embodiment of the invention, these ferrous compounds are iron filings, preferably in a proportion greater than 0.5% by weight of the mixture to be treated by heating and ~ WO9 ~ / 13116 ~ PCT ~ 4/01322 ~ 6 ~ ia particularly preferred, in a proportion of about 1 ~ by weight of the mixture to be treated.
For example, the waste to be treated according to the process of the invention mainly contain the following oxides in a given proportion as a percentage based on the total weight of the waste:
slag sludge SiO2 26.25 ~ 45.65 1.4 - 2.7 Al2O3 7.43 - 17.98 1 - 3 Fe2O3 14.53 - 34.92 3 - 15 MnO 0.54 - 1.88 0.05 - 0.2 MgO 1.64 - 2.86 0.5 - 1 CaO 6.41 - 10.16 20 - 32 Na2O 2.66 - 10.82 1.5 - 4 K2O 0.56 - 1.61 0.2 - 0.3 Tio2 3.66 - 7.69 0.01 - 0.1 P2O5 0.96 - 2.54 5 - 18 CO2 0.33 - 4.32 5 - 11 S total 0.03 - 2.53 4 - 14 Carrying out the process of the invention can be facilitated when the waste to be treated, whether slag or sludge, are previously mixed with homogeneously with the nucleating agents and in especially with ferrous compounds.
In the case of slag, homogenization can be made from slag having a particle size less than 10 mm or less, preferably less than 2 mm.
Quite interestingly, homogenization could be improved by a porphyrization step of the mixture to be treated for example so as to obtain a particle size less than 10 ~ m.
Other advantages and characteristics of the invention appear in the figures and in the following examples.

W095 / 13116 ~ ~ 17611 ~ PCTn ~ 4101322 Figure 1: 8tructure of a direct spinel of formula Figure 2: Feldspar balance diagram plagioclases Figure 3: Stability diagram of Fe - Fe203 in log function P2 EXAMPLES
I. Slag treatment Il Compositi.on de ~ clinkers A ~ Chemical composition Slag results from the incineration of waste organic They mainly contain non-combustible mineral matter combined under multiple oxidized forms. Depending on the waste incinerated, the contents of oxides and chemical elements vary in the proportions given in table 1 below.

Variation of contents Major elements Oxides Content t%) 8io2 26.25 - 45.65 A1203 7.43 - 17.98 Fe203 14.53 - 34.92 MnO 0.54 - 1.88 MgO 1.64 - 2.86 CaO 6.41 - 10.16 Na20 2.66 - 10.82 K20 0.56 - 1.61 TiO2 3.66 - 7.69 ~ woss / 13116 PCTn ~ 4/01322 ~ 1 ~ 6tl8 P205 0.96 - 2.54 C02 0.33 - 4.32 S total 0.03 - 2.53 Elements traceQ

Content Elements ~ ppm) B ~ 8800 - 11500 Be 1.79 - 4 Co 1449 - 13000 Cr 6716 - 16800 Cu 5 7000 Ga 19 - 39 Num 49 - 235 Ni 399 - 10200 Rb 14 - 51 8c 8.6 - 12.8 8r 276 - 1135 Th 5.1 - 12 Y 5.1 - 24 Zn 600 - 6300 zr 208 - 3350 Pb 142 - 1215 C ~ 0.6 - 1.7 8n 24 - 177 Ace 7.5 - 42 Hg 0.02 - 0.12 PF 1010 C ~ -3.76) - 1.47 Table 1: Limit contents of slag WO95 / 13116 pcTn ~ 4lol322 ~

2 ~ 12 Due to the limit values of the contents of some heavy metals, this study will only be concerned transition metals which, if they are would completely dissolve, should be subject to specific treatment: Cr, Cu, Ni, Pb and Zn B. Structural composition If glass is the predominantly present phase, 2/3 of the volume, magnetite (Fe11O-Fel112O3) is the form most widespread crystallized and in the evolutionary stage the more advanced (size = 10 to 20 ~ m). She coexists with other important mineral species like hematite ( Fe2O3), lepidocrocite (FeO.OH), quartz (SiO2) and CaAl2Si2O8 calcium or NaAlSi3O8 sodium feldspar.

The advantage of the presence of magnetite, spinel iron, is to allow it substitutions to inside its crystal lattice. The metals of transitions can replace iron in its degrees of various oxidation (II and III) without there being modification of the structure and its stability. This is why element distribution studies in bottom ash, informed us about their coefficients of division:
- Chromium and nickel are located in the network of Fe3O4 in substitution for either Fe11 and / or Felll.
- Zinc and copper are shared between the glass and magnetite in unequal and variable proportions according to the samples.

- Lead is not detected in spinels. His absence is explained for steric reasons.

~ WO95 / 13116 PCTn ~ 94/01322 ~ 2 ~ 1 8 - The other metals are difficult to detect due to their low content and do not represent more than a moderate risk.

I.2. Heat treatment A. Purpose The basic concept is to reduce the fraction unstable glassy and sequester polluting metals by inserting them into crystalline networks in the presence or to synthesize. It's about recreating a real natural material from a waste by modifying very little his chemism II.a) Instability of the glassy slag phase The vitrification t ~ hn; are already used in the stabilization of waste, especially radioactive. he these are very high quality special glasses that not found in clinkers from industrial incinerators. Indeed, observations at microscope revealed intense microfracturing of the glass having very little effect on the crystallized phases.
Its origin is to be found in the development of the clinker. At the end of the incineration ovens, the molten material, undergoes hydraulic quenching. The stresses developed by this thermal shock are sufficient to develop intense fracturing which weakens this makes matter. Furthermore, the glass leads to a alumino-siliceous gel caused by the departure of metals from transition into a complexing acid solution. This gel, as opposed to glass, has the mechanical property of expand or contract in the ambient phase, occupying the volume offered to him. During a leaching, there is extraction of atoms from the glassy phase which induces a reduction in the specific volume. this is observable by a discoloration of this phase, linked to woss / l3ll6 PCT ~ 94/01322 ~
2 ~

departure of transition metals. That’s why the attraction acid causes intense corrosion of the glass solubilizing certain metals which were initially there fixed: iron, copper, lead and very little nickel and chromium.
II.b) 8tabilite pha ~ e crystallized slag The phenomenon described above is not detected in the crystallized phases ~ ui retain their ch; mi ~ me after leaching. No attack figure has could be detected on the crystallized phases, in the same leaching conditions as for glass, concluding to a notable stability of these buildings lenses even by very sensitive optical methods like differential interference contrast.
B) PRlN ~ l ~
Incineration residues from industrial waste are generally rich in iron. During the rise in temperature of the waste in the iron incinerator, thermodynamically unstable under partial pressure in prevailing oxygen at temperatures below lS00 C, is ox ~ die in magnetite Fe3O4 (Fe11Fe111O4) ~ ui crystallizes in the cubic system.
This substance belongs to the large family of spinels whose general structural formula is:

AII ~ 32IIIX4 'X = O, ~, ...
with ~ 1) AII = Mg, (Fe) ~ Cr, M ~, Ca, Co, Ni, Cu, Zn, Cd, ~ Hg), ~ n]
(2) BIII = Al 1 Ga, In, Ti, V, Cr, Mn, Fe, Co, Ni, Rh]
Figure l illustrates the spinel structure normal.

~ woss / 13116 PCT ~ / 01322 `~ 2 ~ 1 8 The slag from the incinerator is generally rich in magnetite. This mineral trap actually the elements in square brackets of line (l) to replace Fe11 and those of line (2) in substitution of Fe11l. These harmful metals are then permanently fixed in the network of the magnetite.
The most immediate idea is therefore to increase the magnetite content of the slag in order to accentuate this trapping phenomenon. It must therefore be recast and cool very slowly. Tests in this direction have demonstrated that the content of slag magnetite dramatically. But the proportion of glass remains high; this is because certain elemental or associated oxides (polymers) of alumino-silicate bath or "melt" ~ 'enrich in the residual bath, at the end of the crystallization of the magnetite, and significantly increase its viscosity. he these include Al2O3, MgO and TiO2. Crystallization is therefore slowed down or even inhibited; nucleation and diffusion having become inoperative.
The originality of the process proposed in this demand is precisely to prevent magnetite from form by forcing the alumino-silicate bath to crystallize spinels rich in Al2O3, MgO and Tio2 from to prevent the viscosity from increasing "residual melt" ~ ui would prevent its total crystallization in reasonable durations. The spinels thus formed continue to accommodate harmful heavy metals between square brackets (l) and (2). Pb2 'has a radius ioni ~ ue very superior (l, 29 A) to that of the metals of transition - between 0.4 and 0.8 A. It cannot therefore be greeted by these spinels. It is inserted in the much larger crystallochemical sites than spares the structure of plagioclase feldspars. These W09S / 13116 PCT ~ R94 / 01322 are intermediate poles of the solid solution NaAlSi308 (albite) - CaAl2Si208 (anorthite) that represents Figure 2.
By fusion of a slag made of glass and magnetite crystals a liquid consisting of elementary oxide molecules such as MgO, CaO, A1203, sio2, FeO, Fe203 and Tio2. These molecules will associate with varying degrees to form aggregates whose stability depends on the importance of the dipole moments of the various constituents.
Pure magnetite basically melts at 1590 DC UNDER
a total pressure of 1 atmosphere according to:
Magnetite = FeOtL) ~ Fe203 ~ L) Elemental oxides FeO and Fe203 are liquid at the melting temperature of pure magnetite since the phase changes ~ ustite <- ~ FeO (L) and Hematite <--> Fe203 ~ L) appear respectively at 1369 C and 1565 C. The bath silicate therefore dissolves monoxide and sesquioxide iron.
R ~; re Fe203 to FeO by means of an additive suitable for for effect:
- to increase the fluidity of the "melt" by increasing system FeO activity, - to prevent further formation of magnetite by destruction of an essential constituent (Fe203) to its formation.

~ WO9S / 13116 PCT ~ 4/01322 ~ ~ 7 ~ 118 For this purpose, Fe metal (Fe) is incorporated which in the prevailing conditions (T = 1550 C) is unstable and reacts with Fe2O3:
Fe '(L) + Fe2O3 (~ 3 FeO (L) The stability diagram of Fe - Fe2O3 as a function of the oxygen pressure is given by figure 3.
In the "melt", the major oxides forming spinels capable of hosting harmful metals "spinellisables" are now: Al2O3, Tio2 FeO and MgO.
cooling of the "melt" pipe, taking into account of the Al2O3 / TiO2 ratio, to the crystallization of the hercynite (Figure 4), which traps transition metals very fluid bath, then ulvospinelle TiFe2O4 as soon as the eutectic temperature is reached (TeU = 1355 C, Cheney and Muan, 1972). At this stage of cooling most of the harmful metals has been immobilized in spinels.
The total crystallization of the bath occurs between 1205 C, (melting temperature of pure fayalite:
Fe2SiO4) and 1118 C (melting temperature of plagioclase NaAlSi3O8) This is a close association of acicular crystals of fayalitesOlsO ~ and plagioclases (60% anorthite) fibrous enriched in Pb.
Indeed from these analytical results, we is placed before an alternative:
or optimize the growth of magnetite in the glassy shank The magnetite network has the possibility to receive more than lS% of elements to replace the F ~ ll and Fe ~ ll, and thus plays the role of a "sponge crystal clear "; it’s a good idea to continue WO95 / 13116 PCT ~ R94 / 01322 e i ~ 7 ~
.
~ 18 growth of germs already present. That’s why if the slag is heated above their temperature of fusion with additions of ferrous compounds and by a slow cooling of the molten phase, supply and thereby considerably increasing the size of the crystals (100 ~ m). The residual glass is considerably reduced and purified of these metals.
or completely recrystallize the slag by the synthesis of new structural patterns.
When wearing the slag / addition mixture to more high temperatures (1500C), we obtain after cools a fully crystallized material. At this stage we reach the formation of new minerals (complex spinels, feldspars and olivine) which confer the safety of a natural rock, metals being then all strongly immobilized.
C. ~ anipulation To make basic substitutions of metals from the glassy phase to the phases crystallized, the slag must be remelted and then cooled by mastering the processes of germination and recrystallization. This is why structural studies and the contents define the operating conditions following.
a) Preparation of samples Laboratory tests are carried out at from raw slag, sampled at the outlet of incineration ovens. After 24 hours of drying at 70OC, the clinker is crushed and then dry ground to reach a particle size <2 mm. After quartering of a sample of 1 kg, 1% by mass of iron filings of MERK extra pure quality article 3819 (see table 2).

~ WO95 / 13116 ~. PCT ~ R94 / 01322 e ~ 176118 Homogenization is done in a closed container and stirred manually. Even if a relationship between the maximum acceptable particle size and efficiency of process has not yet been demonstrated, we believe that grinding to 2 mm produces enough fines to have correct homogenization of solids; that is to say a random spatial distribution of the grains of clinkers and iron filings. The porphyrization of the whole after mixing (grinding <10 mm) would improve without doubts homogeneity. But the tests carried out on the 2 particle sizes lead to the same results.

CONTENT ELEMENTS (%) Fe 99.5 insol. (H2S04) 0.1 Pb 0.002 Cu 0.002 Mn 0.002 Zn 0.002 As 0.0002 N 0.001 S 0.002 TOTAL 99.6112 Table 2: Composition of MERCR iron filings (art 3819) b) Heating conditions They are inspired by the manufacture of vitroceramics. These are prepared by recrystallization of all or part of an amorphous material.
This elaboration first requires the synthesis of a WO95113116 ~ PCT ~ / 01322 ~
2t 76118 high temperature glass (1500C-1600C). The liquid obtained is maintained at 1500C for one hour. The cooling is then programmed and the temperature drops from 1 to 5 C / min.
c) Procedure Laboratory experiments are completed from the slag / filings mixture. We place 10 grams of the formulation described above in a crucible cylindrical alumina (99.7% pure) sintered 20 mm diameter and 30 mm in height. The crucible is then inserted in the center of a horizontal tubular oven CARBOLITE STF 16/75. There are 2 heat shields at inside by the 2 holes of the cylindrical tube in alumina to minimize losses thermal in its center. Finally, the tubing is closed at using 2 stainless steel plugs.
The regulator / programmer allows to fix the heating and cooling profiles. Time necessary to reach 1500 ~ C from ambient temperature is a function of the power ~; m ~ the heating that can develop the oven. She increases with aging of resistances heated. It takes approximately 4 hours and 30 minutes to complete.
Cooling time varies with speed programmed.

III. Result ~

IV. Thermal behavior IV.ll Differential thermal analyzes Differential thermal analysis allowed identify the reaction behavior of the mixture slag ~ filings during its heating. Two areas reaction, exothermic and endothermic flow seats, are _ WO95 / 13116 - PCT ~ R94 / 01322 - 217611 ~

detectable within temperature ranges distinct:

-1- Between 800 ~ C to 970 C, the flow is exothermic. he translates the energy released by a reaction in the state solid: oxidation of magnetite to hematite.
-2- Between 1020-C and 1350-C, the measured flux is endothermic. It corresponds to the energy to bring for allow the slag to merge.

The same analysis was carried out on the raw slag and hardly differs from the values cited above. Namely, an interval of 780C to 990C for the first flow, an interval of 1020C at 1350C for the second peak.

IV.1.2. Warm-up enthalpies The warm-up enthalpies, per gram of product, were determined using a calorimeter room temperature at temperatures before and following the merger. They are shown in the table

3.
ENERGY TEMPERATURES
(Joules / g) (KWh / t) RAW SCORE
Q before merger from 23C to 1010C 564 156.67 Q after merger from 24C to 1390-C1468 407.78 Q of fusion from 1010-C to 1390C900 250 SCORIE + 1% addition Q before merger from 23C to 1010C 500 138.89 Q after merger from 24C to 1390C1334 370.56 Q of fusion from 1010C to 1390C834 231.67 Table 3: Slag heating enthalpies temperature function These enthalpy measures allow us ~ to appreciate the quantities of energy to be supplied to transform the -WO95 / 13116 PCT ~ R ~ 4/01322 -slag and especially the energy gain brought by iron filings when incorporated in the middle.
V.2. ES8AI ~
Heat treatments were carried out on 4 types of slag with different chemical compositions, STL 2, STL 3, STL 6 and STL 8, mixed with 1% of iron filings (MERCK article 3819). For each clinker class, we carry a sample slag / filings, according to the procedure described, at 1500 C, at 1400 C and at 1300 C, in addition, for the STL mixture 8 / iron filings.
X-ray diffraction analysis before and after heat treatment confirms that above 1500 C, the magnetite has disappeared to make way for hercynite FeAl204 and ulvitis (or ulvospinella) Fe2TiO4.
Finally, to check the stability of the products synthesized, we carry out, on the raw samples and on the recast products, the leaching test NFX 31.210 standard. This experimental standard applies a method for obtaining, under conditions particular, of the solubilized fraction of a waste sample under aqueous conditions lending to analytical characteristics. She applies to waste taken in solid form or plastic, and remaining in this state, whatever the degree of division of matter. The results of the characterization of leachate allow, by comparison with the acceptability threshold in landfill, to assess the level of stability of the waste and its destination final, in particular, its landfill. This may involve potential risks that reside mainly in water training, of polluting elements contained in the waste.

~ WO95 / 13116 21 7 61 L8 PCT / FR94 / 01322 The test is performed on the waste crushed to 4 mm. We takes, by quartering, 100 g of residue which llon disposes of in a 2 liter bottle and put in contact with 1 liter of leach solution. She is prepared for from demineralized water, saturated with C02 gas which is stripped by an air bubbling. Shake for 16 hours the flask using a tray shaker allowing linear reciprocating. At term of the opera ~ ion the residual material and the solution are separated. The leachate is then available for carrying out analyzes ~ The residual material will be submitted to 2 other successive leaching operations which will result in the production of leachate which will be them also analyzed.
V.2.1. E ~ know on sample STL 2 * Chemical composition of the raw sample SAMPLE ~ LON 8TL 2 Major elements Trace elements Containing Oxides (%) Containing Elements (ppm) SiO2 38.89 Ba 9600 AL203 14.30 Be 1.79 Fe203 19.61 Co 2240 MnO 0.89 Cr 7400 MgO 1.64 Cu 3900 CaO 10.16 Ga 19 Na20 3.72 Nb 60 K20 0.94 Ni 2643 Tio2 5.99 Rb 29 P205 1.16 Sc 8.6 C02 1.90 Sr 394 S total 0.87 Th 7 Zn 1700 Zr 525 Pb 425 CD 1.7 Sn 54 WO95tl3116 ~ PCT ~ R94 / 01322 -Ace 21 Hg 0.02 Major (~) 99.95 Traces (ppm) 29391 Composition (%) 102.89 * Structural characterization of the raw sample The raw STL 2 sample is mainly composed from:
- 20% 8io2 quartz - 20% Fe3O4 magnetite - 10% augite (Mg, Fe, Ca). (Si, Al) 03 - ~ of feldspar (Na, Ca). (Al, Si) 3O8 The rest, about 50%, is made up of amorphous phase. The chemical composition of this phase glassy could be estimated using analysis point spectroscopic (electronic microprobe of Castaing) or:
- 17 to 1 ~% of i - 6 to 6.5% of Al - 11 to 12% Fe - 3 to 3.5% Na - 11 to 11.5% Ca - 2 to 2.5% Ti - of the order of 1% for R, Mg, Mn and P
whose * Structural characterization of the remelted sample a 1500 C: It is fully crystallized and is composed of 3 phases - hercynite Fe A12O4 - ulvitis, or ulvospinella, Fe2TiO4 - a plagioclase ~ WO 95/13116 ~ 17 6118 PCT / I; R94 / 01322 , at 1 ~ 00 C: The material is not entirely crystallized. there are still approximately 40% of glassy phase.
- increase in the percentage of magnetite Fe304 - appearance of ilmenite crystals FeTiO3 - the fayalite Fe28iO4 - feldspar ~ Na, Ca). (Al, 8i) 30g WO95 / 13116 s PCT / FR94 / 01322 e 217 ~

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WO95 / 13116 PCT ~ 4/01322 ~
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~ 5 ~ L ~ 29 * Leaching tests If we compare the results of the leaching of remelted products at 1500 C, at 1400 C
with those of the raw sample, we notice:
- Copper and nickel can be mobilized for the sample crude are stabilized in the recast products especially at 1500 C where they are not even detected in leachate.
- Arsenic is no longer detectable for products recast - Chloride and sulphate concentrations drop also brutally to become null or practically null in STL2-1500-C.

V.2.2. Test ~ on the STL 3 sample * Chemical composition of the raw sample SAMPLE Sl'L 3 Element ~ major ~ Elements traceQ
Containing Oxides (%) Containing Elements (ppm) sio2 24.71 Ba 8800 Al203 17.98 Be 2.2 Fe203 27.97 Co 4505 MnO 0.65 Cr 12900 MgO 2.37 Cu 3400 CaO 9.80 Ga 52 Na20 3.11 Nb 117 K20 0.69 Ni 3300 TiO2 7.69 Rb 17 P205 1.37 Sc 10.8 C02 0.58 Sr 1135 S total 0.9 Th 5 Zn 600 Zr 520 Pb 142 ~ WO 95/13116 PCT / FR94 / ûl322 ~ 761 ~ 8 Cd o, g Sn 47 As 42 Hg 0.02 PF 1010C -3.03 Major 94.79 Traces (ppm) 35981 Composition (%) 98.39 * Structural characterization of the raw sample The raw STL 3 sample is mainly composed from:
- 35% magnetite Fe304 - 13% augite (Ng, Fe, Ca). ~ Si, Al) 03 The rest, about 52%, is made up of amorphous phase. The chemical composition of this phase glassy could be estimated using analysis point spectroscopic (electron microprobe of Castaing) or:
- 21 to 22 ~ of Bi - 5 to 5.5% of Al - 7.5 to 8% Fe - 4 to 5% Na - 8.5 to 9% Ca - 2 to 2.5% Ti - of the order of 0.5% to 1% for R, Mg, Mn and P
whose * Structural characterization of the remelted sample at 1500 C: It is fully crystallized and is composed of 4 phases - the hercynite Fe Al2O4 - ulvitis, or ulvospinella, Fe2TiO4 - the fayalite Fe2æiO4 WO9S / 13116 ~ f PCT ~ W4 / 01322 -~ 176 ~ i8 - a plagioclase `1400 C: The material is not entirely crystallized. there are still approximately 40 to 50%
glassy phase.
- increase in the percentage of magnetite Fe3O4 - appearance of crystals of ilmenite FeTiO3 and pseudo-brookite Fe2TiO5 - a plagioclase with 50% anorthite ~ WO95113116 32 /? ~ 17 6 ~ L PCT / FR94 / 01322 . ~

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* Leaching tests If we compare the results of the leaching of remelted products at 1500 C, at 1400 C
with those of the raw sample, we notice:
- Mobilizable copper, nickel and zinc for the raw sample is stabilized in the products recast especially at 1500 C where they are not not even detected in leachate.

- Arsenic is no longer detectable in leachate recast products - the soluble fractions of the recast products are 4 to 20 times lower than for the sample gross.

- The concentrations of chlorides and sulfates also fall suddenly to become void or practically zero in STL3-1500C.
otherwise - the lead is slightly destabilized in STL3-1400 C, but it dissolves only weakly.
- The solubility of copper has been reduced more strongly in STL3-1500DC than in STL3-1400C

* Chemical composition of the raw sample , W095 / 13116 PCT ~ R94 / 01322 ~
6 1 1 8 ~ ii Major elements Element ~ traces Containing Oxides (%) Containing Elements (ppm) SiO2 45.65 Ba 12000 A1203 10.41 Be 2.29 Fe203 14.53 Co 1449 MnO 0.54 Cr 6716 MgO 2.86 Cu 971 CaO 6.98 Ga 39 Na20 7.41 Nb 49 K20 1.61 Ni 1957 TiO2 3.66 Rb 51 P205 0.96 Sc 12.8 C02 0.50 Sr 386 S total 1.1 Th 12 Zn 2577 Zr 208 Pb 558 CD
Sn 24 As 8.6 Hg 0.05 PF lOlO-C 1.47 Major (%) 97.68 Traces (ppm) 27219 Composition (%) 100.40 * Structural characterization of the raw sample The raw STL 6 sample is mainly composed from:

- 11% 8io2 quartz - 17% magnetite Fe304 - 12% augite ~ Mg, Fe, Ca). (Si, Al) 03 - 3% hematite Fe203 - of Sulfur The rest, about 57%, is made up of amorphous phase. The chemical composition of this phase ~ WO 9S / 13116 PCT / FR94 / 01322 217 ~ 11g 1 ~ '. '''' glassy could be estimated using analysis point spectroscopic (electronic microprobe of Castaing) or:
- 23 to 24% of 8i - 5.5 to 8% of Al - 7 to 8% Fe - 2 to 2.5 ~ Na - 6 to 6.5 ~ Ca - 3 to 3.5% Ti - of the order of 1 to 2% for K, Mg, Mn and P
whose * Structural characterization of the remelted sample at 1500 C: It is fully crystallized and is composed of 3 phases - hercynite Fe A1204 - ulvitis, or ulvospinella, Fe2TiO4 - a plagioclase at 1400 C: The material is not entirely crystallized. there are still approximately 30 ~ of glassy phase.
- increase in the percentage of magnetite Fe3O4 - appearance of ilmenite crystals - the fayalite Fe2SiO4 - feldspar (Na, Ca). (Al, Si) 30g WO 95/13116 PCTIFR9 ~ / 01322 ~ t 3 8, ll ~ `
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* Leaching tests If we compare the results of the leaching of recast products at 1500 C, at 1400 C
with those of the raw sample, we notice:
- Arsenic, chromium, copper, nickel, lead and zinc available for the sample crude are stabilized in the products especially overhauled at 1500 C where they are not even detected in leachate.
- the soluble fractions of the recast products are 1 to 8 times lower than for the sample gross.
- The concentrations of chlorides and sulfates also fall suddenly to become void or practically zero in STL6-1500C.
otherwise - the lead is slightly insolubilized in STL6-1400 C while it is completely for STL6-1400 C. This phenomenon can also be observed for copper and for lead.

V.2.4. Tests on the STL 8 sample * Chemical composition of the raw sample EC ~ ANTILLON STL 8 Major elements3 Trace elements ~
Containing Oxides (%) Containing Elements (ppm) sio2 26.25 Ba 9347 A1203 10.66 Be 2.2 Fe203 34.92 Co 4256 MnO 0.96 Cr 25,000 MgO 2.33 Cu 1839 CaO 7.68 Ga 28 -~ wos5ll3ll6 ~ 217 6118 Na20 2.66 Nb 85 K20 0.56 Ni 399 TiO2 6.84 Rb 20 P205 2.00 Sc 10.9 C02 0.53 Sr 434 S total 0.03 Th 5 y 16 Zn 955 Zr 3350 Pb 535 CD
Sn 44 As 7.5 Hg 0.05 Major (%) 94.31 Traces (ppm) 46544 Composition (%) 98.96 * Structural characterization of the raw sample The raw STL 8 sample is mainly composed from:
- 40% magnetite Fe304 The rest, about 60%, is made up of amorphous phase. The chemical composition of this phase glassy could be estimated using analysis point spectroscopic (electronic microprobe of Castaing) or:
- 17 to 17.5% of ~ i - 6 to 6.5% of Al - 13.5 to 14% Fe - 2.5 to 3% Na - 8 to 8.5% of Ca - 4.5 to 5% of Ti - of the order of 1% for Mg and P
- of the order of 0.5% for R and Mn * Structural characterization of the recast sample WO9S113116 ~ 1 7 ~ 118 PCT ~ R94 / 01322 at 1500 C: I]. is fully crystallized and is composed of 4 phases - the hercynite Fe Al2O4 - ulvitis, or ulvospinella, Fe2TiO4 - the fayalite Fe2 ~ iO4 - a plagioclase at ~ 00 C: The material is not entirely crystallized. there is still approximately 30% of glassy phase.
- increase in the percentage of magnetite Fe3O4 - appearance of ilmenite crystals FeTiO3 and pseudo-brookite Fe2Tio5 - a plagioclase with 50% anorthite ~ 217 ~ 1i8 Wo 95/13116 ~ PCT / FR94 / 01322 8 ~ D 8 OD ~ b E v vv c ~
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REPLACEMENT LIST (RULE 26) o95 / 13116 PCTn ~ 4tO1322 * Leaching tests The leaching tests were, for this sample, carried out on 3 products remelted at 1550 'C, at 1400 C and 1300 C. The comparison of analyzes of leachate with those in the raw sample, does not prove that there is an increase in the slag inertia gross after treatment. Indeed, the raw sample is initially stable. However, this fact must be hung up with the structure of this slag, made up essentially magnetite.
However, the solubility of chlorides is reduced and sulfates in proportion to the increase in temperature.

II Heat treatment of hydroxide sludge metallic Heat treatment of hydroxide sludge metallic must allow to sequester metals waste pollutants by inserting them into networks crystalline in the presence or to synthesize.
The goal is to achieve, as in the case of nearest slag, composition and structure of a stable natural rock.
The process involves melting the mixture of sludge and additions of appropriate minerals to produce, during a slow cooling, an artificial rock. During this crystallization, the transition metals migrate glassy material towards the current phases crystallization.
The principle is to use the elements already present in the waste and make additions complementary to guide the complete crystallization WOgS / 13116 ~ PCT ~ R94 / 01322 ~ 49 An originality of the process applied to sludge lies in additives that could be slag incineration.
II.l Characterization of sludge and mixture sludge / cories A. Chemical composition:
l. Sludge These are hydrophilic mineral sludges, made up aqueous suspensions of metallic hydroxides themselves same formed by precipitation of metals in solution by lime then with sodium sulfide (Process of depollution of industrial effluents loaded with metals).
The basic composition of the five sludge samples of hydroxides taken daily from the site is shown in Table II.l below:

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REHEATHEAD ~ PLACE ~ AENT ~ RULE 26) ~ 217 ~ 118 woss / 13116 PCT ~ R94 / 01322 The five samples show some consistency for the contents of major elements, mainly calcium and phosphorus. A few variations should be noted in sodium, iron, sulfur...
All samples contain grades high in chromium (1.5 to 4 ~), zinc (0.6 to 4%), copper (from 0.1 to 1%), nickel (from 0.4 to 0.8 ~), lead (from 830 to 1500 ppm), cadmium (from 22 to 202 ppm) and tin (from 0.1 to 3.7%).
2. Slag Slag results from the incineration of waste industrial. They mainly contain non-combustible mineral matter combined under multiple oxidized forms varying depending on the waste cremated.
ST8 slag was used; they are the richer in iron. Their quantometric analysis is indicated in Table II.2 in comparison with the T2 and T5 sludge used for the tests described here.
Slag contains more silicon, aluminum, iron and titanium as sludge, and significantly less phosphorus and calcium. The contents in trace metals vary considerably from sample to another. The ST8 sample is rich in chrome, copper and zinc.

217 ~ 1 18 PCT / FR94 / 01322 ~
Water table II. 2: Analysis ~ flt ... ~ of erh ~ ntillr nc of sludge T2 and T5 and slag F1.6m ~ ntc majeu ~ s in Mud Mud Slag ST8 ~ u ~ oxide 1 ~ T5 SiO2 Z, 36 1.45 26.25 Al2O3 1.76 2.15 10.66 Fe2O3 4.87 8.60 34.92 MnO 0.15 0.10 0.96 MgO 0.64 0.60 2.33 CaO 31.52 30.77 7.68 Na2O 2.74 1.58 2.66 K2O 0.20 0.26 0.56 TiO2 0.05 0.02 6.84 P2O5 15.46 13.56 2 Total C02 6.33 5.10 0.53 Total sulfur ~ 7.27 6.45 0.03 Chlorine ~ 1.27 0.85 Fluorine ~ 1.95 2.46 Loss on ignition (550C) 10.67 12.1 Loss on ignition (1010C) 14.53 13.95 -1.11 ~ in el form ~ ".c ~ llai ~ e m ~ ntc traces (subform ~ lf. ..1-. ~ enppm) Barium 1176 468 9347 Berylium 6.58 0.6 2.2 Cobalt 36 63 4256 Chrome 28000 27500 135û0 Copper 9970 1310 1839 Galium 32 23 28 Niobium 5 5 85 Nickel 3970 3910 399 ~ '20 13 20 St ~ Anr ~ Tn 11 10.8 10.9 ~ 124 112 434 Thorium 17 13 5 Van ~ 1743 66 209 Yttrium 16 16 16 Zinc 22,700 6,300 1,267 Zi ~. ~. iu ......... 17 13 3350 Plornb 1330 830 535 t ~. 1. . . - .., I 109 22 Tin 3,500 37,000 44 Arsenic 4.7 4.5 7 ~ 5 Mercury 3.8 2.2 0.05 ~ WO95 / 13116 21 ~ 6118 PCT ~ R94 / 01322 3. ST8 Sludge / Slag Mix Mixing was carried out with T2 sludge and T5 and increasing proportions of slag ST8 (lO to 50%).
Table II.3 shows the composition of these mixtures.
B. Structural composition of ~ hydrous ~ sludge ~
metalligues The structure of the dried raw hydroxide sludge, . _ crushed, has a crystallized phase consisting about 12% apatite Ca5 (P04) 3 (F, Cl, OH), 35%
bassanite (CaS04,1 / 2H20), the remainder being 53% being consisting of an amorphous matrix.
For our tests, the sludge is dried in a oven at 105C.

WO 95/13116., PCT / ER94 / 01322 Table in II .3: Analysis ml ~ lti ~ of m ~ c of Sludge ~ I ~ T5) / Slag in the ~, ~ u ~ c 30% and 50% slag m- ~ n ~ c major in Mud Mud Mud Mud yo ~ oxide 1 ~ 30% ST8T2150% ST8T5J30% ST8T5 / 50% ST8 SiO2 9.53 14.30 8.89 13.85 A12O3 4.43 6.21 4.70 6.40 Fe2o3 13.89 19.89 16.50 21.76 MnO 0.39 0.55 0.36 0.53 MgO 1.15 1.48 1.12 1.46 CaO 24.37 19.60 23.84 19.22 Na2O 2.72 2.70 1.90 2.12 K2O 0.31 Q, 38 0.35 0.41 TiO2 2.09 3.44 2.07 3.43 P205 11.42 8.73 10.09 7.78 Total C02 4.59 3.43 3.73 2.81 Total sulfur "5.10 3.65 4.52 3.24 Chlorine '' - - - -Fluorine ~ - ~ ~
Loss on ignition (550C) Loss on ignition (1010C) ~ UNDER fi ~ t7tle él ~ ". ~.,. Ldi ~
Pl ~ m ~ nc traces (under famle ~ in ppm) Barium 3627 5261 3132 4907 B ~ .rliu.l. 5.27 4.39 1.08 1.4 Cobalt 1302 2146 1321 2159 Chrome 23 650 20 750 23 300 20 500 Copper 7,531 5,904 1,469 1,574 Galium 30.8 30 24.5 25.5 Niobium 29 45 29 45 Nickel 2,899 2,184 2,857 2,154 ~ ul ~ 20 20 15.1 16.5 S., .. -.1; ........... 10.97 10.95 10.83 10.85 Sl ~ liull ~ 217 279 208.6 273 Thorium 13.4 11 10.6 9 V ~ n ~ -linnl 1283 976 108.9 137 Yttrium 16 16 16 16 Zinc 16,270 11,983 4,790 3,783 Zil ~ u ~ uulll 1017 1683 1014 1681 Lead 1091 932 741 682 Cadmium 76.6 55 15.7 11.5 Tin 2463 lm 25913 18522 Arsenic 5.54 6.1 5.4 6 Mercury 2.67 1.92 1.55 1.12 ~ WO95 / 13116 ~ 17 6118 PCT ~ 4101322 II.3: Results and discussion A. Reminder of ~ last ~ results The first conclusions concerning the treatment thermal sludge without additions are as follows:
- overall improvement in mechanical strength and the stability of the waste beyond l000C thanks to a total crystallization, - reduction in loss on ignition, - decrease in the soluble fraction (disappearance almost total chlorides and sulfates from 1380C, - The results of the leaching tests according to the X31-2l0 standard are recalled in the tables summaries II.4 and II.5, namely:
- decrease in TOC
- Zn, Ni, Cd concentrations in leachate below the regulatory thresholds defined in the decree of March 30, 1993 for tests carried out beyond lO00-C.
However, the problems encountered were:
following:
- release of chromium VI in proportion to temperature rise, - training. calcium ferrialuminates (ferrites).
Addition of iron filings (l to 5 ~) and slag ST8 (l to 5 ~) seemed to contribute to the trapping of chromium in stable crystal lattices (Cf Table II.5).
These findings made it possible to predict other experiments in order to favor the formation of spinels compared to ferrites.
Since adding slag is much more advantageous than iron filings in terms of feasibility economical, the process has been optimized by varying the contents of ST8 slag from 10 to 50% in the mixture.

Wo 95/13116 ~ 17 6118 5 6 PCTIER9 ~ / 01322 ~

Water table II. 4: Effect of t. ~ On lt stabi'- '- sludge T2 and T5 Leaching test (afnor X31-210 standard) , T2 'T2-1000C T2-1200C T2-1380C
TOC (ppm) 1,495 86,162 <63 Metaw ~
(mg / Kg DM) Zinc 17.1 552 <1.2 <1.2 Nickel 13.7-24.1 435 3-7 <6 Cr Vl <0.8 0.3-0.5 2,678 5,976 Chlorides 11,958 11,920 1,070 473 Sulfates 141,580 73,700 75,350 626 TOC (ppm) 2724 35.5 129 <60 Metals (mg / Kg DM) Zinc 39.6 <1.2 <1.2 <1.2 Nickel 28-34 38 <6 <6 Cr VI <0.9 <0.3 2618 2536 Chlorides 8,514 9,940 872,147 Sulfates 96 377 47 900 58 841 540 Table II. 5: Effel: your iron additions or ST8 slag on the stabil; ~
sludge T2 and T5 ~ 1380C
Li, .iv; .. l ,. ~ test (afnor standard X31-210) 1% Fe 5% Fe 1% ST8 5% ST8 TOC (ppm) <63 168 174 133 166 Tracff metals (mg / Kg DM) Zinc <1.2 <1.2 c1.2 <1.2 <1.2 Nickel <6 <6 <6 <6 <6 Cr VI 5976 322 192 765 1204 Chlor ~ res 473 1030 890 620 530 Sulfates 626 83-108 <79 486 627 T5-1380C T5-1380C- T5-1380C- T5-1380C- T ~ 1380C-1% Fe 5% Fe 1% 5 ~ TB 5% 5T8 TOC (ppm) <60 132 136 142 138 Metals f ~ aces (m ~ / K ~ ç MS) Zinc <1.2 ~ 1.2 <1.2 <1.2 <1.2 Nickel <6 <6 <6 <6 <6 Cr VI 2536 215 229 207 596 Chlorides 147 17 10-21 24 27 Sulfafes 540 159-185 <79 418 150 Detection thresholds: Total Cr <O, 200mg / l, CrVI <O, OlOmg / l, NicO, 200mg / 1, Cd <0.040mg / l, Pb <0.500mg / l, Zn <0.040mg / l, As <0.005mg / l, Hg <0.0005mg / l, free CN <O, lOOmg / l.

~ woss / 13116 ~ 1 ~ 6 1 ~ 8 pct ~ 4/01322 The minimum slag concentration threshold at use to prevent solubilization of chromium VI is 30%.
We still need to increase this amount of slag up to 50% to promote the formation of spinels by compared to ferrites.
B. Thermal behavior of samples l. Loss of sludge mass after treatment thermal The loss of mass of the treated samples is recorded in Tables II.6 and II.7 Water table II 6: E ~ uLlliv ~ of the loss of sludge mass in r ~ ---- I - -.
from t ~ Luu ~ from l -_; t ~

Weight loss in% 1000C 1200C
T2 18.1 21.3 1 ~; 18.2 19.3 Water table II 7: E ~ oluLu .. of the mass loss of the b ~ boles L ~ in ST8 slag Weight loss in% 5% ST8 slag 30% ST8 slag 50% ST8 scone T2 / ST8 29.6 21.9 15.2 T5 / ST8 - 21.3 14.7 We observe that:
- The higher the temperature, the more volatilization of elements is important, - The addition of slag significantly reduces the loss of mass of the samples.

WO95 / 13116 ~. pcTn ~ 4lol322 2. Differential thermal analysis (ATD ~ and thermoqravimetric (ATG) Differential thermal analysis allowed identify the reaction behavior of the two T2 and T5 sludge samples as well as ST8 slag.
Regarding sludge, important "events"
only come off at low temperature (<500 C). At high temperature, we observe two peaks which can possibly be attributed to partial mergers around 110C and around 1400C. The two samples T2 and T5 behave almost identically.
In the case of slag, the start of the fusion is around lOOO C and the end of fusion towards 1300-C.
In view of the ATD, it would seem that the thermal zone efficient treatment of raw sludge or mixtures sludge and slag is in the range 1200C-1400-C. The problem is different if one performs other types of additions.
The thermogravimetric analysis at 1500C shows a mass loss of 30 to 40% for the 2 samples of raw sludge tested. At the level of slag, the loss of mass is low, of the order of 2%. Two loss zones of rapid mass are to be noted from 20C to 300C and 1200C to 1500-C.
3. Multi-element analysis of the treated residues In order to be able to quantify the elements that have volatilized, a multi-element analysis of residues from heat treatment at different temperatures was performed by ICP-MS spectrometry.
For the analysis of raw sludge treated alone, the results were as follows:
A lOOO C

~ wossl13116 2 17 6 1 18 ^ pcTn ~ 4lol322 The results are illustrated in Table II.8. At level of major elements, we see the total departure of CO2, a drop in K20, S and Cl contents.
With regard to heavy metals, these are the mercury, lead, cadmium which almost volatilize totally. Tin and zinc contents decrease slightly.

Table II.9 confirms the total disappearance of the CO2, around 50% of S and Cl (only for T2). We also finds a decrease in Na2O, K2O (T2), and F. As for trace metals, with total volatilization of Pb, Hg, and Cd, a decrease in the concentration of Cr, Cu (T2), Ni, Zn, Sn (T2), and As (T2). Variations should be noted at the level of the two processed samples.
The first results at 1380C only concern the mixture of sludge with 30 ~ slag (Cf. Table II.l0).

There is essentially a larger departure of Na2O, K20 and Cl. Regarding trace metals, Cd and Hg are volatilized. On the other hand, less Pk is released to the atmosphere only at 1200-C, which could can be explained by its trapping. The same goes for Cr, Ni, Zn and As which may also be partly integrated into crystalline phases.

Wo 9 ~ / 13116 1 8 PCT / FRs ~ / 01322 Table II.8: Analyæm ~ m ~ n ~ i ~ desbo ~ I2etT5) after ~ a ~ nl ll .. ~ e at lOOO 'C

Fl ~ m ~ ntcmajel2 ~ Sen Fl ~ h ~ n ~ n Fl ~ h: -ntill ~ n Frh: -ntill- ~ n F.- ~ h ~ ntillnn .la ~ oxide 12 T2-1000C 1 ~ T5-1000C
SiO2 2.36 1.97 1.45 1.49 Al2O3 1.76 1.76 2.15 2.05 Fe2O3 4.87 4.78 8.60 8.46 Mr ~ 0.15 0.14 0.10 0.10 MgO 0.64 0.6 0.60 0.53 CaO 31.52 31.32 30.77 30.29 Na2O 2.74 2.6 1.58 1.54 K2O 0.20 0.15 0.26 0.2 TiO2 0.05 0.04 0.02 0.02 P205 15.46 14.92 13.56 13.07 Total C02 6.33 0.11 5.10 0.27 Total sulfur ~ 7.27 4.64 6.45 4.34 Chlorine} 1.27 1.13 0.85 0.88 l ~ luor * 1.95 2.31 2.46 2.72 Loss on ignition (550C) 10.67 0.98 12.1 Loss on ignition (1010C) 14.53 3.23 13.95 6.22 ~ as clc, .. ~ a.
Fl ~ smf ~ ntc traces (ppm) Barium 1,176 1,583 468,431.3 B ~ yliulll 6.58 5.46 0.6 0.02 Cobalt 36 23.74 63 203.78 Chrome 28000 29879 275W 28398 Copper 9970 9987 1310 1391 Galium 32 4.71 23 3.91 Niobium 5 0.7 5 2.28 Nickel 3,970 4,537 3,910 4,055 F '' 20 1.65 1 ~ 3 1.17 S ~ .qn ~ m 11 8.6 10.8 9 Sho ~ ll; ulll 124 116 112 90.02 Thorium 17 0.34 13 0.13 V ~ n ~ -linm 1743 ~ 1598 66 84.3 Yttrium 16 3.73 16 3.62 Zinc 22,700 21,046 6,300 6,383 Z ~ uu ~ ll 17 g, 33 13 5.17 Lead 1,330 634 830 34.37 Cadmium 109 15.06 22 ~ 0.5 Tin 3,500 3,029 37,000 34,127 Arsenic 4.7 6.39 4.5 6.56 Mercury 3.8 <0.05 2.2 Wo 95/13116 ~ 61 18 PCT / ~ R94 / 01322 Water table II. 9: Analysis m ~; .e of sludge m and T5) after a ~ t ~ e ~ only at ~ 200C

~ l ~ mpntcmajeurs-pnFrh: mffllnrl ~ rl ~ n ~ t ~ h ~ nfillnn ~ - ~ h ~ nffllnn pu ~ ... ~ e d'7yde l ~ 12WC 1 ~ T ~ 1200C
SiO2 2.36 2.84 .1.45 2.05 Al23 1.76 1.71 2.15 2.44 Fe2o3 4.87 5.03 8.60 7.85 Mr10 0.15 0.15 0.10 0.10 MgO 0.64 0.72 Ofio 0.69 CaO 31.52 31.79 30.77 31.81 Na2O 2.74 2.02 1.58 1.26 K2O 0.20 0.16 0.26 0.32 TiO2 0.05 0.06 0.02 0.03 P205 15.46 14.78 13, ~ 6 13.36 Total C02 6.33 0.02 5.10 0.02 Total sulfur "7.27 4.08 6.45 3.45 Chlorine ~ 1.27 0.71 0.85 0.74 Fluorine ~ 1.95 1.68 2.46 2.28 Loss on ignition (550C) 10.67 - 12.1 Loss on ignition (1010C) 14.53 13.95 '~ under fo ~ me élc "~, laii ~
~ I ~ SmPn ~ traces (subform ~ If. ~. ~ T ~ enppm) Barium 1176 1419 468 442.24 Bt: ~ yliulll 6.58 5.18 0.6 traces Cobalt 36 19.8 63 40.43 Chrome 28000 20 ~ 98 27500 19298 Copper 9,970 7,852 1,310 1,325.1 Galium 32 3.90 23 3.67 Niobium 5 0.50 5 2.00 Niclcel 3970 3264 3910 2499 R ~; u. ,, 20 2.27 13 1.58 5 ~ .. 1; .., 11 21.47 ~ 0.8 21.55 SL ~ liu ~ 124 119 112 106 Thorium 17 0.77 13 traces Vanadium 1743 1325 66 61.01 Yttrium 16 ~ 3.14 16 3.74 Zinc 22,700 17,061 6,300 5,091 Z ~ u ~ u ~ 17 11.25 13 6.38 Lead 1,330 16.52 830 9.68 ~ lmilmn 109 ~ 0.39 22 <0.40 Tin 3,500 2,078 37,000 36,638 Arsenic 4.7 2.04 4.5 4.92 Mercury 3.8 ~ 23.6 2.2 <24 PCTIFR94 / 01322 ~
WO9S / 13116 ~ 6 11 ~ 62 Tab leau II. 10: Analysis ml11fff ~; - e des m ~ ~ Ps Mud. ~ 2 e ~ T5) lScone ST8 (30%) after a ~ ot tl ~; q..e of 1380 "C

Fl-sm- ~ nJc majeu ~ al Mud Mud Mud Mud p ~ .S I .. b. o ~ ydeT2 / ST830% T2 / ST830% T51ST830% T ~ / ST830%

SiO2 9.53 8.64 8.89 8.19 Al2O3 4.43 4.66 4.70 5.08 Fe2O3 13.89 13.28 16.50 15.99 MnO 0.39 0.39 0.36 0.36 MgO 1.15 1.14 1.12 1.08 CaO 24.37 24.64 23.84 24.08 Na2O 2.72 1.23 1.90 0.89 K2O 0.31 0.13 0.35 0.08 TiO2 2.09 2.06 2.07 2.05 P2O5 11.42 12.23 10.09 10.87 Total C02 4.59 0.08 3.73 0.01 Total sulfur ~ 5.10 0.14 4.52 0.10 Chlorine ~ - 0.008 - 0.005 Fluorine ~ - 1.36 - 1.13 Loss on ignition (550C) - 0.12 - 0.03 Loss on ignition (1010C) ~ under for7ne fl ~
pl ~ m ~ n ~ t ~ aces ~ in the form ~ - t 'f ~ - ~ in ppm) Ba ~ um 3627 4331 3132 3361 B ~ ~ liulll 5.27 traces 1.08 traces Cobalt 1302 1144 1321 1145 Chrome 23650 29510 23300 26208 Copper 7,531 5,804 1,469 1,139 Galium 30.8 6.67 24.5 6.35 Niobium 29 27.64 29 28.42 Nickel 2,899 5,621 28S7 4,978 ~ b; '- 20 1.35 15.1 0.99 St AnAillm 10.97 11.16 10.83 10.77 Sl.ollLu .. l 217 214 208.6 194 Thorium 1 ~, 4 0.92 10.6 0.77 V ~ n ~ AillTn 1283 1162 108.9 110 Yttrium 16 5.09 16 4.95 Zinc 16,270 18,658 4,790 5,231 Zl ~ vluul ~ l 1017 109 1014 108 Lead 1091 436 741 239 r ~ lm 76.6 0.49 15.7 0.62 Tin 2,463 1,617 25,913 22,874 Arsenic 5.54 8.82 5.4 7.76 Ground 2.67 - 1.55 ~ WO95 / 13116 ~ 1 7 61 1 8 PCT ~ 4/01322 C. Leaching tests By comparison with regulatory thresholds defined in the decree of 30 March 93 relating to sludge of hydroxides and bottom ash from waste incineration as well as the thresholds recommended for a recovery in clinker works incineration of household waste, the results obtained on sludge-slag mixtures (30 and 50%) treated thermally at 1380C are summarized in Table II.ll.
In conclusion, we can confirm that the leachate have the following characteristics compared to untreated witnesses:
- decrease in TOC
- metal concentrations in leachate below the thresholds, even relating to valuation in public works - and above all, considerable decrease in the solubility of chromium VI compared to tests at 1380-C
on raw sludge (from 2678-5976 ppm to 4.3-9.4 ppm).
It takes a ~; n; ~ um of 30% slag in the meiange sludge / slag to be treated to insolubilize chromium.
The best results are obtained with 50% of slag added to the sludge.

WO95113116 pcT ~ Rs4lol322 ~
2 1 7 1 ~

Table II.ll: Effect of lm ~ jout of 30% and 50% te ~ cories 6Ur ~ tabil: ~ -tinn sludge T2 and T ~ ~ 1380C

T2 / 30% sc. T5 / 30% sc.T2 / 50% sc.T5150% sc. Nun Nun TP
1380C 1380C 1380C 1380C (March 30, 94) mg / KF ~ MS
TOC (mg / Kg) 184 161 2 ~ 66 2; ~ 2 c1500 Trace metals (m ~ / Kg MS) t ~~ '<0.15 c0.15 <1.2 <1.2 <25 <1 Total chromium 9.4 4.3 <6 <6 <50 Chromium VI - - 0.7 <0.3 <5 <1 Nickel <1.5 <1.5 <6 <6 <6 <50 Lead <0.60 0.25-0.6 <15 <15 <50 <15 Zinc <1.5 <1.5 <1.2 <1.2 <250 ~ enic <0.30 <0.30 <0.02 <0.02 Mercury <0.03 <0.03 <0.04 <0.06 <5 <0.2 NC free - - <0.3 <0.3 <5 Chlorides - - 30 35 Sulfates - - 55 1Z2 - <70,000 Thresholds of ~ l ~ complete ~ n: G total <0.200 mg / l, GVI <0.010 mg / l M ~ n ~ 7nnn ~ Cd <0.040 mg / l, bp <o ~ soomg / l Zn ~ 0.040mg / L ~ s ~, ~ 05m ~ / 1, Hg ~ a ~ lÇ ~ / l CN free ~ O, lOQ.n ~ / l.

D. Structural study l. Mineraloqic analysis by ~ photonic microscopy and by scanning electron microscopy (SEM).
The fusion-crystallization cycle in the case of adding 50% slag leads to the development of spinels, apatite crystals and ferri-aluminates calcium.
Apatite, whose ideal composition is Ca5 (PO4) 3 (F) but where Ca ions are replaced at various degrees by cations and PO4, F by anions SO4, sio4 and CrO4, are generally slightly colored under the microscope photonics, unlike the fusion tests on raw sludge.
Sludge / slag mixtures (50% / 50%) lead to a phase with a crystallochemical structure of spinel having _ WO 95/13116. PCT / liR94 / 01322 the highest reflectance. Variations in reflecting power correlated to chemical data by electronic microprobe to establish that the heart spinel crystal is enriched with chromium at the difference of the edges richer in Titanium.
By this observation process, the ferrites are also highlighted: it slagit crystals skeletal honey yellow very shaped characteristics.
In fact, fluoro apatite for the most part, and / or plagioclases (byttownite variety) fill in the gaps intersertal spinel crystals only.

Claims (18)

1. Process for treating waste, characterized in that that it includes the following steps:
- heating a mixture comprising the waste to treat and one or more nucleating agents containing in particular ferrous compounds, said heating being carried out under conditions such that it allows obtaining a mixture in the liquid phase also called fusion mixture or "melt", including at least 5% of oxides Fe2O3 are transformed into FeO oxides;
- the controlled cooling of the "melt" until obtaining a solid material in which the metals heavy materials contained in the treated waste are stabilized within crystal structures containing crystals of the spinel family;
- the recovery of the solid material obtained. 2. Treatment method according to claim 1, characterized in that the heating step includes a stabilization phase of the mixture at a temperature allowing the complete liquefaction of the mixture to be treated. 3. Treatment method according to claim 1 or claim 2, characterized in that the waste treated are slag resulting from the incineration of industrial or domestic waste. 4. Treatment process according to any of the claims 1 to 3, characterized in that the agents of nucleation are ferrous compounds such as iron filings of iron. 5. Treatment process according to any of the claims, characterized in that the waste to be treat are metal hydroxide sludges and in this that the mixture to be heated comprises the aforesaid sludge metal hydroxides and, as agents of nucleation, slag resulting from the incineration of industrial or household waste. 6. Treatment method according to claim 5 characterized in that the mixture to be heated comprises between about 70% and 30% hydroxide sludge and between 30% and 50% slag by weight of the mixture. 7. Treatment process according to any of the claims 1 to 6, characterized in that one recovers between approximately 20% and 50% of spinels at the end of the treatment. 8. Process of treatment according to any one of claims 5 to 7, characterized in that the slag are replaced by a ferrous compound up to 5% in weight of the mixture. 9. Process of treatment according to any one of claims 1 to 8, characterized in that the step of heating is carried out under such conditions that it allows a) the liquefaction of the magnetite contained in the slag and the release of Fe2O3 oxides, and b) the reduction of the Fe2O3 oxide formed, to the FeO oxide by addition of agents such as iron. 10. Treatment method according to any of the claims 1 to 9, characterized in that the temperature of the mixture to be treated by heating is raised up to about at least 1450°C, preferably up to about 1500°C. 11. Treatment process according to any of the claims 1 to 10, characterized in that the compound ferrous is iron. 12. Treatment method according to any of the claims 1 to 11, characterized in that the compound ferrous is iron filings in a proportion greater than 0.5% by weight of the mixture to be treated by heating, preferably 1% by weight of the mixture to treat. 13. Process according to any of the claims 1 to 12, characterized in that the agents of nucleation represent from about 0.5% to about 15%
as a percentage expressed by weight of the mixture subjected to the heating step. 14. Treatment process according to any of the claims 1 to 13, characterized in that the waste to be treated are slags containing mainly the following oxides in a given proportion in percentage in relation to the total weight of waste:
SiO2 26.25 to 45.65 Al2O3 7.43 - 17.98 Fe2O3 14.53 - 34.92 MnO 0.54 - 1.88 MgO 1.64 - 2.86 CaO 6.41 - 10.16 Na2O 2.66 - 10.82 K2O 0.56 - 1.61 TiO2 3.66 - 7.69 P2O5 0.96 - 2.54 CO2 0.33 - 4.32 Total S 0.03 - 2.53 15. Treatment process according to any of the claims 1 to 13, characterized in that the waste to be treated are metal hydroxide sludge mainly containing the following oxides in a proportion given as a percentage by weight total waste:
SiO2 1.4 - 2.7 Al2O3 1 - 3 Fe2O3 3 - 15 MnO 0.05 - 0.2 MgO 0.5 - 1 CaO 20 - 32 Na2O 1.5 - 4 K2O 0.2 - 0.3 TiO2 0.01 - 0.1 Total S 4 - 14 16. Treatment method according to any of the claims 1 to 14, characterized in that the step of heating is carried out on slag having a grain size less than 10 mm, preferably less than 2mm. 17. Treatment process according to any of the claims 1 to 16, characterized in that the slag are homogenized with the nucleating agents, particular with the ferrous compound(s). 18. Treatment process according to any of the claims 16 or 17, characterized in that the mixture of slag and ferrous compound(s) is porphyrized from so as to obtain a particle size of less than 10 μm.