CA2114137A1 - Method for detoxication of combustion residues by removing the movable toxic compounds and by binding and concentrating said compounds obtained from treatment solutions - Google Patents

Abstract

The invention relates to a process for stabilizing slag by extraction of the soluble metallic fractions. It involves carrying out leaching of these slags with an aqueous leaching solution, containing elements exchangeable in the form of chlorides with the heavy metal cations present in these slags. The leaching solution consists of a dilute hydrochloric acid solution, for slag with a basic character, or by a chloride solution of an alkali or alkaline earth metal, for slag with a neutral character.

Description

W093 ~ 25716 2114 ~ 3 7 PCT / FR93 / 00543 METHOD FOR DETOXICATION OF COMBUSTION RESIDUES BY
EXTRACTION OF MOBILE TOXIC COMPOUNDS AND FIXATION-CON OE NTRATION OF THESE SAME CO ~ POSSES
TREATMENT SOLUTIONS
Slag is non-volatilized solid residue extracts from combustion stoves, on sites industrial. Usually evacuated by a hunt hydraulic to a receiving pit and container so from 3 to 30% water, they look like solids black more or less divided and very heterogeneous.
In the context of this description, the expression "slag" must therefore be understood in the as broad as possible. It concerns all combustion products and residues, for example machefers, likely to contain heavy metals more or less Eligible by runoff or meteoric water.
They may still consist of fly ash from, for example, the incineration of residues urban Slag is often characterized by a silico-aluminous gangue containing oxides metallic, mainly ferric oxides and lower levels of oxides of chromium, copper, n ~ i ~ kel, zinc, even de-cobalt and lead (table l).
Their compositions may of course vary considerably from one site to another.
This is what can be observed, for example at the table 1 below. It presents the results given as examples of multi-analysis Slag heaps o ~ held on three si ~ es different manufacturers, in Strasbourg (ST l), in Salaise, in the department of Isere (S II), and in Saint-Vulbas, in the department of Ain tSV l) ~

WO 93 ~ 2 ~ i716 1 1 4 13 7 PCI / FR93 / 00543 '.

Table I: Anal ~ se multiélémen ~ slag area of Tredi Strasbourg (ST 1) of Tredi Salaise Il (S Il) and Tredi Saint-Yulbas (SV 1).
___ __ _. _. e _ _ __ ~
Major elements in Slag ST 1 Slag S II Slag SV 1 percentage of oxide:
. . . _, _ SiO ~ 28.89 23.9_ 23.58 ~ 0 ~ 9 70 8.46 ~ 3.12 . -. ,. ~
Fe ~ 33.95 1 23.8 18 91 Mr ~ 1.86_ 1 1.44_ ~ .13 McO _ 1.89 1 0.87 1.01 C ~ aO ~ 5.84 1 9.51 _ _8.58 a? O - - - 3.70 I 1.45 0.75 K ~ O 0.87 l 1.29 ¦ _0.75 i ~. _ 5.85 1 ~ I _ 0.98 P2Os _ - 1.22 I 9.61 ~ 7.85.
Sulfur * __ 0.04 1 1.42 1 0.16 * R ~ sultars in elementary form E: trace elements (content ~ imaged in ~ elementary form in ~ pm lI ~ 11500 _ 2429 _ Bervlium 3 4 0.6 1 ~ _. . ~
Cobalt 6800 .S
Chrome _ _ 20800__ lo90 ¦__5__ C ~ 48ûO l3874 1 8800 C ~ 58 5.0 1 2 Nlobium 124 ~ ol Nickel S800 14. ~ 8,784 ~ _ _ .... ... . . . _, ~
Rubidium _ _ 24 17 ¦ 16 ~ Scandium 6.4 1 7.9 _ 6 Stron ~ ium 402 171 290 . ._ _ _ ~
Tlionum_ 5 5 _ ~ 5 ~ ~ Vana ~ um ~ 484 _ 115 _ 105 I - ~; I Ymium 6 ¦ ~ 7 inc _ ____ 19 ~ 1 ~ ~ S20 ~ onium 282 l 12 98 tain ~ ~ 48 _ 105 360 Cadmium 0.3 3.2_ _ 1.3 M ~ 0.04 0 ~ 3.8 ; ~ Arsenic __ 6. l4 ~ 5 50 Lead 186 324, l __ 190 ~.
:

WO93 / 2571S ~ PCT / FR93 / 00543 Slag from waste incineration industrialists should normally be stored in landfills or technical landfill centers (TEC).
These slag can indeed present risks, especially when their heavy metal contents, toxic, in easily elutable forms, are still high. These heavy metals are concentrated in scQries according to various physico-chemical mechanisms, and according to their natures, form various associations pPU or not known. This is the reason why these risks are 1 ~ subject to evaluations with consequences of orientations towards CET ~ which can be distinguished according to their respective capacities to authorize these burial in conditions responding each time to standards - where these have been defined - of : security ~ appropriate.
~:
Selective extraction methods, used in pedology (soil science), allow to distinguish certain associations or certain constitutions specific (speciationsj and provide information on chemical forms and possible conditions of solubilization of metals. Knowledge of these data is important to assess the possibility of a decontamination treatment ~.
The metals present in the slag can be water-soluble, exchangeable, associated with oxides and amorphous or crystallized hydroxides, or in the form of precipitates, such as carbonates or sulfides. Often the significant pollution to which slag can give rise, result from the extraction of these metals by solubilization in meteoric or runoff. The isotopically exchangeable cations WO93 / 25716. PCT / FR93 / 00543 ,,, - ~ li4 ~ 3 1 are exchanged all the more quickly as the forces electrostatics on negatively charged sites will be weak.
More generally, these findings have led specialists to define the mobility of an element, it is that is, the ability of this element to pass through middle compartments where it is less and less energéti ~ uement retained, the ultimate compartment being represented by} a liquid phase (solution).
Various standards exist to correlate risk presented by the slag treated with the contents ~ or solubilizable quantities) of metals dissolved in leachate or eluate where required. For these standardized tests, these slags are leached by aqueous solutions simulating the action of meteoric waters. These tests of leaching, carried out in the laboratory, allows a assessment of the actual risks incurred during implementation controlled slag discharge. They can specify the conditions under which certain mints can be used in public works (circular machefers dated 8/04/92, see table 2 below). For example in France, the AFNOR standard study protocol (X31210, 1988) recommended by the Ministry of the Environment a for the purpose of extracting soluble substances contained in the crushed slag (~ iametre <4 mm).
Other types of standards are under study by the services competent from the European Economic Community (EEC ~.
In the different categories of leachates, the analyzes of soluble toxic metals allow locate the concentrations measured in relation to thresholds fixed by French and European standards. Of this referencing will depend on the authorizations of recovery (table 2) or landfill in W093 / 25716 2 ~ 13 1 PCT / FR93 / 00543 CET ad hoc, depending on whether the processed products obtained will be classified, for example, as "hazardous waste"
(Class I type CET), "non-hazardous waste" ~ CET from Class II), or "inert waste" (see Table 3 following).
The operating mode of the standardized study protocol AFNOR (X31210, 1988) is as follows:
- demineralized water saturated with air and C02 a pH 4.5 and resistivity between 0.2 and 0.4 Mn.cm is mixed with 100 g of slag for 16 hours at asbestos temperature with rotary stirring.
- the first leachate is o ~ held by filtration of supernatant after centrifugation of the mixture (2000 g for 15 minutes). The color, the smell, the conductivity and pH are then measured O The solid is then resumed for 2 new extractions with by consequently obtaining two leachates ~ or eluates ~
additional. At the end of these operations, the request chemical oxygen (COD), total organic car ~ one 0T) and a mineral analysis are performed on the 3 eluates.
Similar tests have been developed in other countries or in the EEC
They helped set standards, like illustrated in Table 3, but likely to modifications. The values presented define various "elution thresholds" corresponding to the sum of the quantities solubilizable maximums of each of the metals or others polluting constituents (e.g. chlorides and cyanides soluble) which can be tolerated with regard to each categories or classes of waste involved ~
For polluting metallic elements, the chlorides and cyanides, 1PS French standards and WO93f2 ~ 716 PCT / FR93 / 00 ~ 3 2il 4i 3 ~ 6 European (non-hazardous waste ~ also require that the quantities of each of the elements leached during of the three successive extractions go decreasing.
Otherwise, that is to say the one where would observe "increasing solubilizations" of some metals in at least two successive leachates or eluates, one could not conclude with the sta ~ ilisation of the slag in time. We could indeed always fear risks of pollution resulting from renewed exchanges between buried slag and runoff.
The: Tables 4, 5 and 6 which follow allow appreciate what the main features are pollutants from slag, ST l, 5II and SV l considered to title of examples.

, ~:

: ::

~; :

: ~

W093 / Z5716 2114 ~ 3 7 PCT / FR93 / 00 ~ 3 Table 2: Recovery of incineration slag household garbage in public works threshold concentrations given by the leachable fraction obtained by the test normalizes AFNOR ~ x 31-210).

* * * * * * * * * * * * * * * * * * * ~ * * **
* unburnt <5% *
* soluble fraction <3% *
* Hg <0.2 mg / ~ g of dry matter *
~: * Pb <4 mg / Kg of dry matter *
* Cd <l mq / Kg of dry matter *
* Cu <20 mgjKg ~ e dry matter *
* As <2 mg / Kg of dry matter *
* CrVI <1 mg / Kg of dry matter *
: * sulfates <4000 mg / Kg of dry matter *
* chlorides <2800 mg / Kg of dry matter *
* TOC <100 mg / kg of dry matter *
* * * * * * * * * * * * * * * * * * * * * * **

If the leachable fractions respect the thresholds aforementioned, the chews are considered to have a low leachable fraction. The corresponding production can then be used in public works.

Reference: Circular ~ achefers, Service des clean technology and waste from :: Ministry of the Environment, project of 8/04/92.

: ~:

WO 93 ~ 25716 P ~ / FR93 / 00543 21 ~ 4l ~ 7 , 8 Table 3: Comparison of European and ~ French standards on landfill disposal waste. Concent ~ ations-thresholds given for the leachable fraction obtained by the German test for European standards ll ~ Og of dry waste / ll of water) and by the Afnor standardized test for French no ~ mes (1OOg of raw water waste III). The results are expressed in solubilizable quantities in mg / kg.

. ......................... ~
Normal Waste Non Nominal Waste dangerous French dangerous French Waste EEC class I standards EEC class II inert codes mg / lcg (I) (slag) mg / kg () nominal ash C3EE
~ g ~ kg ~ 2) m ~ / kg (2 ~ mg./lcg ~
~ _ _ __ pH 4-13 5-13 4-13 4-13 : COD c5000 Loss on ignition ~ 5%
TOC 400-2000 400-2000 <400 <2000 arsenic III 2-10 <10 1-2 <2 <1 lead 4-20 <100 <4 <30 total cadrnium 1-5 <50 <1 <5 of ~: chrome VI 1-5 <100 ~ 1 these copper '20 -100 ~ 20 ~ 20 elements nickel 4 ^ 20 <100 ~ 4 must 0.2-1 <10 <0.2 <0.2 be zinc 20-100 <500 <20 <50 m ~ / k ~
~ ~. , _ ~
in mg / kg of dry waste

2) in mg / l; g of burned waste - European Direcave project on landfill of waste.
- Draft ministerial order on the landfill of special industrial waste ~ Class 1). Text du Minis ~ erc de ll ~ nvironnemen ~, ref DEPRfSEI / SDO / AN Feb-31, May 14, 1991.
Circular on the discharge of solid residues from the exhaust of fumes from factories incineration of urban residues (Class 11). Text from the Ministry of the Environment, ref DEPR / SEIlSM / SlPD / APR / MBr, June 12, 1991.

: ~

::

WO 93/2 ~ 716 P ~ / FR93 / û0543 I TABLE 4: STANDARDIZED LIXIYIATION TEST (WITNESS ~
Strasbourg slag (ST 1 S ~ ivi analyzes extracts _ _ ~. ._ - ~
Quan ~ it ~ Standards Nonnes Parameter 1st 2nd 3rd total ex ~ e Class I (1) Yalonsa ~ on controlled Ex ~ aclion Ex ~ action Ext ~ ac ~ on ~ Class II decalc (2) Work ~ Pub.
raw ~ (mg / kg) (m ~) (mg / kg DM) ... ~. . ~ _ _ Odor Odorless lnodoleIrK ~ golden ~ ~. . . ~. .
: Color Colorless lncolore Colorless _ .. ... _. ,. . -~ ~ H 7 0 6.4 6.0 ~
~. . __. _ __ ~. .
Resistivity (Ohm.cm) 4000 24000 45000 ~~ 24 ~ O ~ 40 ~ 5000 (1) _ TOT m ~ / l: ~ - ~ clOOO
_. , - _ __ _ ~:, ~ __.
~ ~ Concenuaion Concenuauon Concen ~ tion Q. t ~ L ex ~. Standards Standards Standards : ~ ~: El emen tsdu first of second of third of d ~ chel Class I Class II ~ TP (MS ~
: exuai ~ (mg / l) exu ~ it (mgll) ex ~ (mg / l) gross ~ m ~ g ~ (mg / Kg) (mglKg) (-ng / kg) Plom b _ 0, 1o7 0.045 0.004 1.56 <100 <30 <4 : C ~ dniium ~ ~ N ~ ND. _ = <50 c5 <
zinc ~: 0 358 0.095 ~ 0 ~ 264 7 17 ~ 5 ~ 0 (~ follow ~ ~ 2274 0.611 O.OS6 29.41 - <20 <20 ~ i-- 0 051 0.04 0.068 _ 1.59 ~ 100 _ _ 0 060 ~ .000-- O.oOo 0.60 at c100 _ I ~ / le ~~ `` <0003 <0.003 ~ ~ 0.003`` <0 ~ 03 <10 c0,2 c0,2 ~ Canvases ~ ~ ~ ~ clO __ 0.00 ~ 3 0.0009 `~ 0.0008 0.052 clo <2 c2 ~ hlo ~ ures ~ ~ 161 ~ _ 1 .96 ~ 4 9.6 c10000 ~ 2800 ~,, _ _; .
~ Sulfates ~: 44 5 1 500 <4000 : telauves alLX., endres volan ~ es provenan ~ i lcinélauon de re; idus urbain. _ ~ ND: not ~ dosable, MS mauèresseches Behavior in solubilisanon : ~: (:: omponement ~ uantltes solublhsablesen :: ~ mg per: K ~ of gross waste Elts:: ~ Dissolu- ~ Solubili- Solubili- ~; i; ~ bi ~ Dansles I Poten ~ ellement : i ~ on ~ otalesaion: sation sa ~ on condi ~ solubilizable ons : ~ ~ I decreasing staPnante growing e of test I (waste conc.) . ~. . _ _ ~ _ _ ~
~ ~ ~: Lead X 1.56 186 ~ _. . _ ~ _ : ~ ~ zinc X 7.17 19 ~ 0 _ ~ ~ _ Copper:: X 2 ~, 41 4800 Nickel. ~ X 1 59 5800 ; _. _ ~. . ...
: (~ hrome X 0.60 20800 . ~. _. . __ ~ _ ~ ~ Arsenic X 0.052 6.2 ~ ~ _ _ _ ~
Chlorides X 49.6 3990 _ ~ _ _.
Sulfales Y: 500,300 . ~. - - ~

WO 93/25716 `P ~ / FR93 / 00543 211413 ~ 1 o TABLE ~ U 5: NORMALIZED LEACHING TEST (WITNESS 3 I _, _ _ _ Salaise Slag (S Il) Analynq ~ e monitoring of e ~ rac ~ ons _ _ Quantity Standards Standards Parameter 1st 2nd 3rd total ext ~ Class 1 ~ 1) valued ~ on eontrole Extraction Extraction Extraction of waste Class II (2) T ~ avawx Pub ~ _ _ gross ~ (mg) (mE / KE) (mg / kg DM) Odor Odorless Odorless Odorless ~ ~ ~
Color Yellow ~ Colorless Colorless ~ ... . . . . . __ ~ H 6 8 7.1 7 6 _. . . . .
Resistivity (Ohm crn) 0 900 3500 _ _. . ... ~ ~ ~ ~ ~ ~. .
COD m ~ O2 / 1 84 36 O 1200 <50 ~ (1) _. E_ ....... C400 (~) <iooo ~. . . . .......................,. .
~. . _ ~ _.
Concentlauon Concentrauon Q. ~ OL extr Standards Nonnes Nonn ~ s Elements of the first of the delL ~ th of the third dud ~ chet Class I Cla ~ se Il ~ TP (MS) extract (mg / l) ex ~ it (mg / l) extract (mg / l) bn ~ (mg / kg) (mglKg) ~ mglKg) (mg / kg) . __. . . _ _ __ _. ~,, ~ ~ Lead 0.443 0 116 0.0s2 6.11 elO0 ~ 30 <4 ~,. _. __. . ~ ~ ~ _ ~
Ca ~ nium 0.058 _ 0.015 0.005 0.78 <50 cs <I
Zinc 0.093 0.029 0.028 150 e500Copper 0.088 ~ 0.0 ~ 6 0.034 ~ I, 88 ~ - c2b <20 : ~ iekei ~ 0.338 _ 0.085 0 031 ~ <loo _ '0.100 0 ~ 000' 0.000 '' 1.00 -clOO ', ._, _'<I
Mereun ~ <0.003 ~ o.ob3 <0.003 e0.03 <10 <0.2 <0.2 :: ~: ~ vanures ~: ~ ND _ <io.
e0 0008 <0.0008 <oo 08 <0.008 ~ I0 <2 <2 ~: chlorides 338.3 85.6 9 5 4 333 ~ <lO000 ~ 2800 Sul ~ ates 1650 ~ 250 68 19660 == <4000_ ~: s ~ ~ lifes in the cen ~ res volanles from the incineration of urban residues.
N ~: not dosable, MS: mauères sehes Behavior ~ at solubil ~ satton - ~ -Behavior Quantites soluble in m ~ per K ~ of gross waste Elts Dissolu- Solubili-Solubili- ~ In Potentially total tion sanon sation solubilizable condihons ! _ decreasing sta ~ growing nanle ~ of the test _ (conc. waste) Lead X 6 ll 343 _ _ __ .. ._ _ .. ..

Cadmium X 0.78 3 ~ 4 . =. ,.
~ c X 1.50 94Q
_ __ ~,. . . . _,, ~. ~
(~ work X 1.88 14150 _ ... . . ~. . _. .
Nickel X 4.54 1523 Chrome _ _ l, oo IG92 Chiorures _ 4333 205bo ¦ Sul ~ at ~ s _ _ = i ~ 680 18Z00 ::

WO93 / 25716 2114 ~ PCI / FR93 / q0543 1 1!

TABLE 6. NORMALIZED LIXIY1AT10N TEST (WITNESS) Slag of Saint Vulbas (SY I) Annual follow-up of e ~ racnons ___ _. . _. . . . . .
Quantity Standards Norrnes Parsmeter 1st 2 ~ 3rd total ext ~ a ~ te aasse 1 (1) Yalorisauon en congrolé Ex ~ racnon Ex ~ ac ~ on Extrac ~ on of waste Class II (2) Pub Works.
_ _ _. _ gross ~ m0kg)! mQtK.Q ~ (mg / kg DM) O ~ eur lnodore Inodorelnodore . . ........................... .
Color colorless Colorless Colorless . ~ _ _. ~ ,,,. . .-. .
DH 9 ~ 4,936 85 _ ... _.,.
Resistivity (Ohm.cm) 2222 5435 8S95 ~; ~ 4 0 - O 40 <5000- (1) : ~ CO ~ / l _. . 10 <40o (2d <1000 ~ -. . . _ _ _ _ ~ ~. r , _. _ ~ __.
Concentra ~ ion ConcenuaLion Concen ~ ation 5 ~. tOL ex ~: r. Good Standards Elements of the first of the second of the ~ third of the waste Class I Class 11 ~ TP (MS) extract ~ mg / l) ex ~ milk (mg / l) extract (mgl) bnlt (mg ~ kg) (mglKg) (mg / Kg) (mglkg) Lead _ 0.086 0.03 1 0.018 1.35 <100 <30 <4 C ~ dmium 0.008 0.00: ~ 8 0.Q027 0.135 ~ 50.
zinc 0.0100.003 0.00l4 0.144 csO0. _ Copper ~ e ~ 0.0024 ~ 0.0010 ~ 0.0 ~ 07 0.04l = c20 _ <20 Nickel 0.0180.008-1 _ 0.0048 0.312 c100. ~
Chrome 0.027 0.0046 0.0077 0.443 <100 _ <1 ~ Mercu ~ <0.003cO OQ3 <0 ~ 003 <0.03 clO c0.2 co ~
Cvanur ~ s __ ~ ~ 10 _ ~; ii ~ <0.0008 <0.0008 <0.0008 <0.008 <IO <2 c2 Chlorides 54.6 ~ I l ~ g 4.0 70s. ~ cloOOO _ <2800 ~ SulfateS: T -: ~ ~ - ~ ---- <400V
rela ~ Jves: in Yolanaes provenanl land of the inclination of urba ~ ns residues.
non dosable, MS: ma ~ ières s ~ hes Behavior of sanofi _ ~ _ _ ~
: Composition of Soluble Quan ~
: m ~ by K ~ of bmt waste : ~ EIts Dissolu-: Solubili- Solubili- ~ iii ~ ii ~ Dtu ~ s lesPotentiellemen [
: uon totalesation sation saaonconditionssolubilisables decreasing ~ e sta ~ nante croissantedu ~ est ~ conc.d ~ che ~) !: ~ _ -. . _ _ _,. ~ ~
Lead X 1.35 190 ~ i ~ i ~ x _ __ -0,13s - 1,3 Zinc: ~ x _ 0, l44 620 x --- ~ 0 ~ 04l 8800 Nlckel ._. X _. 0.3 l2 784 Chrome x. 0 443 1 ~ 05 Chlorides x ~ 705.
: ~ _ ~ _.

W093 / 2 ~ 716 PCT / FR93 / 00543 2 ~ 7 12 Reading tables 4, ~ and 6 is made easier when the following remarks are taken into account, a the four right columns of the sub-tables medians and lower sub-tables:
- the "total quantity extracted from gross waste" in "mg per kg" corresponds to each ch ~ that element at lO times the sum of the quantities extracted by the three solutions of extracts (or extractants) used to treat l00 g of the same waste.
- these numbers are to be compared with the standards which appear in the three columns to the right of the median tables (and which correspond to the values indicated in the columns "French standards class Il ', French standards class IIIl of table 3 and "Standards : ~: Valuation in Public Works "from ~ ableau 2).
these same numbers are, in the sub-arrays lower, compared to the con ~ entrances of the elements "potentially solubilizable" correspondents, who are other than the values corresponding to the same :::
slag and grade taken from the table lo From the examination of Tables 4, 5 and 6, we therefore had make the following observations about the possible character ~ polluting slag examined at ti ~ re examples. ST l, SII and SV l samples lead to colorless and odorless leachate. The chemical oxygen demand (~ C0), pollution index mineral and organic, is 240 mg / kg for ST l, l ~ 00 mg / kg for IBS and 40 mg / kg for SV l.
with soluble fraction of ST l slag (Table 4) risk of inducing pollution constituted by copper (total quantity extracted in mg / kg higher than the standard class II and not in conformity with a recovery in : ~ ~

WO93 / 25716 2 1 ~ 413 l PCT / FR93 / 00543 .
13.
public works), zinc, nickel and chlorides (increasing solubilizations in successive eluates).
For the SII leachate leachate (Table 5), all the dose elements have solubilizations decreasing. But they have a higher elution threshold to European standards on non-hazardous waste for lead (8.72 mg / kg of dry waste), cadmium (1.11 mg / kg of dry waste), chromium (1.42 mg / kg of waste dry) and nickel (6.48 mg / kg of dry waste). By elsewhere, these leachates are not in accordance with the legislation which provides for the development of mints in public works (lead, cadmium, chromium and chlorides have too high threshold concentrations).
The llxiviats nevertheless comply with standards French Class II Ps.
The leachates obtained from the dried SV 1 slag are conform to the above standards (table 5).
It therefore follows from the above that some of these slag would be treated decontamination before any storage, burial or valuation ~ It should also be the same for SV 1 slag, even if it does already to the tolerated standards to date, but ~ ui could no longer be so in the future.
The object of the invention is precisely to develop of a process allowing the preservation of the environment while limiting the expensive storage of slag, especially in a Class I landfill. Eile has more particularly for object a stabilization process combustion residues, whatever their origin, by extraction of the soluble metallic fraction.
The inventio ~ more particularly aims, in reference to french and european standards in W093 / 2S716. PCT / ~ 93/005 ~ 3 ~ 3 1 14 force, to obtain in a particularly simple way the detoxicatibn or "inertization" of slag to the point that they can then be stored in es Class II landfills for non-hazardous waste or even recycled.
According to a first essential provision of the invention, it consists in first making one or several slag leaches, if necessary previously ground to a sufficiently large particle size low, especially at values below 50 mm, to allow sufficient contact between the residues of combustion and an aqueous solution or liquor of leaching, having a sufficient concentration of cations (K +, Na +, Ca2 +) or protons exchangeable under form of chlorides with heavy metal cations present in these residues. This leaching must be sufficient to transform at least one part of the determined metals, in particular heavy metals contained in this slag, in soluble chlorides ext ~ ractlbles with this leachate liquor, and their effective extraction in sufficient proportions so that :
on the one hand, a standardized elution test u ~ ltérieurement applied to the slag thus treated attest to the decreasing quantities successively solubilized: of each of these metals determined during repeated extraction tests carried out with a standard solution for leaching or conforming elution : ~:
::: to this test and, on the other hand, the sum of the solubilized quantities in the eluates resulting from the extractions with the above normalized solution, has values corresponding at concentrations below the threshold concentrations :::
: ~
. . .. ,, .... .. ........ ~ .. ,,. ,, .. ... ~

WO93 / 25716 211 41 ~ ~ PCT / FR93 / 00543 also predetermined by the above standardized test for each of these metals.
For clarity of language, it was done in what precPde Pt will also be done in the following, a distinction between:
- "leach solutions", that is to say, extraction solutions containing the above-mentioned cations or exchangeable protons and - the corresponding "standard elution solutions"
to the solutions implemented in the above tests normalized.
The number of successive elution tests and the concentration thresholds (at least for those of metals already subject to special standards) are determined by existing standardized protocols or fukurs. The standardized study protocol used in the present study corresponds to standard AF ~ O ~ (X31210, 1988) whose detailed implementation has been recalled below above.
n the occurrence of repeated elution tests with the .
normalized solution are then 3 and the solution no ~ malised is itself constituted by a water demineralized saturated with air and CO2 at pH 4.5 and resistivity between 0.2 and 0.4 Mn.cm.
Elution tests with the standardized solution are then made by mixing the treated slag ~ for example used at a rate of 100 g) for 16 hours and with stirring.
Exchangeable cations or protons ~ in the form of chlorides in the liquor used for leaching initial slag can be brought under any form to achieve the goal to be accomplished. The leach solution may consist of acid WO93 / 257l6. PCT / FR93 / 00 ~ 43 2il 4137 16 dilute hydrochloric, more particularly for treatment of basic slag, for example slag which, when suspended in the water for a sufficient time J have the effect of bring the pH to values of the order of 9 to 10.
For neutral slag in the same conditions, it is preferable to have recourse to solutions of metal chlorides ~ alkaline or alkaline-earthy, rather than hydrochloric acid. The experience indeed shows that hydrochloric acid, even in the state diluted, sometimes tends to attack, more than it should be, the matrix or gangue of slag of a neutral character.
It will immediately be apparent to those skilled in the art that let's concentrate solutions in exchangeable cations under chloride form ~, or even the nature of the cation used, ~. :
(preferably potassium, calcium or other alkali metal or alkaline earth) will most often be adjusted according to the treated slag and nature heavy metals that can be mobilized.
Generally the acid concentrations hydrochloric acid solutions applicable to treatment according to the invention, will have c ~ oncentra ~ molar lons most often included in intervals of 0.01 M to 1 M, while the alkali or alkali metal chloride concentrations errant corresponding leach solutions will most often be in the interval O, O1 M, ~ especially 0.05 M, at 5 M.
As observed in the case of experiments performed on various types of slag, a solution 0.1 N hydrochloric acid is a reagent particularly suitable for slag treatment basic, while a solution of potassium chloride W093 / 2 ~ 716 ~ 1 i 4 ~ 3 ~ PCT / FR93foo ~ 43 1 M or calcium chloride O, Ol a 2 M, in particular O, 09 M and O, 15 M, will allow the extraction of metals available in the slag presenting a low acidity. This static or dynamic leaching (slag / extractant ratio l, l) will be followed by drainage leachate to a storage tank. They could also be treated themselves as discussed ~ below.
Example: Slag from the incineration center in Strasbourg (ST l) were crushed, crushed and divided for the reconstitution of an average sample homogeneous with particle size O to 2 mm. The slag of Saint ; Vulbas (SV l), were previously dried before being gathered in average sample. Salaise slag (SII) were ~ treated as is. The samples of Strasbourg (ST l), Salaise II (SII) and Saint-Vulbas : ~ ~
(S ~ l) respectively have a pH of 10, O, 7.6 and 8.2.
Experimental setup: _ metal extraction exchangeable:
The extraction tests are carried out by tests ; leaching in a clogged column or in leaching dynamic (with stirring ~ on 100 g of slag.
reagents used ~ 100 ml for 100 g of slag) are hydrochloric acid O, l N, potassium chloride l M
or 0.09 M and 0.15 M calcium chloride. They are left in contact for 2 to 24 hours with the slag and can undergo 2 recycling ~ or at least 3 times 24 slag / extraction liquid contact hours). PH, conductivity and chemical composition are determined on the leachate obtained. The sample of , ::
slag is then rinsed with at most 2 times 100 ml distilled water then the standard leaching test is applied.

211 ~ 13 ~ 18 Results:
Extractants used in mobility tests form chlorine slag with the elements metallic solubl ~ s whose formation speed is depending on their solubility constant.
As examples, 1M potassium chloride results in significant solubilization of calcium and copper in ST l slag. Potassium (reactive in excess ~ and sodium, not doses in these tests, reveal, during dosages, to be matrix elements having a negative impact on analyzes ~ emission yellow in plasma). The elements very solubilized are shown in Table 7. In SII slag, the most mobile elements are manganese and ::
magnesium for the major elements, the elements traces being dissolved in varying proportions (table 7). The analytical disturbance, due to a massive solubilization of alkaline earth elements is also noted in these solutions from SII slag.
Hydrochloric acid more efficiently mobilizes metals, in particular, copper in ST l slag.
Dissolution of alkaline earths by this reagent disrupts the dosage of calcium, while the plasma emission is synonymous with a strong presence of sodium (Table 7).

~, ~:

WO93 / 25716 ~ 3 ~ P ~ / ~ g3 ~ 00 ~ 43 . ~.

!

Table 7; Determination of the mobility of 9 major elements and 7 trace metals during lixiYiation in a column engorged with 100 g of slag per lO
ml of extractant (3 successive passes). Analyzes of the lixiYiates obtained by dosa ~ e ~ metallic lémeslts soltltion spectrophotometer plasma emission. Results expressed in terms of weight content initials.
__ _ _ Elements extracted ~ in%) by Elements extracted ~ in% ~ by potassium chloride 1M hydrochloric acid 0 ~ 1 N
~ ~. . _ : ~ Elemenls re ~ herchés Scories ST 1 ScoIies S II Scories ST 1 Scories S II
:: ~
___. _. . _.
Aluminum 0 00 O 00 0 33 0 01 . ,. _. _.
Calcium O 0 ~ O 00 non-dosable non-dosable .. __ .....
Man ~ anesis 0.00 0.14 0.41 0.60 ~ ~ ~ __. ~ ... .. _ .. ...
Ma ~ néiuTn O 01 1 05 0.64 S, 45 _. . _ ~ ~
Iron 0.00: 0.00 01 7 0.00 ~ Silicon ~ 0 ~ 00 0.00 ~, 19 0.01 ___ ...... ~ _ ~
Non-dosable potassium non-dosable ¦ not dosed not dosed :: ~ odium not dosed not dosed not dosed not dosed - ~ ~ ~ ~ ~
: ~ __ not dosed not dosed L ~ nondose Co ~ alt 0.00 0 19 1 ~ - 0 ~ 59 ~ Chr rne 0, (~ 0 0.03 0.00 0.04 . - ~.; . ,, _ ~ ~ ~ _ . ~, :: C ~ uivle 0.02 0.00 10 10 _ ~ .00 iNi ~ kel :: 0 ~ 00: 0.04 0, û8 Q, 32 ~ ~. - ~ ~ - ~
Zinc ~ Q.00 0 01 0.13 0.04 ~ ~ _ ~ ~ ~ ~
Cadrrium 0.00 Q 00: L ~ 0.00 ~ PIomb _ _ ~ 0.0 ~ 0.18 ~ ~ 0.23 , , ~: ~. .

:

WO 93/25716. 'PCI` / FR93 / 00543 r) 20

3 ~

Table 8: Determination of the mobility of 9 major elements e ~ of 7 n ~ trace vices during rinsing (2 ~ lois 10 ml of distilled water) coloD ~ are engorged 100g of slag after treatment with 100 ml of extractant. Analyzes of water obtained by dosing metallic elements in SolutioD at ~ plasma mission spectrophotometer. R ~ sllltats e ~ awarded as a percentage by weight of the initial contents.
~ r : Elements extracted (in% ~ by ¦ Elements extracted (in% 3 by potassium chloride ml MI hydrochloric acid 0 ~ 1 N
_ I -, I
Elemen ~ s reche ~ hes Scones ST 1 Scones S II ¦ Scone3 ST 1 Scones S
. ~ ~ ~ ,,, _ ,, Aluminum O 00 0.00 1 0.01 O.0Q
~: ~. ~, _ _ ~ C ~ cium 0 00 0.00 1 0.01 not dosable __ .. ~. . . . . ,. I ~ ~.
~ n ~ e: 0.00 ~ 02 ¦ 0.01 0.23 _ ~: ~ Aa ~ neesium O 00 O 0 ~ 1 0, ~ 4 0.51 ~ ~ _ ~,. I, _. ~ ...
~: er ~ 0 00 0 00 1: O.QO 0 00 _ __ ~ - ~. . ~ I_ ~: Sili ~ ium: 0.00 0.01: 1 0.01 0.01 : ~,. _ I ~ _. . . .. ...
~ ~ IPot ~ ssium ~ not dosable not dosable l not dosed not dosed ~ ~. ~ ~ ~
S ~ odium ~ ~ not dosed ~ not dosed ~ nondose not dosed ~ Phos ~ hore not dosed not dosed: not dosed not dosed , - ~
C: not dosed not dosed no: dosed not dosed - - not dosed: not dosed not dosed not dosed ~: Cu ~ ~ ~: 0, ~ 0 ~: O.QO: 0.59: 0.00 , _. ... ... ~ ... ~ ~
~ Nickel ~ ~ 00 0.01 ~ \ :: ~ 0.01 0.11 : ~; ~ - ._ ~ ~ ~
~ ~ 2 ~ n ~: ~ 0.00 ~ 0 ~ 01: 1 0. ~ 7 1 0.02 ~. ....... I ........... ~
~ Cadrnium ~ 0.00: 0.00 0.00 0.00 , _ ~. .... _ ~
~: ~ lom bi ~: 0 04 0 14 0.07 0.19 ~:, _ _ ~

:,; ~ ::
.

.. ... ... .. =. , ... .. ~ .. = .. .... . ~,. . . ~.;

WO93 / 25716 21 1 ~ l 3 7 PcTtFR93 / 0o543 The purpose of the rinsing water is to eliminate excess of reagent before the implementation of the test normalizes leaching. During this operation, a low mubility of ~ elements should be noted be the extractant and the slag considered ~ array 8).
Percentage of metals available for slag could not be assessed precisely but the analyzes partial performed during successive passages of reagents have suggested that only a contact of 2 to 24 hour slag / extractor and a single rinse would be necessary to obtain a sta ~ ilisation effective of these wastes. This simplification by limitation of the number of operations initially planned demonstrates the interest of a single leach and constitutes an optimization of this process.
est_normalise de lixivia ~ ion Taking into account the fixed objectives within the framework of these examples, the leaching tests should follow French class II standards and European standards on non-hazardous waste or to the standards of ~.
The promotion of mints in public works.
At the end of the two treatments applied on the slag from Strasbourg (ST 1) and Salaise II (SII), the standardized leachate tests lead to for ~ nation : de} ixiviats having a higher resisti ~ ite compared to witnesses, therefore has less effluents: charged in ~, mineral elements (Figures 1 and 2).
The reduction of chemical oxygen demand (COD) is 23% after treatment with pot chloride ~ ssium : ~ on Salaise II slag (SII), it is 100%
for all other processing e ~ whatever the ~: considered slag (f igure 3).
:::

; ::

WO93 / 25716. PCT / FR93 / 0 ~ 3 1 3 ~ 22 Note that in Figures 1 and 2 on the standardized leaching test on slag from Strasbourg ~ ST 1) and Salaise respectively II ~ SII), the variation in resistivity has been illustrated leachate before and after treatment with liqueur leaching, revealing what the resistiYites expressed in ohm / cm on the axes of ordered after application of the standardized test (standard AFNOR X31210, l9B8), - directly on the slag in question (TN), - on slag pre-treated with a solution of potassium chloride (KCl), and on the slag treated beforehand with the solution of hydrochloric acid (HCl).
In Figure 3 ~ are also illustrated the COD allowances (COD% on the ordinate axis) following the treatment applied to the slag of Strasbourg ~ ST 1) and Salaise II (SII).
For polluting metallic elements, the chlorides and cyanides, the standards exist decreasing olubilization and / or an elution threshold. The ~ ~,,. :
determination of these parameters for slag ortement basiques de Strasbourg tST 1) shows the following results: ~ ~
treatment with chloride solution potassium is manifested by strong extraction of metals : pollutants; but we observe that several metals (lead, copper and chromium) as well as chlor ~ res give place with increasing solubilizations ~ table 9), on the other hand, hydrochloric acid treatment (table 10) accentuates the solubility of the elements pollutants, but the elution threshold imposed with a solubilisa ~ decreasing ion remains compliant with standards W093 / 25716 211 ~ ~ 3 7 P ~ T / FR93 / 00543 . .

French and European waste standards Not dangerous. The corresponding production of cheeses would also be suitable for public works.

Tables 11 and 12 illustrate the results obtained under similar conditions, in tests of Normalized leaching after slag treatment, IBS
after treatment with potassium chloride (table 11) and hydrochloric acid ~ Table 12).

: ~ ~

. '' .
, :

~ ~:

::
,: ~::

::

. . , WO 93 ~ 25716 PCI` / FR93 / 00543 1 ~ 1 3 r ~ -. _. . . . . .. ~ _ ~ ~. . _ .... .
TA ~ LEAU 9: STANDARDIZED LEACHING TEST AFTER TREATMEIYT AT KCL
.. ~
Strasbourg slag lST I) Sl ~ iVi analyti ~ u ~ des e ~ racions . ,,. _ Quanti ~ é Standards Noq ~ nes Parameter 1st 2nd 3rd total extracted Class I (1) valuation in controlledExtraction Ex ~ caon Ex ~ ac ~ on dud ~ chet Class II (2) Pub._ works. . . . _ gross (mJkE) (mR / X ~) (mg ~ kg DM) Odor Odorless Inodorelnoda ~
. . . . . ~. . .
Colorless neck. Colorless colorless ~. ,. . .
P ~ 7.0 6.46.0 Resistivity (Ohm.cm) ~ 45000. ~.
COD m ~ O2 / 1. O. <5000 (1) ; :: N COT m ~ / l _ EE. C400 (2) __ ~, ~. ~. . . ~. _.
Concenua ~ ion Concenuauon Concen ~ a ~ ion Q. tot. e ~ tr. Norrnes Nqrmes Norrnes Elements of the first of the second of the third of ~ ch ~ Class I Cla ~ se II * TP (MS) ~ ex ~ mg, ~) extlait (mgll) ex ~ (mg ~ gross (mglkg) ~ mg / Kg) (mg ~ Kg) ~ mglkg) Lead 0.0 ~ 4 0 ~ 001 0.014 0.59 <100 <30 ~ dmium ~ r ND ,,,,, ND ,, 'tSO
Zitlc _ 0.282 ~, 2g3_ 0.278 8 53 cS0Q _ -Copper 0.676 _ 0.1 500.239 10, ~ 5 c20 <2 ~
Nickel ~ 0.052; 0.031 0.031 ~, ~ 4 <100 _. .
C: i ~ t ~ me 0.050 0,000 0,000 0.60 ~ 100-- c 1 Mercury <o 003 <0.003 <0 003 ~ 0.03 s10 <0.2 <0.2 ~; i; ~ ._ ~ ... _, ~ ._. ~ 10. . _ Arseric o 0009 <0 0008 ~ 0 0 ~ 08 0.009 c10 <2 <2 ~ __. ~. ... . ....... . _.
CHLORIES 0 8 2 33: 0 62 37 5 C10000 c2800 .. -. . ~. . ... . . . . ......... ~
:: Sulfates ~:: 14:: 2.2 cl, 0 36.0 <4000 ~. . . .. _ __ .......... ..
rel ~ uves: aux: ash volanles from the inciné ~ auon of urban residues.
ND: not dosable, MS: dry mauères Compor ~ ement to the soil ~ bilisa ~ ion _ ~ ~ _ : Behavior ~ nt Quantltés solublllsablesen -:: ~ m ~ per K of gross waste ~ ~ ~: ~. _. .................. _, ~
::: Elts Dissolu- ~: Solubili- Solubili- Solubili- In: Potentially tiontotale sation sation sanon condi ~ onssolubilisable : decreasing sta ~ nante. increasing duteslt I (conc. waste ~
d1, I: _. . _ _ _ _ Lead _ xo, sg 186 zinc: ~ X 8.53 CulYre _ ~ ~ x 10.65 ~ 800 :::, ~. _. , _ _ _ ___ _ _ ~
Nlckel x 0.312 s800 : ~; ~ -. ~ - 0.60 20,800 ::: Ass ~ ic _ x. __ 0.009 6.2 : Chlorides. _ ~ 37.5 3990 . . ... . . ~ ... . . _.
:: Sulfa ~ es x 36 0 300 "_ ~. _. ~ _.
::
~:

WO 93/25716 PCI` / FR93f00543 ¦ TABI, EAIJ 10: STANDARDIZED LIXIYIATION TEST AFTER HCL TREATMENT ¦
Strasbourg slag ~ (ST I) Analytical monitoring of exlracnons . ___. . ,. _. . . . .__ Quanu ~ Standards Standards Parameter 1st 2nd 3rd ~ tale ex ~ aite Class 1 (1 ~ recovery in control Ex ~ ac ~ on Ex ~ cuon Ex ~ c ~ on of Class II waste (2) Public works.
gross (mg ~ kg) (mv / KQ) (mgfkg MS) . _ _ _. _. ., ~., Odor Iridore Odorless Odorless . , ... . - ,. . ~
: Color lncolore lncolore Colorless pH 7.0 6.4 6.0.
RésistiYilé ~ Ohm.crn) 70,000 80,000 90,000 _ -1 ~ Il ~ e O ~ / 0 - 0 0 <5000 (1) CO ~. . ~. r, E _E ~ j ~ C1OOO
Concenu ~ uon Concenuaion Concentrauon Q. o ~ e ~ r. Norn ~ es Standards Standards Elements of the first part of the second of the third duet Class I Class II II TP (MS) ~: ~ ex ~ (m ~ exuail (m ~ / l) ex ~ ait (m ~? bru ~ (mg ~ g) ~ mglKg) (rngl} Cg) (mg kg) PIOmb 0.075 0.029 0 ~ 015 1.19 ~ 100 <30 <4 adm; Um - = ND = ~ 50 <5 C
ZinC ~ 0.132 ~ 0.070 0.048 2.50 <500 ~ 0.723 _ --0.295 0.j97 12.15 = <20 ~ --C20 N; Ckel 0.064 ~ 0.015 0.041 1.50 ~ 100 _ -ChrOrl1e ~ 0.040 0.000 0.000 Q 04 C100 <I
Me ~ UrO <0.003 <0.003 <0.003 C0 03 C10 ` <0 ~ 2 C0.2 : ~ VanUreS ~: ND ND ND. ~ 10 , ~ ~, __ __ ~ _ _ ~ ~
ArSeniC: 0 0071 0.0025 C0.0008 0.096 <10 <2 <2 ._. . . . _ _. .
~ h1OnlréS 5 92 1 05 1.Q0 79 ,? <10,000 ~ 2,800 , ~ ~. , _. . ... _ __ _ ~:: ~ SU1faleS: 24: 2 4 12 276 ~ 4000 ~ ~. . . . . ... . .. ........ . .
fly ash telaLives: Provenam from the incineralJon of sesidus ~ they.
ND: not ~ dosable. MS: dry matter Behavior in soluJil ~ sation : m ~ ~ ar K de deChet brUt ~ ~ ~ _ ~. . _ ~ ... .., ~
:: E ltS: DiSSO1U SOIUbili SO1Ubi1i SOIUbih Dar.S the potential ::: ~ On tOtaleSatiOn Sa; On Sa ~ On COndinOnS SO1UbihSab1eS
DeCrOiSSanle Sta ~ nante grOissant DU TCSt ~ COnC.déChet) _. ... , ........ - .... ~ ~, ...
PlOm b X 1.19 186 _,. . . ~
::; : ~ nC X 2.50 ~ 900 : CU; VT ~ X ~ ~ ~ l2 l5-- 48 () 0_ ~; Ckel ~; 1.50 5800 ChrOrne - X. - 0.04 20800 . . . _. ... ~
~ ~ ~ rSeniC X 0.096 6.2 . ... _. . _ ~ _ ~ _ CHORES X 79.7 3990 _. __ ~. ...... _ S ~ lfateS X 276 300 _ __. ~

, ~.

WO 93/25716 PCr / FR93 / 00543 .
13 ~ 2 6 TAI ~ LEAU 11: STANDARD LEACHING TEST AFTER TREATMENT AT KCL
. -. ~
Slag from Salaise (S II) Analytical monitoring of e ~ ra ~ ons _,. . . ~ .. ~; ... ..
Quan ~ ity No ~ nes Nonnes P ~ reduces 1st 2nd 3rd ~ tale e ~ e Clas ~ e I (l) valuation in cont rolé Extrac ~ ion Ex ~ ac ~ on Ex ~ ac ~ on of d ~: het Class II (2) Pub Works.
. gross (mg / ~ g ~ (m ~ / Kei (mg / kg DM) _ _ _ _ _ _. _., Odor Odorless _ Odorless lnod ~ e Color _ lncolore Tncolore Colorless. _.
~ 71 7, i 7.2.
Resistivity (Ohn ~ .cm) 800 2600 ... . .. _ D CO m ~ O211 20. . 280 (1) ~. - _ __ ~
: ~ CO T. m ~ ll ~ E. ~ _ ~ _ <400 (') <1000 .
_ _ Concentrauon Concentsauon Concemration ~ ~. ~ ot. ex ~. NonTles Norrnes Standards Elements of p} ~ mier du de ~ th of third dudéchet Class I Class II ~ TP (MS) extr ~ ut ~ mg / l) exuail (mgll) ex ~ a (mg / l) crude (mg / lcg ~ (mg / Kg) (mgtKg) (mglkg) ~ ~ ~ ~.. _ _ Plbmb 0.181 0.06 0.024 2.65 _ clO0c30 <4 ~; ~ 0.023 -0.008 0.004 0.35: ~ 50 ~ 5 <I
~ inc ~ ~ 0.037 0.017 ~ 0.011 0.65 ~ 500 _ _ ~; i ~ ~: 0.045 0.036 0.014 0.95 <20 <20 Nickel 0.139 ~ 0.053 0.023 2.20 <100 _ ~ ~ 0.0 ~ 0 ODOO 0.000 0.60 clOû <I
Wed ~ cO.003 <0.003 cO.003 <0.03 <10 <0 ~ 2 <0.2 ~ Cvanures ~. ~ _ _ ~ C lO. _ _ ~ 0 ~ 0008 ~ 0 ~ 0008 <O.OOOg ~ 0.008 ~ 10 ~ <2 <2 (:: chlorides127.0 17 ~ 0 3.2 1472 clOOOO <2800 Sulphates ~: ~: __. _ - ~ <4000 ~ Relauves to the vslantes areas coming from the incineration of urban residues.
ND: no: dosable, MS: dry matter To be part of the sDIubilisadon Solubilizable quantities ~ ~ :: mg per Kg of waste bmt Elts Dissolu- ~ Solubili-Solubili- Solubili- Dtu ~ sles I Potentially tionlot ~ lesation sation sanon condi ~ water-soluble _ ~ decreasing s ~ nante oissan ~ from ~ east; (waste waste?
Lead X 2.65 343 CaZium _ 0.3s 3.4 . _ _, ~
~: Zinc X 0.65 948 . . _. ... . . ...
(_ulvre X o 9s 1450 ... _. . . . _ _.
Iiiickel X 2.20 15 ~ 3 Chrome _. . . . 0.60 1092 ~ :; Chlorides X ~ ~ 1472 20500 _ ~

WO 93/25716 21 ~ 413 7 PCI / FR93 / 00543 TABLE 12: STANDARD LIXIVlATION TEST AFTER HCL TREATMENT
. ~
Salaise slag (S II) Analogical monitoring of ~ tra ~ fions . _ .... ~ ..... - ~ ~.
Quanti ~ Norms Nom ~ es P ~ ramère 1st 2nd 3rd total extracted Class I (1) upgraded to controléExtracion Ex ~ rac ~ on Extraction of waste Cl ~ sse Il (2) Tra ~ rallx Pub.
~. gross (mglkg) (me / K ~) (mglkg MS) Odor Odorless Odorless ~ odorless ~ ~ .__. . __, ~
COLOR Colorless Colorless Colorless ~. _. ~.
PH _ 6 ~ 8 6 6 7 Resistivity (Ohm.cm ~ 1000 3000 6000 COD m ~ O2 ~ __ 0. <5000 ~) CO ~ = EEEE <400 (~ <1000 ::
_ Conccnua ~ ion Con ~ en; sauon Concentra ~ ion Q. tOt. extr. Good Standards Standards Elements of the first of the dellxth of the third of the d ~ he ~ Class I Class II * TP ~ MS) extracted ~ (mg / l) extracted ~ (mg ~) extract (mg / l, ~ bn ~ t (mg / kg) (mg / Kg) (mglKg) (mg ~ cg) ~ __ ~. ._. ~ ,,. . . .
PIOm b 0 421 0 l 56 0.058 6.35 <100 ~ 30 <4 ~ ~. . . . . _ _ Cadm; Um 0 056 0 020 0.007 0.83 <50 <S <I
~, ~,. _. . . . ... ... , __ zinc O 1 1 8 ~ 0 044 0 0382.00 <500 ~: __. ~. _ _. .
: ~ Copper ~ 0 071 0 0 ~ 8 0 023 1.42 <20 <20 ~. -.,. __ _ ~ ~ _ Nickei 0.913 O259_ 0.122 12.94 clGO. ~~.
Chrome 0 020 O 010 O 000 0.30 <~ 00 ~ 1 - :: Merc ~ re <O 003 co 003 <0.003 c0.03 ~ 10 cQ, 2 <o,: l : ~ ~. . ~. . 7 '- _:. . _ _ N / A ND <10 ,, _ ~ ._. ~ _ ~ _ . n: ~ - Arsenic ~ 0 0008 cO 0008 <0.0û08 <0.008 <10 <2 <2 . _ =. . ~. . ~ ~
(~: chlorides 33.3 17 2 7.8 583 clO (~ O c2800 _ _,. . . . - _,. . ,. .
Salfales: _ - _ _ - - <4000 : ~ rela ~ ives to Yolan dres ~ e pr ~ coming from the inciJlélation of urba ~ ns residues.
ND: not dosable. MS: dry materials Compor ~ emen ~ à ~ a solubilisahon _ ~
~ Behavior Quantities soluble in m ~ per K ~ of gross waste Elts l ~) issolu- golubili- Sol ~ bili- Solubili- In Potentially total tion: its ~ ionization condi ~ onssolubilisable decreasing staanante increasing test (conc. waste) ~ i ;; ~ X 6.35 343 ~ Cadrnium = - 0.83 3 ~ 4 -zinc X 2 00 "~ 8 . . . _. ,. . _ (_follow X 1.42 1450 Nickel ~ _ ~ ____ _ 0.30 1523 Chrorne. X: _ 0.60 1092 Chlorides ~ X _ _ 583 20 500 WO93 / 25716 PCT / FR93 ~ 00 ~ 3 21 ~ 413r7 CONCL ~ SIONS:
Depending on the leaching tests performed on slag and its planned storage in class II
or their recycling, the following conclusions ~ table 13) can be drawn from previous experiences, after application to treated or "assessed" slag, study protocol according to the above-mentioned AFNOR standard:
- Strasbourg slag (ST I) without treatment preconditions generate eluates whose toxicity thresholds are superior to French class II standards, in addition to European standards. These eluates are, by elsewhere, not in conformity with the legislation which provides for a recovery of slag in public works. After pre-treatment of slag with hydrochloric acid, the eluates produced comply with French standards Class II, to European standards on non-waste dangerous, the treated slag may also be recycled into public works.
the soories of Salaise II (S II) without treatment preconditions generate eluates whose toxicity thresholds are lower than French class II standards but higher than European standards for non-waste angers and to standards of valuation in works public .: After treatment with potassium chloride, : eluates produced comply with: European standards and the standards of recycling of the chews.

:,:

, ~ ~
: ~:

:
::

WO g3 / 25716 PCI '/ FR93 / 00543 21 l 4l37 e-- _ . ,, ~ ~ E, ~, x ~ ~ V n ~ ~ CO ~ OO ~ - ~ r O ~ q o-- O
. ~ ~ ~ ---- V ---- ~ ~ `O` VO. . . I ~. . . . . .
- e _ _ _ cô ô û, u ~ ~ 8` ~ O ~
~ ~ .C ~ X c ~~ ~ ~ c o-- ~ Y o` ~
~ o ~ c ~ ~ E e _ ~ c ~ o ~ ~ æ u ~ ~

C ~ C ~ _, _ ~ ~ I ~ V ~ OOO ~ OO. _. . -~ u, 51 - ~ - - ~ ---- ~ O ~ C

u ~ o. ~ ~ c, ~ Y ~ _ 8, ~ lc ~ g c, 0 ~ _ -C ~ - C ~ ~ UU ~,.
.-- c ._ ",, _ _ O ~ C o ~ U ~ OR ~ t ~, r ~,..
E ~ _ : ~ E _. ~ ~ 'Yoo ~ _ ~ ~ o ~ ~ "EE, ~, ~ o O ~ o ~, v ~ n....
.9. . .

z = ~ ~ E d ~ go ~ o ~ 8 c ~,, ~ vvvvvvv. e. v ~ v "~. 0 U ~

J _ za ~ ~ E 8 'EE ooo 8 8 o ~ o ~ o V ~: _ 'C? .. VVC ~ v vvvvvvvvvvv U, r _ ~ L ~ ~

E Ia ~ c, zq ~ ~ o ~ ~ v ~ vvv. . ,. v,. ,,,,, fi,: ~
uc ~ ,: oO æ ~ ~ `
0 ~ c, ~ ~ ~ c ~ g ~ ~ v -vv ~ v -ve ~ ~ vg æ ~ oD ~ D ~ `8 o ~, _ -. ~ E ~
c ~ ~ ~ 3 COO ~ ~ V ~ ~ O ~ oooo OOO ~:
U ~ VV, VVVV, VVV ,, .......,. ,, t.
_ ._ _ ~

~ ~ o ~ r ~ ~ _ ~ ~ OO 8, ~ ~ 8 g 8 5 ~ ~

G. ~ ~ ~
~; ., ~ c ~ ~ _ c ~ _ ~ c ~ ~ EE

WO93 / 25716 - PCT / FR93 / 00 ~ 43 Leachate resulting from the application of the procedure of leaching contain chloride salts metallic as well as an excess of extractant ~ La average composition of leachate and rinsing water, all treatments combined, obtained during our experiments on 100 g of slag, is given in the table 14.
Table ~ u 14: Chemical analysis of leachates and rinsing water.
Mo ~ enne composition obtained from dif ~ éren ~
treatments performed on the slag from Strasbourg (ST 1) and Salais ~ S n).

RINSING WATER LEXIVIATES
. _ _ _ ~ _ ~ H _ _ _ 1.86 to 9 3? ¦ 4.30 to 8.9 ~ `

______ ~ _____ ~ ___ Concen ~ ationenm ~ ¦ Conmm cnm ~ 5 Al lum _ _ 0.4 ~ 170_ _ 0.05 ~ 3.0S
~: ~ 0.5 to 415 _ û, 06 to 10.78_ 285 _ O 12 i 21.76 :! ~ 5 ~ 0.02 to 60 0113 i 2U ~; 2 S ~ i ~ ium 1 2.6 ~ 256 _ 1 _ cmm _? _ ~ _ ___ 5nd ~? 7 C ~ m _ _ _ 0.1_ to 484 Zirlc _ _ 0.04 to 2 ~ 4 Lead ~ 0.6 to 0.9 _ ~
Nickel _ _ 0 6 to 4.7 ~
Chrome _ _ 0.3 to OS _ _ 0.18 to 1.2]
~ D ~ O _ ~ leaching has been extended to other reagents -: ~ under different conditions.
~: ~

WO93J ~ S716 211413 ~ PCT / FR93 / 00 ~ 3 . ~

The transformation of slag into inert rubble operating under the influence of cations or protons exchangeable, the investigations focused on the use of saline discharges for reaction purposes and acids from incineration centers.
Experimental extraction device Leaching was carried out with stirring (dynamic leaching) in 2 liter bottles with at most 1 liter of extractant in the presence of lOOg of slag. Given the preliminary experiences, incubation was continued for 2 hours at ambient temperature. A single rinse with at most one liter of distilled water is made after treatment. Solid liquid separation is carried out by : centrifugation at 2000g. For analytical purposes, a filtration is carried out on Millipore membranes of 0.45 m diameter.
Saline treatment of slag from the incineration of chlorinated waste.
Dynamic leaching of SII slag; leachate and waters : Leaching was carried out on SII slag by Rhône effluents-discharges from the center of REDI Saint-Vulbas (Ain), this extraction reagent corresponds to an immediate withdrawal made in January 1992 at the exit of the clarifier (table 15).
The SII slag also underwent extraction by a reconstituted calcium effluent (~ calcium chloride to lOg / l, which corresponds to a molar concentration of 0, O9M). They were also leached with 1M potassium chloride.
Results WO93 / 2571 ~ PCT ~ FR93 / 00543 f. ~. ~
211 ~ l37 32 The use of saline discharges in accordance with the regulation as an extraction reagent leads to considerably lower the elution thresholds compared to the witness test (tabl ~ at 16). This Dynamic leaching significantly mobilizes 1 ~ nickel. The chrome, despite its abundance in waste, remains insoluble. The COD remains unchanged while the TOC
decreases by 50%, due to adsorption of organic matter on the slag (Table 17).
The use of a reconstituted calcium effluent leads in identical conditions to results :: similar (table 18).
: ~: Treatment with potassium chloride leads to less nickel extraction but mobilization : more efficient of copper (table 19 ~.
::: The rinsing water leads to all treatments to remove residual solubilized elements : and to remove the excess of reagent (tables 17 to 19).
:: Demonstration of the stability of the slag Salaise slag II by saline discharges or : reconstituted see their soluble fraction decrease for : become compliant with a valuation in public works.
The leachate COD is: lowered, as is the solubilization of chlorides, while the content of sulfates reaches a concentration below threshold values: ls of the public works standard (such as modified in 1992). The decreasing solubilization of , nickel is also established (tables 20 and 21).
Salaise II slag leached by KCl lM
~ present, as before, values for - ~ ~ sulphates in line with recovery in public works ~ ableau 22).

:

WO ~ 3/25716 2 ~ 14 ~ 3 I PCT / FR93 / 00543 , - ~

In all cases, the treatment of slag by ~ leaching, thanks to an extraction of the fraction polluting, leads to a notable increase in resistivity of leachate from the standardized test.
It follows from the foregoing tests that both the potassium chloride, than calcium chloride, allow significant displacements of metals heavy off the slag, even though the rates observed would be different. He will belong in all the specialist to determine 1 ~ salt of choice for operate the successive leachings according to the contents and extractibilities of each type of slag ~ n the various heavy cations against which "inertization" is wanted. It is remarkable that the chlorides of hlcium often also allow stabilization of treated slag ~
It has indeed been observed for various slag processed, especially for SII slag, that the quantity of exchanged calcium is greater than the capacity of cation exchange calculated experimentally, from moreover this quantity exceeds the metal contents heavy extracts during successive leachings.
In fact, the slag treated, 18 months after their sampling (table 20), see their ~ uality improve at the level of the soluble fraction, the solubilization of ni ~ kel, chlorides and sulfates.
This test is repeated 3 months after this treatment on these slag ~ stored at room temperature ~ e shows that these last, under the effect of treatment with the solution of calcium chloride, have stabilized [decrease in the soluble fraction, and above all, the elution threshold for chlorides and sulfates (Table 23)].

: ~

W093J2 ~ 7t6 `; - P ~ T / FR93 / 00543 21 1 ~ 137 Furthermore, no destabilization of the matrix slag did not appear. This phenomenon of stability could be explained as follows.
Mineral analysis of SII slag carried out in the same conditions on the witness and on the residue milking, 3 months after the leaching operation, showed a carbonate enrichment of the slag treated by calcium. Thus, the control slag contains 1.83%
carbon in the form of car ~ onates while the slag treated have a concentration of 2.38%, i.e.
30% increase in carbonate content.
Calcium exchanged during leaching with ~ heavy metals would therefore have accelerated the natural carbonation of slag to give it better stability. Such a result is of interest very particular, for example for bottom ash household waste incineration plants when these have an intermediate leachable fraction, and when these: bottom ash are subject to prolonged storage outdoors:.

~! :

'~:

WO 93/2 ~; 716; ~ L 3 ~ 7 pCI / FR93 / 00 ~; 43 TABLE 1): Study of the composition of effluent reje ~ Rhône from the TREDI S center ~ ir ~ l-Vulbas. Analysis performed on 13/01192 by emission spectrophometry at plasma or atomic absorption.

Parameters Effluent-discharge rhône p; ~ 7.6 Rcsislivi ~ c (Qhm.cm) COD m ~ 07 / l 750 COT m ~ ll 13__ F, elements Conccnlra-ion mg / l ? ~
Lead <0.010 ~ 0.000 ~
Cadmium: ~ 0 ~ 010 ~ 0,000) Zilic 0.120 Cui ~ rc 0 180 :: Nicl; cl 0.120 : Chromc <0.010 (0.003) C; llcium 2030 : Chlorurcs: 3540 '~ mitcs dc dct ~ ction ct (raw valcurs), , ~.

::

WO 93/2 ~ 716 PCI` / FR93 / 00543 2 1 ~ ~ 1 3 7 SALT slag ~ SII) Characteristics Results Results Standards Standards Valued standards Waste Class I ~ Class n ~ Public Works (TP) Soluble fraetions (overdeal ~ s ~ cj 4.5% <loC`o <590 <3% PerLe on fire (at 550C on see) - ~ 5% C5qO
TOC (on. ~ C) pH 7.6 4 ~ pH <13 - -Headquarters _ _ 73 ~ 6%? 35qo - _ _ raises to the nuns on the seories before stabilization '' ~ reveils to e ~ ndres volames from the inineralion of urban waste S ~ ivi ar ~ aly ~ iquc des cx ~ r ~ lclions Quantity Standards Quantities Parameters 1st 2nd 3rd total extracted Class I (~) tolale extracted TP on eontr61és on Ex ~ rait Extract Extract dudéehet Class II (2) dudéehetsee décelsee leachate brul (m ~ JkP ~ (m, ælk ~) (m ~ Odor odorless odorless odor - - - -Color jatmatreineoloreineolore pH 6.8 7.1 7.6 Resistivity (Ohrn.em) U 900 3500 COD (m ~ 02Jl) ~ 4 36 0 1200 <5000 ~ 1) 1630C.OT (m ~ / l) <I <I el dO <104 (1) / 400 (2) <41 <1500 1) 1-000 1`000 ~ '- - ~
~ `Conc. Conc. Conc. (; ~ Uan ~ ilé l ~ iormes Standards Quarltilé Standards ~: Elementsduler of the 2nd of the 3rd total extract ClasselClassell total extract TP on exuait ~ xtraiteXtraildudéehelbrul ~ mg / kg) ~ mgJkg) dudéehetsec dache ~ sec Im ~ (m ~ (m ~ mg / kP) (mQ / kP) (m ~
Lead 0.443 0.116 0.052 6.11 <100 <30 8.30 <15 Cadmium 0.058 0 ~ 015 <0.010 0.73 - 0.83 eS0 <5 0.99 - 1 ~ 13 ~ I
Zinc 0 ~ 093 <0 ~ 050 <0 ~ 050 0 ~ 93 - 1.93 <500 - 1.26 - 2.62 Copper O.OX8 0 ~ <0 ~ 050 1 ~ 54 - 2 ~ 04 - <202 ~ 10 - 2 ~ 77 Nlcl; cl0 ~ 338 0.0 ~ 35 <0 ~ 050 4 ~ 23 - 4.73 <100 - 5 ~ 74 - 6.4, Chrome 0 ~ 100 <0 ~ 010 <O.OiO 1.00-1.20 <100 - 1.36 - 1.63 <1 Mereure <0.001 <OP01 <0.001 <0.03 <10 <0 ~ 2 <0 ~ 0 ~ <0 ~ 2 NDQ ND 1 ~ D - <10 : Arsenic <0.01 () <0 ~ 010 <0 ~ 010 <0.30 <10 <2 <0.40 ~ '' - Chlorides 338 86 9 4 330 - <10000 5883 ND: not dosable mportemfnl a solub; lisation Componemenl Quanlilés Quanti ~ és -, solubilisablespolen ~ iellement Elcment ~ issolution Solubilisalion Solubilisation Solubilisa ~ iondudéche ~ solubilizable bruldanc lolaledecroissant sta ~ nanteeroissant conditions ~ conc.lol.de ~ het sec) i `of the test (m ~ P) (m ~ / kS ~) .
Lead - ~; - - 6.11 343 Cadmium ~ 0 ~ 73 - 0.83 3 Zinc ~ - 0.93- 1.93 948 Cui ~ rc - ~; - - 1.S4 - 2 ~ 04 14150 Nici; el - ~ 4.23 - 4 ~ 73 1523 Chrom. ~ 1.00- 1 ~ 20. 1092 Chiorurcc ~ 4330 2050 () SUlr; ll ~ c. ~ - - 19 ~ i80 182 () () WO 93/2 ~ 716 2 i 1413 7pc ~ / FR93 / 0os43 , .....

TABLE 1 ~: Monitoring of leachate and rinse water during taiting slag dc S ~ laise II (SII) by the effluent - Rhône discharge.
_ _ Leachate rinse water parameters p ~ 7.5 7, I
: Résislivi ~ c (Ohm.cm ~ 94 925 COD mg 2/1 414 C OT m ~ / l 6 7 _ Elements Conc ~ in ~ a ~ ion mg / l 'ConcentraLion mgll ~

PJomb <0.010 (0.000) <0.010 (0.000) Cadmiurr 0.012 ~ 0.010 (0.000 Zinc 0.060 <0.050 ~ -) Copper 0.200 ~ 0.050 (-) Nickel 0.850 0.120 romc <0.010 (0,000) <0.010 (0.000) Calcium 1930 150 Chloride ~ 3940 250 ~ ~, limilcc dc detcction et (~ al- ~ urs brutes).

~ :: ::

:::
~:::

: ~

WO 93/2 ~; 716 PCI '/ FR93 / 00543 21 ~ 137 3 &

TA8LEAU 18: Monitoring of leachate and rinse water during the tr ~ itement scones of Salaise 11 ~ Sll) by CaC12 to lOgll.

Parameter ~ Leachate Rinsing water pH 7.2 7, ~
Rc ~ ic ~ c (Ohm.cnl) B ~ 1030 COD m ~ O ~ ll 407 35 CO .T m ~ /! 5 6 : ~
~: element ~ s conccnlralion m ~ ConCentraliOn m ~
~. ~
_ _ Lead <] (0 009) cO, O10 (0.001) C ~ dmium 0.011 ~ 0 010 (0 000) Zillc 0 ~ 060 <~ .0 ~ 0 (0.010) Cui ~ rc 0.150 <0 ~ 050 (0.030) icl; ~ l 0.710 <0.100 (0.060 Cllromc <0 ~ 010 (0.001) <(), 010 (0,000) C ~ lcium 2 ~ oO 171 Chll ~ rurc.c 49 ~; 300 millet ~ cd ~ d-it-? ~ tion ct (~ urs ~ rutcs).

~, ~

~ ~:

-. :::::: ~:, ~ ~:

: ~.
: ~

WO 93/2 ~ i716 PCI ~ / FR93 / 00543 `" ~: 114: 137 TAsLEA ~ 9: Follow-up of leachate and incipient water during the treatment of seies 521aise 11 (511) by KCI lM.

Leachate rinse water parameters pH 7.8 7.4 Satin-clad (Ohm.cm) saturated 107 COD mg 2 ~ - 3934 171 COT m, ~ 4 :;: Elements ConcentratJon mg ~ ConcentraLion mg / l ~
:::::
Pl ~ rnb 0.0 ~ cO, 0.0 (0.002) C ~ dmium 0.032 <O, Olt :) (0.000) zinc <050 (0.030) ~ 0.050 ~ 0.010) Copper Q, 210 c0.050 (0.010) Nic ~; ei 0.390 ~ 0.100 (0.080) Chromc ~ 0.010 (o.ob2) ~ o.olo (0.002) Calciun- 173 15 Chlorurcs _ 254 ~ 1 ~ 1 1770_ _ limited to detection and raw alcurs).

',:':
~ ~ `

: ::
:

WO 93/25716 2 11 ~ 13 7 4 0 PCI / FR93 / 00543 TAI ~ LEAI ~ ~ 0: TEST OF LIXIVIAT101 ~ `NOI ~ MALISE A ~ RES TREATED1 ~ T BY EFFLUEI ~ T-REJECT RHOI ~ 'E
SELF, '~ AGlTATiO ~' SALAISE 11 Slag (Sll) _ ~ __ _ _ _ Standard Features Norrnes Norrnes l`iormes valuation Class 1 ~ Class D ~ Public Works; c (TP) Solublc fraction i on dcche- seC) 1.9% <lOqc <5 ~ o <35'c Perlc au rcu ~ at 550C on 5CC) - <55C - <5 ~ o TOC (on scc) pH 8.51 <pH ~ 13 Dryness 63. ~%> 35 ~ 0 '' norms on slag before stabilization relating to fly ash from the incineration of urban waste Analytical follow-up of extruclions Quantity Norrncs Quantitc Norrncs arametres Icr 2èmc 3cmc lotalc extractcClass I (]) lotalc e ~ traitc TP on conlr ~ les sur Extrai ~ Extrajl Extractdudechcl ClasscU (2) dudéchclscc dcrhclsec lixi ~ iat _ _ _ hrul (m ~ / k ~ l (m2 / k ~) ~ mc / k ~) (rn ~
Odcu ~ inodorcir, lodorc inodorc - - - -Coulcur incolorcincolorcincolorc pH 6.4 7.3 7.7 Résislivitc (Ohrn.cm) 1110 3540 6130 COD (m ~ 02 / t) 0 0 ~ 5000 ~ () TOC (m ~ / l) 11 5 S 218 <104 (1) 1400 (2) 341 <1500 Volume (l) _ 1.000 1.000 l.OO () - ~

Conc.Conc. Conc. Quanlilc Normcs NonnesQuamitc Normcs E! Emenls dulcr du2eme du3cmc lolalccxlrailc Classcl Classcll tolalccxuailc TPsur CXlrail cxuail cxuaildu dcchcl brul (m ~ (m ~ lkg) du dcchct scc dcchel scc (m ~ e / ll (m, ~ (m, ~ / l) (m, clk ~? (m, ~; ~ ~ (m ~
Ptomb ~ I), Oi () <0.01 () <0.010 <0.30 <lou <3U <0.47. <1 Cadmium <0. () 10c (), O10 <O.QIO <0.30 - <50 c ~; co, i ~ 7 <l Zinc ~ <0.05 () <0.050 ~ (). 050 <1.5 () <500 - <2.35 Cui ~ rc; 0.06 () <0.050 ~ 0.05 () 0.60- 1.6 () - <20 0. ~ 4 2.50 '-Nickcl ~ 0.160 <0.050 <0.050 1.60 - 2.60 <100 - 2.50 - 4.UO
Chron ~ c ~ <0.010 <0.010 cO, O10 <0.30 <I (? U - <0.47 <l Mcrct ~ r- <0.001 ~ <0.001 <0.001 <0.0 ~ <1 () <0.2 <0.04 <0.
Cyanutcs NDG ND NIS ~ 10 AJscnic <OPI () <0.01 (~ <U.OI () <0.3 () <lO <''<Oi ~ 7 c2 ChloTurcs: 59 9 4 7 ~ 0 - <lUOOO 1127 Sulale ~ 32 ~ - 81 38 4 ~ 50. - - 69fi ~; <70 () 0 ~ 'Nl): nondosablc Consistency with s ~ lYbilisaliQn Componcnlcnl Quanlilés Quanlitcs solubilizable polcnlieliemcn elements Dissolution Solubilisalion Sulubilisalion Solubilisalion dudcchubrutin solubilisable olalcdccroissanlc sla ~ nanlc crolssanlc Ics condilions ~ conc.tol.dcchclscc) from lesl (m ~) (m ~ / ke) Cui ~ rc - ~ - 0.60- 1.6 () 13R74 Nicl; cl - ~; - 1.60 - 2.60 146R
Chlurllrcs. ~; 72 () 2050 () sulr3lc ~ ~ 4 ~ () 182 () (!
, ~.

WO 93/2 ~ 716 4 1 2 1 ~ 4 1 ~ ~ PCI` / FR93 / 00543 ~ BLEAU 21: TEST OF LIXIVIAT10 ~ '~' ORMALIZED AFTER TREATMENT ~ .'T BY EFFLUEr ~ 'T Rl: CONSTITUTED ~:
(CaCI ~ a 10 ~ il) UN AGITAT10 ~ ' SALT slag (S 11) Characteristics Rcsullats Standards Standards Aioration standards Waste class 1 ~ Class 11 t ~ Public works (TP3 _ _ _ _ Soluble fractlon (on dry waste) 1.4qc <lO ~ c e5% <3 ~ / c Fire bead (at 550C on scc) - c5 ~ c <5S-c TOC (~ ur scc) - -pH 7.8 4 <pH <13 - -Siceile 66 ~ o> 35 ~ c relating to standards on standards before stabilization relating to eendres volanles psovenam de I inCinéralion de ~ urban waste Analytical analysis of the reactions Quantity Norrnes Quanu ~ e Norrnes I> arameters I 2nd 2nd lotale eXtraileClass I (I) ~ otale extJaileTP su ~
control ~ on E ~ traj ~ Extraul Exuail dudeehe ~ Class II (2) dudeehelsee déehelsee lixi ~ iat bru ~ (mrfk ~) (mr ~ kr) (mr / ke ~ (m ~
Odu ~ r odorless odorless isK dore Color colorless colorless colorless pH 7 0 7.3 7.8 ; ~ Resistivity (Ohm em) 1] 90 3420 6210 COD ~ m ~ 02/1) () 7 () 70 <5000 (1) 105 TOC (m ~ ll) 9 5 4 180 <104 (1) / 400 (2) 270 ~ 1500 Volume (1) 1,000 1,000 I.OOû - - -Conc Conc Conc Quanti ~ c Standards Quanlite Standards Standards Elements ~ ne 3rd ~ otaleexuaj ~ e ClasselCJassell totalextraite TPsur would have had extra gross waste (mg / l; ~ (m ~ / kg) of deehel s waste se-(rn ~ / l) (mrli) ~ (! n ~ / li (m ~ / kr) (m ~ (m ~ / l; ~) Piomb ~ <0.01 () <0.010 eO O 10 <0 30 <1 () 0 <30 <0.45 <15 Cadrnium eOOi () ~ (j. () L () <0. () 1 () <U30 ~ 50 <5 <045 <1 i! inc ~ <005 (~ <0 05 (1 <005 () eI 5 () ~ 5 () 0 <.25 Cui r: e0.050 <0.050 <005 () <1.5 () - <20 e 25 iiekcl 015 () 0. () 6 () eO.050 21 () - 2.6 () ~ 100 - 3 14 - 3.90 Cluom- ~ O.OIU <0 010 <0.01 () <0.3 () <100 - <0 45 <1 tereure <0 001 eO OOI ~ 0 () () 1 <(1 03 <11) <(). <() W ~ 0.2 Cyanides ND ND ND - <10 - -Arsenic ~ eO OI () <0 010 <0.010 <0.30 <10 <2 <0.45 <2 Chionlres 101 13 5 119 () - <10,000 1,783 Sulfates 290 82 ~ 4} 10 - - _ 6159 <7000 not dosablc Con ~ por ~ ement ~ solubilization Con1l ortenlelll Quanliles Quanliles ~ i; solubilizable politically ment ~ iVissolution Solubilisal on Solubilisalion Solubilization of waste bsul darLs solubilisable lolalCdeesoissanlesla ~ nanlecroissanle the condilions (conc lol dechel sec) from ICSI (mr / krl ~ mr / kr) :
I iekel - ~; - - 210 - 2.60 146 ~
Chlorides - ~; - - 119 () 20 5 () () SUlr.lle. ~; - - 41 1 () 1X ~
__ WO ~ 3/25716 PCT '/ FR93 / {ltQt543 TABLEAI; 22: TEST aE L1 ~ 2V ~ ALlSE AFTER TREATMENT ~ T BY KCL lM UNDER AGITAT101 Seories of SALAISE (S 11) -Carileteristics Resul ~ aLs Standards Standards Standards Valuation Class I deehet class I ~ Class II ~ Public works ~ TP) Soluble fraetion (on dry dechel) 1.59c <10% ~% <3%
Loss on receipt (i 550C on dry) <5 ~ O c5c ~ c TOC (on dry) pH 7.8 4 ~ pH <13 Sieeilc 68.2%> 35%
'~ relating to standards on standards before stabilization ~ rela ~ ives to eendres volarttes provanl from the incineration of urban waste S ~ ivi analytiq ~ -c cxtra ~ tions _ Quantile Standards Quanlilc Norrnes P; ~ rDmeters ler 2nd 3rd total extract Class 1 (l) lolale extraile TP on eontroles on Exlrail Extrail Exlrail dudéehel Classen (2) dudéehelsee déehe ~ sec _lixiviat _ _ brul (mr / ke) (mr / k, r) (m / k ~ ~! mscllce Odor odorless odorless odorless Color uleoloreineolorc yellowish pH 7, 4 5 7, 4 7, 3 Rcsislivilc (Ohm.cm) 783 2990 5460 COD (m ~ O211) 54 7 41 1020 <5000 (1) 1496 COT ~ m ~ / l) 6 4 3 130 <104 (1) 140o (2) 190 <1500 Volume (11 1.00 ~) 1,000 1,000 Conc Conc. Conc. Quanlile Standards Standards Quamitc Standards Element ~ s duler du2ème du3eme tota] eeXUaile Classel Classell lotaleextrailc TPsut exlrail exuail exuaildu de, chet brut (mslkg) (mg / kg) d ~ deehel see déehel sec (rn A ~ (m ~ (mr / l) (mrJlcr) _ _ fm ~ kr) (m ~ / krt PIamb ~ ~ <0.010 <0.0} 0 <0.010 <0.30 <100 <30 <044 <15 Ca ~ nium <0.010 ~ 0.01 () <0.010 <0.30 <50 <5 <0.41 <1 Zine <0.050 <0.05 () e0.050 <I, S0 <500 - ~, 0Culv ~; <0.05 (J <(). 051) <0.05 () <1.50 <20 <,, 20 lickci 0.070 <0.05 () <0.05 () 0.70 - 1.70 <100 - 1.02 - 2, ~ 19 Chromium <0.01 () <0.010 e0, f ~ 10 <0.30 <100 - <0.30 <I
Mcreurc ~ 0.001 e0.001 <Q001 ~ 0 ~ 03 <10 ~ 0.7 ~ 0.04 <0.2 CYanurcs ND ND ~ IU
Atscnic <0.010 <0.010 <0.010 ~ 0.30 <10 <. 0 44 ~ "
Chlotures 165 "5 7 1970 - ~ 10,000 288 ~ -Sulfal ~ ~ ~ 12 ~ 5 ~ 3 (~ _ _2m () 303 ND: not dosable Comporrcmenr à les sols ~ bilis (lrion :: ~ ~::: ~:
Composlemcn (Quanliles Quantitcs ~; solubilisab3es po ~ enliellement Element.sl ~ lssolulion Solubilisalion Solubilisalion Solubilisalion dudéchetbruldans solubilisables ~ lCd ~ croissanLc slarnanlc erolssanle Ies eondiLions ~ conc.lol.dechel sec ~
from lCSI ~ m ~ (metkr ~
_ I ~ ic ~; el - X - - U, 70- 1.70 1468 Chlorides - ~ - - 197 () 20S00 Sul ~ - 2 () 7 () I X '? () (~

WO93 / 25716 43 '~ 4 ~ 3 ~ PCr / FRg3 / 00543 TAI ~ LEAIJ2 ~ 1 VE l, l ~; IVIATIO? ~ I ~ OR ~ 1ALISE ArRES TI ~ ME ~ EFFLUE ~
ETI ~ 'DE D ~. THE STA ~ tlLlTE
~ icories of S ~ L ~ ISE (Sll) Characteristics Results Norms Norms Norms ~ alonsationph ~ sic of waste Class I ~ Class n ~ Public works (TP) Soluble fraction (surd ~ chcl scc) 0 ~ 9% <] 09O <5 ~ o <3 ~ c Pearl fire (at 550C on sc ~) - <5% - <S ~ c TOC (on dry) pH 7.5 4epH ~ 13 Sicci ~ e 95%> 359c _,. . .
slaves with slag standards before stabilization relals to the ash vol ~ mes from the incineration of urban waste Anal follow-up ~ tigue des e ~: t ~ acrions .
Quanti ~ e Standards Quanlilc ~; ormcs Pararnetres IL7 2nd 3èmclotale exrraile Class l (l) lolale exuailc Tl 'sur checked on E ~ urai ~ Exuail Extraildudechcl ClasseM (2) dudechelscc dcchclscc lixi ~ iDt _ _ brul (m / k ~) (m, e / lc, ~) (m, e / ~; e ~ (m ~
~ dcur inL ~ orc modorc odorless - - - -Color incolorcincolorc incolorc - - - -pH 7, ~ 7.4 7.6 Résislivi ~ é (Ohm.em) 1277 3fiS3 5555 COD (m ~ {) 211) 4X ~ 8,640 <5000 (I) 673 TOC (ml / l) 'i 3 3 110 <] o4 (l) / 400 (2) 116 clS00 Yolume (I) ~ 1.000 1.000 _I .00V

Conc. Conc Conc Quan ~ i ~ cNorrnes Nonnes Quami ~ c Norrnes ; Elementsduler du2cmc du3cme ~ o ~ aleexuai ~ e Classel Classell ~ o ~ aleextrailc TPsur exuailexuexlraildu deche ~ brul (m ~) (m ~) du dechel scc dechcl scc 3 ~ ~ m ~ / l) (m ~ / l) (m ~ ni ~; - ~) (m ~ / kc ~ (m ~ / ~; e ~
Plomh <0.01 () <(). Vl0 <0 ~ 010 ~ 0.3 () <100 <30 <0.31 <I ~
Cadmium <0.0l () <(). () ll) <0.010 <(), 3 () <50 <5 <l) .31 <1 Zinc ~ ~ 0.05 () <0.050 <0.050 <1.50 <50 () - <I.SX
Copper ~ <0.050 <(). 05 () <0.050 <1.50 - <20 <l.SX
licl ~ el 1 ~ .1300.07 ~) V, 05 () '~ .30 ~ 100 - 2.4 ~ -Chsomc <0.01 (i ~ 0, () 1 () <0.VI () <0.30 ~ lV0 <0.3] <l Mcrcurc <0 001 <() ~ 001 <0.00l <0.03 <I () <0.2 <0.03 <0, ~
Cyanurcs t ~ D N13 I ~ <] 0 Arsenic eV, 01 () <I). () L () <(). VI () <(). 30 ~ 10 <2 <0.3] ~ 3 Chlorides Sl ~ 4 ~ 4 () - <l0000673 Sui ~ ale ~ 24 () 6X 3X: 4 ~ () - - - 3 ~ 4 "<700 () ND: not dosablc ~; Comporl ~ m ~ nr a la solubilisaJion , omponemcnl Quan ~ Quanlilcs Islands solubilizable po ~ cnliellcmcm ~ lement ~ L ~ issolulion Solubilization Solubilisalion Solubilisalion dudechetbruldans solubilisable 0 ~ 31cdccroissanle sla ~ nan ~ c -roissant Ies condi ~ ions (conc. ~ Ol.dechel scc) : ~ du Iest (mPlkr) ~ mr l ~; r ~
I ~ iic ~; cl - ~; - - ''. 3 () 14 (~
Chlor Ircc ~ - 640 ''05 () () Sulfalcs ~ - - 346 () 1 ~ '~ 2 (~ tl _, WO93 ~ 25716 PCT / FR93 ~ 00543 21i ~ i37 However - and according to an additional provision preferred of the invention-- we proceed to biosorption prerequisite of C2 ~ metals out of these leachate. Indeed, these metals are found in a form very accessible to a number of biosorbents. In other words the sPlon 1 process invention is advantageously completed by an additional step of metal biosorption leached out of treated slag, as has been described above.
In this regard, it is recalled that biosorption is the sequestration of metal ions by solid material of natural origin. This general term includes very diverse mechanisms: ingestion of particles, active ion transport, complexation, adsorption and inorganic precipitation on the biosorbent.
Biosorbent Vn whose use paralt particularly advantageous is chitosan.
Chitosan is the main derivative of chitin (poly N ~ acetyl D-glucosamine). It's a polymer saccharide consisting of a long polymer chain 1 linear to glucosamine units, linked by bridges

4) carbohydrates.
Not very common in nature, chitosan is ob ~ enu by deacetylation of chitin / itself extracted from The exoskeleton of crustaceans, myriapods and others arthropods or even microorganisms, fungi.
From there diversity of sources of chi ~ ine, it follows great: variety of potential qualities of chitosan.
The rate of deacetylation ~ llant from 80 to 10% and the average molecular weight of 5,000 to 1,000,000 consequence the possibility of fixing turbidity ~ viscosity and solubility of solutions. This solubility of : ~ _, ........

WO93f2 ~ 716 11413 7 PCTfFR93 / 00 ~ 43 chitosan, with a low degree of N-acetylation, is not obtained only in an acid medium diluted in the pH range c ~.
It is linked to the presence of amine functions on C-2 glucoside units t giving this polymer a weak polybase behavior.
Several authors admit that the use of chitosan in water treatment is indeed a way of the future. A product seems to be currently is developing in Europe in this sense, it is PRO FLOCTM
(Protan). Its characteristics are as follows flakes / powder; free amine form (-NH2), purity average. In Japan, chitosan (chitosan beads, Fujibo Inc, Shizuoka) is used in water treatment domestic and industrial. Another form of usable chitosan (which was used in testing ,::
reported below) is the SIGMAR chitosan (ref: C.0792). ~ But other biosorbents can be used in place of chitosan. We can by : example use some of the biosorbents dentified below. Their characteristics of ::: biosorption does not always coincide with those of chitosan. Choosing the most appropriate biosorbent will often result from the leachate contents obtained by : application of the first part of the process according to the invention to the slag which was related r.
Preliminary tests have been carried out with `different biosorbents able to fix metals: chitin SigmaR (ref: C.3387), chitosan SigmaR (ref: C.0792), fungal iomass with walls made of chitosan (Rhizopus arrhizus), bacterial biomass ~ Z ~ ogloea ", ~ ramigera ~ and feather meal.
, METHODOLOGY:

::
:

W093 / 2 ~ 716 PCT / FR93 / ~ 0543 ~ 1-14 ~ 3 '~ l In 250 ml plasma bottles, we introduce 10 ml of saline solution (Cobalt: Co (N03) 2 or Chromium: Cr (N03 ~ 2, 9H20 or Copper: CuS04, 5H20 or Zinc:
ZnS04, 5H20 or Cadmium: 3CdS04, 8H20 or Lead:
(Pb (N03) 2 at 100 mg / l adjusted to pH 4.0 and 100 mg of biosorbents (either lg / l) as is or ground.
Incubation is carried out at 25 ~ C under slight restlessness; The samples are taken after 3, 6, 12, 24, 48 and 72 hours of contact.
The analysis of the elements in solution is carried out by plasma emission spectrophotometry, Figures 4 to 9 provide curves relative to the adsorption kinetics of lead, copper, chromium, cobalt, zinc and cadmium on different biosorbents 7 The following salts have been respectively introduced work:
- lead nitrate (Figure 4 ~, copper sulphate (Figure 5), chromium nitrate (Figure 6), cobalt nitrate (Figure 7), - zinc sulfate (Figure 8), cadmium sulfate ~ Figure 9).
The figures are representative of the variations respective of the absorbed metal ~ en ~ of the initial content on the ordinate axis) as a function of time ~ in hours [H]) on the x-axis.
Results:
By choosing initial conditions little favorable to biosorption (initial pH: 4.0), different metals tested at a weight ratio salt / biosorbent of 0.1 gave the following results:

~:

- lead is quickly fixed by Zoo ~ loea rami ~ ra à
75% right in 5 hours; dP flour and chitin feather accumulate up to 30% then fixation stops for the rest of the kinetics. R. arrhizus f ixe regularly this metal to reach 80% after 72 hours.
Chitosan does not seem to mobilize lead in the conditions of the experiment (figure 4).
: - copper has a very similar behavior towards :: chitin, fungal and bacterial biomass and : ~: feather meal; his immobilization is close to 10%
and remains practically constant. Chitosan is the ~ -best adsorbent of cui ~ re and takes a colored hue :; in its presence, S0% of copper sulphate are chelates in 72 hours (Figure 5).
only,: chromium has an affinity for ~.
chitosan and: its adsorption reaches 6% in 72 hours incubation (Figure 6).
cobalt has an adsorption and alternate desorption for all biosorbents test. The: fixed percentage varies between 2 and ~% (figure zinc has a good affinity for Rhizopuc arrhizus and chitosan (10% adsorbed in 72 hours incubation ~ Other polymers do not chelate zinc neither to the chosen concentrations nor to the parameters set gfigure 8 ~.
cadmium is fixed by chitosan at a rate of 20 ~ after 72 hours of incubation. The other ~ sorbents do not accumulate this metal (flgure 9).
it results from the comparative examination of the above curves indicated that one can by the choice of biosorbents : ~:
~ used in these preliminary tests, facing the :,.
~:

WO93 / 25716 PCT / FR93 ~ 00543 211 ~ 7 $ 4 treatment of all leachates obtained resulting from treatment of slag with a solution containing chloride ions, whatever their content respecti ~ es in polluting metals.
We can also note that some of the biosorbents used may be weakly active in some conditions, but become so in others. Phone is the case, for example, for the chitosan with regard to lead and copper.
Some of the biosorbents are of great interest particular, especially when they can be regenerated.
In this regard, chitosan is effective particular. The tests briefly reported below testify to the ability of chitosan to be regenerated by treatment with an exchange reagent or an acid.
Another parameter can notably reside in the setting in the presence of larger amounts of biosorbents vis-à-vis the element to be extracted. This is also the case.
for lead: and zinc. In the conditions of the experiment carried out as indicated below, the amount of lead absorbed can increase considerably when the relative proportion of the biosorbent increases with respect to the metal concentration to be adsorbed.
Yéthod oqle ~:
Int 250 ml bottles, one int ~ odui ~, of a hand, 100 ml of ~ saline solution (metals tested: CuSO4, 5H2O; ZnSO4, 5H20; CdSO4, 8H2O; Pb (NO3) 2; NiSo4 ~
6H2O), or adjusted to pH4.0 ~ with the acid corresponding to the conjugate base), either leaves at its own pH, and on the other hand, respectively 100, 200, 400 and ~ 00 mg of chitosan. After 24 hours of incubation at 25C SGUS
slight agitation, the preparation is cen ~ rifugée and 20 ~ 1 of the supernatant are taken for assay at WO93 ~ 25716 PCT / FR93 / 00543 211,413 ~

plasma emission spectrophotometer. The "800 mg" pellet is kept to measure desorption.
On it, 20 ml of distilled water are added then the whole is stirred for 1 hour before being this ~ tampered with. The supernatant is analyzed and the residue taken up in a 0.1 M ammonium sulfate solution and / or 1N hydrochloric acid. After another agitation, the analysis of the supernatant is repeated.
Results:
Copper is the element with the best affinity for chitosan; with a report salt / biosorbent of 0.8 the metal chelation is practically complete in 24 hours of contact. the ~ aleur of the initial pH does not seem to affect the capacities fixative of the biosorbent, however its basic power tends to orient the pH of the medium towards similar values 7 or the competition for the prot ~ ns becomes less.
Desorption with ammonium sulfate is weak proving that the attached metal is difficult exchangeable. Changing the pH by adding acid hydrochloric acid tends to ionize the intervening groups and lead to the release of chelated metal. Do not have taken into account the losses during the experiment, the recovery percentage is around 80%. By elsewhere, hydrochloric acid used to displace the balance of the reaction seems to alter the structure of the chitosan because a slight disintegration of the product was noted. According to literature, acid sulfuric could be effective in moving the chemical equilibrium of the reaction without dissolving the chitosan.
Zinc, another element tested, has an affinity less compared to cui ~ re and its percentage of fixation WO93 / 2 ~ 716 PCT ~ FR93 / 00 ~ 3 2iI4137 '' ~

reaches 60% in 24 hours for a salt / biosorbent ratio 0.8. The pH of the medium changes identically to copper experiments.
Desorption with water seems to be rather a washing than active desorption. Zinc is slightly exchangeable but mobilization becomes effective by addition of acid.
Among 1P-S elements tested, cadmium has a behavior similar to zinc, its degree of fixation reaches 60% in 24 hours for a salt / biosorbent ratio ident ~ that.
With the exchange reagent, cadmium is strongly desorbed; its desorption becomes total by adding acid ch} orhydric. The use of acid as the sole reacti desorptiQn does not seem sufficient to extract the all of the fixed metal.
, Lead is adsorbed at 91% for a : salt / biosorbent ratio of 0.8, this metal is weakly exchangeable, it is partly mobilized by adding hydrochloric acid.
Nickel has a lower affinity for chitosan, its fixation percentage reaches 60% in 24 hours for a salt / biosorbent ratio of 0 ~ 8. Her : desorption is effective (78%) following the displacement of : the reaction balance by adding a hydrochloric acid.
:: The results obtained make it possible to envisage industrialization of the metal biosorption stage i pollutants -contained in leachate ~ ts obtained at the end stages of "inertization" of the initial slag.
Figure 10 is a block diagram of a industrial device which can be considered for this purpose.
The leachate will be sent to a reactor containing chitosan or to a mixed device comprising in WO93 / 2 ~ 716 PCT / FR ~ 3/00543 21 ~ ~ L37 a reactor separates or mixes another biosorbent (eg stabilized biomass). This will be provided with a recycling loop in order to obtain a purification full of waters. These metals-free waters may be discharged into the river or possibly recycled as slag rinse water.
By analogy with iOhS exchange resins, the ; chitosan will be regenerated by desorption of metals from using an acid eluent, operation e ~ fully followed a repackaging of the biosorbent by adding sodium hydroxide.
Regeneration will be carried out alternately on one treatment chains (route I or II). The acid eluate will be directed to a storage tank before a ultimate solidification but recovery of metals and water recycling could be considered later.
very similar results can be obtained with other biosorbents, for example with biomass fungal (particularly effective for treatment 3 ~ calcium leachate ~.
Treatment of leachate with biomass FUNCTIONS
Operating conditions Biosorption tests are carried out under ayitation for 2 hours at 25C and without pH control.
; l00 ml of an effluent of composition voi ~ ine leachate slag ~ are placed in the presence of 50, l00 or 250 mg of fungal biomass (Rhizopus arrhizus) grown in laboratory. The dosage of mineral elements is then carried out on the solutions obtained after filtration on millipore membranes with a diameter of 3 m then 0.45 m.

: ~

::

WO 93J2 ~ 716 PCI / FR93 ~ 00543 211 ~: L3 ~ `~ 52 Results The results recorded in table 24 and the figure 11 show that Rhizopus arrhizus is particularly effective in removing from a matrix heavy metal calcium in trace amounts.
Leachate treatment (Figure 12) In practice, effluents or leachate can be tra ~ your continuously in a device comprising a agitated bath feeds with the effluents to be treated and the biomass and a decanter for separation solid / liquid. Liquid supernatants are removed and solid matter (biomass) is either recycled to food since they are not yet saturated in metals, or in a purge when they are saturated. They are then concentrated (ultimate waste) and, possibly destroyed, for example by incineration, or solidified, for example by vitrification for storage.
: Table 24 is representative of the results obtained. Figure 11 provides an illustration of the , ~
results obtained in tests involving three different concentrations of "Rhizopus arrhizus"
(study of the adsorption of different metals contained in effluents. Calculation of the percentage of elimination and ~ 5% confidence interval after 2 contact hours under action in the presence of Rhizopus arrhizus).

W093 / 25716 ~ 13 7 PCT / FR93 / OQ543 Table 24: Biosorp ~ ion of heavy metals. And ~ from CC ~ mpQsition of effluents before and after treatment k on biomass ss fungal. 3 re ~ petitions per test. Concentration in ~ lg / le ~
int ~ 5% confidence interval ~

Rhii ~ opus Rh ~ z ~ pus Rhizopus (SOmg) llOOmg) (250mg ~

Concentration C ~ ncentration Concentration Concentration inihalefinale final final Pb (, ~ l ~; / l) 15 5 + 1 ~ 3 ~ 2 2 + 1 Cd (~ l ~ / li 40 32 + 0 20 + 114 + 13 Zn ~ g / l) 6 ~ 210 + 0 100 + 0 ~ 0 + 0 Cu (~ l ~ / 13 40 10 + 0 20 + 020 + 0 30 + 0 30 * 0 20 + 0 Cr (~
C ~ (~ / 1) 2.70 2.7 ~ 2,732.71 _ _ _ _ _ cost (m ~ 13.7 + 1.9 19.7 _3 9 32.8 t 3 ~
u; id ~ dcsc ~ cnon cn ~ gtlpour Ics clcments millners dosed: Pb ~ 2: ~: CdclO; Zn <~ O: Cu <~ U; NI <10U; Cr <10.
; All of these results bear witness to é: loquente: ef ~ icacit ~ of the whole process according to 'invention. The ~ principle diagram ~ of one of its modes preferred ~ of implementation appears in Figure 13.
therefore follows from e: which precedes that the process according to the invention leads to combustion residues which, after ~ treatment, comply with the definition of waste lr.ert ~ e European and toy conforming to the values leading to a product that can be used in public works.
: On the other hand, the mobile fraction of heavy metals content: initially in the tailings was concentrated in a mass very much lower than the mass initial slag.
: Finally the treatment does not lead to a transfer of pollution in the natural environment.

- "

Claims (13)

1. Process for stabilizing residues of combustion, in particular slag whatever the origin, and particularly by extraction of solubilizable metal fractions, characterized by the carrying out one or more slag leaching, beforehand if necessary, ground to particle sizes low enough, especially at lower values 50 mm, to allow sufficient contact between the combustion residues and an aqueous solution or liquor of leaching, having a sufficient concentration in elements, either cations (K+, Na+, Ca2+), or protons exchangeable in the form of chlorides with the cations of heavy metals present in these residues, this leaching must be sufficient to ensure the transformation of at least some of the metals determined, in particular heavy metals contained in combustion residues, in soluble chlorides and which are extractable by this leaching liquor, and their effective extraction in sufficient proportions so that :
- on the one hand, a standardized elution test subsequently applied to the slag thus treated attests to the decrease in quantities successively solubilized of each of these metals determined at the repeated extraction tests carried out with a standardized elution solution conforming to this test and, - on the other hand, the sum of the solubilized quantities in the eluates resulting from the extractions with the aforesaid normalized solution, is situated at values corresponding at concentrations below threshold concentrations also predetermined for each of these metals and for the other parameters set by the standards. 2. Method according to claim 1, characterized in that said standard elution test comprises three extraction tests carried out with a solution standardized itself consisting of demineralized water saturated with air and CO2 at pH 4.5 and resistivity included between 0.2 and 0.4 M.OMEGA..cm. 3. Method according to claim 1 or claim 2, characterized in that the solution of leaching or treatment consists of a dilute hydrochloric acid solution, plus particularly for the treatment of slag with basic character. 4. Method according to claim 3, characterized in that the hydrochloric acid concentration of the slag leaching solution at a concentration molar in the range of 0.01 M to 1 M, in particular of the order of 0.1 M. 5. Method according to claim 1 or claim 2, characterized in that the solution of leaching or treatment consists of a chloride solution of an alkali or alkaline metal clay, more particularly for the treatment of neutral slag. 6. Method according to claim 5, characterized in that the leaching or treatment solution is consisting of a solution of potassium chloride. 7. Method according to claim 6, characterized in that the alkali metal chloride concentration or alkaline earth of the leaching solution or processing is in the 0.01 M range, including 0.05M, to 5M. 8. Method according to claim 7, characterized in that the alkali metal chloride is chloride of potassium, and that its concentration is of the order of 1 M. 9. Method according to claim 7, characterized in that the alkali metal chloride is chloride of calcium, and that its concentration is included in the range from 0.01 M, notably 0.05, to 5 M, notably is the order of 0.09 M and 0.15 M. 10. Method according to claim 7, characterized in that the alkaline earth metal chloride is calcium chloride, and that its concentration is the order of 0.09M. 11. Process according to any of the claims 1 to 10, characterized in that the leaching solutions collected from slag treated undergo biosorption with biosorbents capable of sequestering at least a significant part of the heavy metal metal ions extracted from these slag. 12. Method according to claim 11, characterized in that the biosorbent is based on chitosan. 13. Method according to claim 11, characterized in that the biosorbents are biomasses, in particular fungi or bacteria, derived from cultures or biological fermentations.