WO2015086350A1 - Méthode de production de matériau barrière d'eau comme couverture de décharge, recouvrement ou confinement de décharge sous et/ou sur le côté d'une décharge, et matériau barrière d'eau produit ainsi - Google Patents

Méthode de production de matériau barrière d'eau comme couverture de décharge, recouvrement ou confinement de décharge sous et/ou sur le côté d'une décharge, et matériau barrière d'eau produit ainsi Download PDF

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Publication number
WO2015086350A1
WO2015086350A1 PCT/EP2014/075991 EP2014075991W WO2015086350A1 WO 2015086350 A1 WO2015086350 A1 WO 2015086350A1 EP 2014075991 W EP2014075991 W EP 2014075991W WO 2015086350 A1 WO2015086350 A1 WO 2015086350A1
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WIPO (PCT)
Prior art keywords
water barrier
dry weight
steel slag
barrier material
pozzolanic
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PCT/EP2014/075991
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English (en)
Inventor
Frédérique BOUILLOT
Philippe Descamps
Dirk Van Mechelen
Original Assignee
Recoval Belgium
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Publication date
Application filed by Recoval Belgium filed Critical Recoval Belgium
Priority to EP14803173.5A priority Critical patent/EP2903756B1/fr
Publication of WO2015086350A1 publication Critical patent/WO2015086350A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/005—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing gelatineous or gel forming binders, e.g. gelatineous Al(OH)3, sol-gel binders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B1/00—Dumping solid waste
    • B09B1/004—Covering of dumping sites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00732—Uses not provided for elsewhere in C04B2111/00 for soil stabilisation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
    • C04B2111/00775—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes the composition being used as waste barriers or the like, e.g. compositions used for waste disposal purposes only, but not containing the waste itself
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/30—Landfill technologies aiming to mitigate methane emissions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to a method for producing a water barrier material.
  • the water barrier is made starting from a granular material which is mixed with a pozzolanic material which comprises solid particles and with a plasticizing material to produce a mixture.
  • a pozzolanic material which comprises solid particles and with a plasticizing material to produce a mixture.
  • the pores present in this mixture are at least partially filled with a silica-gel.
  • Such water barrier materials are for example used for soils containment or to cap landfills. They can also be applied as landfill liner, more particularly as a base layer underneath landfills or as walls bordering a landfill.
  • a water barrier material which is already in commercial use is the so-called “Hydrostab” material. This water barrier material has been studied already thoroughly and is described in a number of scientific publications. Reference can be made for example to the Alterra-report 1218 (Boels, D. et al. "Durability of Hydrostab; a field investigation and prognosis'), to the Alterra-report 1374 (Boels, D. et al.
  • the Hydrostab water barrier material is made by mixing soil or screening sand (40 - 50% by dry weight, in particular 42.5%) with sewage sludge (40 - 45 % by dry weight, in particular 42.5%), fly ash (about 10 % by dry weight, in particular 1 1 %) and waterglass (1 - 5 % by weight, in particular 4%).
  • soil or the screening sand provides a granular matrix which is as such not plastic and which is also water permeable.
  • a quite large amount of sewage sludge is added as a plasticizing material.
  • plastic properties are important since due to differential settings of the waste materials in the landfill the water barrier material should be able to deform without producing cracks through which water might penetrate through the water barrier.
  • An additional advantage of the plasticizing material is that it also improves the water retention properties of the water barrier material so that the material doesn't dry out and doesn't loose its water sealing properties.
  • the permeability of the water barrier material is already reduced somewhat by the presence of the sewage sludge, a further reduction of the hydraulic conductivity is required to achieve for example the low permeability values of clay, which is also used in practice as landfill cover.
  • the hydraulic conductivity of a landfill cover made of clay comprises for example about 10 "9 m/s.
  • the pores in the Hydrostab material are at least partially filled with a silica-gel.
  • two gel materials are to be formed in the Hydrostab material, namely a silica-gel and a calcium- silicate-hydrate gel (CSH gel).
  • the silica-gel is produced by adding waterglass (water soluble sodium silicate) to the mixture whilst the CSH gel is produced by alkaline activation of the fly ash in the mixture. This alkaline activation is achieved by means of the alkaline waterglass.
  • the fly ash should contain a sufficient amount of reactive or free calcium oxide in order to be able to produce the required amount of CSH gel by a pozzolanic reaction with the amorphous silicates contained in the fly ash, suitable fly ashes being described as class C fly ashes containing 20 to 30% calcium oxide.
  • a problem addressed in the Hydrostab reports is that the silica-gels, which provide for the reduced hydraulic conductivity, are meta- stable phases which transform over time into quartz according to the Alterra report and loose their structure in this transformation. Although this is a slow process, it affects the durability of the Hydrostab material which should be sufficiently long, in particular 100 years or even longer. To achieve such a long durability, an essential feature of the Hydrostab material is that it should contain a sufficient amount of CSH gels. These CSH gels are not stable and slowly disintegrate thereby producing new silica-gel material. In the first years the amount of silica-gel increases thereby. Once all the CSH gel has disappeared, the amount of silica-gel slowly decreases.
  • a further essential feature of the Hydrostab material is that it should have a sufficiently low pH in order to enable the production of new silica-gel by the disintegration of the CSH gel.
  • the Hydrostab material should in particular have a pH of about 7.5 or lower as at a pH between 7.5 and 8 the velocity at which the CSH gel dissolves quickly drops down to zero (see Fig. 2.1 of the ECN report).
  • a problem with the CSH gel which is to be produced in the Hydrostab material to achieve the required durability of the material is that the amount thereof should not be too high due to the hardening effect produced by the CSH gel (in the same way as the CSH gel produced during cement setting). Consequently, the amount of CSH gel produced in the Hydrostab material should be kept between quite narrow limits.
  • Alterra- report 1374 prescribes for example that the amount of CSH gel in Hydrostab should be between 20 and 40 g/kg dry matter in order to achieve a sufficiently long durability of at least 100 years and in order to avoid the formation of a too stiff/hard layer.
  • the upper limit at which a stiff and brittle layer would be formed has however not been determined so that this upper limit will be higher than 40 g CSH/kg dry matter.
  • the composition of the CSH would correspond to Tobermorite (Ca 5 Si 6 Oi 6 (OH) 2 .8H 2 O). Consequently, 40 g CSH/kg would correspond to about 16 g CaO/kg or about 1 .6% by weight CaO in the Hydrostab material.
  • a drawback of the Hydrostab material is that the amounts of the different materials used to produce Hydrostab have to be carefully controlled and that the required amounts of these materials even depend on the composition of the different materials. For example the required amount of fly ash depends on its reactive/free calcium oxide content. The maximum durability of Hydrostab is also limited by the maximum amount of CSH gel which may be contained in the Hydrostab material. A further drawback is that a relatively large amount of waterglass, which is quite expensive, is required to produce the silica-gel and to activate the fly ash.
  • Cement kiln dust is a further alkaline material which can be used as landfill cover (see for example the paper “Beneficial Use of Industrial By-Products", December 2003, RMT, Inc.).
  • CKD comprises however a lot of cementitious materials (di- and tricalcium silicates) and produces thus a large amount of CSH gels with hardening properties.
  • An object of the present invention is to provide a new method which enables to produce a water barrier material which contains, just like the Hydrostab material, silica-gel to reduce the hydraulic conductivity of the material without affecting the plasticity thereof but which does not require the use of waterglass to produce the silica-gel and which also does not require the presence of CSH gels and a relatively low pH to replenish the amount of silica-gel which disappears in the course of time.
  • the method according to the invention is characterised in that said granular material comprises a comminuted steel slag material:
  • said pozzolanic material comprises at least silicon and either no calcium or such an amount of calcium that it has a basicity, defined as the ratio between its calcium content, expressed as % CaO, and its silicon content, expressed as % SiO 2 , which is smaller than 0.20, preferably smaller than 0.15, the silica-gel being produced by alkaline activation of the solid particles of said pozzolanic material at least partially in the alkaline water barrier material and optionally in an alkaline solution before being mixed with said granular material with a portion of the solid particles of the pozzolanic material remaining in the barrier material.
  • no waterglass has to be used to produce the silica-gel material since this silica-gel material is produced from a pozzolanic material, which is preferably a waste material such as glass cullet, class F fly ash or silica fume.
  • the pozzolanic material has to have a basicity which is smaller than 0.2 so that by alkaline activation thereof silica-gel is produced and optionally only a relatively small amount of CSH gel.
  • the granular material used in the method of the present invention is an alkaline steel slag which is mainly crystalline, i.e. which comprises more than 50% by dry weight of crystalline phases. Due to the mainly crystalline nature of the steel slag, it has only a limited reactivity so that it nearly doesn't have any pozzolanic or hydraulic properties. Consequently, it substantially doesn't produce any CSH gel.
  • the alkaline steel slag provides for a buffering effect so that the pH of the barrier material remains high, in particular higher than pH 8. At such a high pH there is a slow but continued activation of the portion of the solid particles of the pozzolanic material that remain in the barrier material so that there is a continuous production of new silica-gel material.
  • the silica-gel disappearing, according to the Alterra report 1218, by its transformation into quartz is thus continuously replenished by newly formed silica-gel phases.
  • these cracks can be filled with newly formed silica-gel so that the barrier material has self-repairing properties.
  • the pozzolanic material itself due to the fact that, in contrast to the CSH gels in the Hydrostab material, the pozzolanic material itself, and also the silica-gel material produced therewith, has no effect on the stiffness or on the plasticity of the barrier material, it may be included in the barrier material in the amounts required to achieve the desired durability.
  • the stainless steel slag material comprises no free lime or has a free lime content which is smaller than 6% by dry weight, preferably smaller than 4% by dry weight, more preferably smaller than 2% by dry weight and most preferably smaller than 1 % by dry weight free lime expressed as CaO.
  • a free lime content which is smaller than 6% by dry weight, preferably smaller than 4% by dry weight, more preferably smaller than 2% by dry weight and most preferably smaller than 1 % by dry weight free lime expressed as CaO.
  • the steel slag may be a common steel slag, such as an LD slag, but preference is given to a stainless steel slag material.
  • An advantage of a stainless steel slag material is indeed that it has a considerably smaller free lime content than the common steel slags.
  • the advantage of having a small free lime content is that the production of the silica-gel material by alkaline activation of the pozzolanic material is less disturbed by any pozzolanic reaction between the free lime contained in the granular material and the pozzolanic material resulting in the formation of a CSH gel instead of a silica-gel.
  • free lime encompasses not only free calcium oxide but also free calcium hydroxide (Portlandite) resulting from the hydration of the free calcium oxide. It however does not encompass any calcium carbonate which may have been formed by reaction of the calcium hydroxide with for example carbon dioxide during a natural or artificial (accelerated) aging of the stainless steel slag material. Such carbonates indeed do not react with the pozzolanic material to produce CSH gel instead of the desired silica-gel.
  • the free lime content of the steel slags can thus be reduced by carbonating the steel slag material before mixing it with the other raw materials to produce the water barrier material.
  • the comminuted steel slag material used in the method of the present invention has a particle size distribution showing a D-m value which is smaller than 100 ⁇ .
  • the D-m value is defined as the size of the openings of a sieve through which 10 vol. % of the steel slag particles pass whilst 90 vol. % of the steel slag particles are retained or in other words it is the particle size at 10 vol. % cumulative passing;
  • the Di 0 value can be determined by dry sieving (by means of sieves having different sizes of openings) or by means of laser diffraction, as described for example in ISO
  • the granular material as such has already a lower permeability compared to coarser granular materials which have a same particle size uniformity coefficient and which are compacted under a same pressure.
  • the particle size uniformity coefficient of the comminuted steel slag material is defined as the ratio between its D 6 o value and its D-
  • the particle size uniformity coefficient of the comminuted steel slag material is larger than 2, preferably larger than 4 and more preferably larger than 6.
  • An advantage of a larger particle size uniformity coefficient is that the porosity of the material is lower and thus also the permeability of the material for a same compaction pressure.
  • the pozzolanic material has a silicon content, expressed as % SiO 2 , of at least 45%, preferably of at least 55% and more preferably of at least 65 % by dry weight. Combined with the relatively low basicity of the pozzolanic material, a relatively large amount of silica-gel is produced compared to the amount of CSH gel which may optionally also be produced.
  • the pozzolanic material may in particular comprise class F fly ash, i.e. fly ash which comprises less than 20% by dry weight CaO, preferably even less than 10% by dry weight.
  • the pozzolanic material comprises however glass powder, in particular soda-lime glass powder.
  • the glass powder comprises preferably comminuted glass cullet particles.
  • Glass cullet is a waste product comprising industrial silicate glass and flat and hollow (container) glass that cannot be introduced in a furnace to be valorised.
  • the glass powder used in the method according to the present invention comprises preferably more than 60% more preferably more than 65% by dry weight of Si0 2 .
  • silica fume is an amorphous polymorph of silicon dioxide. It is an ultrafine powder containing more than 85% by dry weight of Si0 2 . As it contains no or nearly no CaO, only silica-gel is formed in the absence of CaO.
  • the pozzolanic material has a Blaine specific surface area of at least 1000 cm 2 /g, preferably of at least 2000 cm 2 /g, and more preferably of at least 3000 cm 2 /g.
  • the water barrier material has preferably a pH higher than 8.5 and more preferably higher than 9.
  • the portion of the solid particles of the pozzolanic material which remains in the barrier material forms a fine fraction which has a positive effect on the permeability of the barrier material.
  • the pH of the barrier material, or of any other of the materials, as defined in the present patent specification is to be measured by comminuting the material to a particle size of less than 10 mm, by suspending the obtained solid particles in pure water at a liquid/solid ratio equal to 10, by shaking the obtained suspension during 24 hours, by allowing the solid particles to settle and by measuring the pH of the liquid which is in contact with the settled particles (as described for example also in DIN 38414 S4).
  • the solid particles of the pozzolanic material are activated in an alkaline solution before being mixed with the granular material.
  • This alkaline solution is made with at least one alkaline substance which is different from waterglass and which comprises preferably sodium and/or potassium hydroxide.
  • An alkaline solution comprising calcium oxide/hydroxide can also be used but this may lead to a larger amount of CSH gel in the barrier material by a pozzolanic reaction with the pozzolanic material.
  • the pozzolanic material can be activated relatively quickly to produce an amount of silica- gel material, which is subsequently mixed with the granular material to reduce the permeability thereof.
  • This embodiment of the invention is in particular useful in case the granular material has a relatively low pH. This is for example the case when the steel slag material has already been carbonated to some extent to reduce the free lime content thereof.
  • Such a prior carbonation can be carried out by a natural aging of the steel slag material or under accelerated carbonation conditions, for example with a higher carbon dioxide concentration, in particular with a gas containing at least 1 vol.% carbon dioxide.
  • the plasticizing material comprises sewage treatment sludge and/or a clay material.
  • the plasticizing material preferably comprises a clay material which comprises at least 20, preferably at least 30, and more preferably at least 40 % by dry weight of clay particles having a size of less than 2 ⁇ , said clay material comprising in particular a clay soil.
  • a clay material has the advantage that it reduces the leaching of some heavy metals from the barrier material, in particular of nickel.
  • the plasticizing material is preferably added in such an amount to said mixture that said mixture has a plasticity index which is higher than 1 , preferably higher than 2, more preferably higher than 3 and most preferably higher than 4, the plasticity index being the difference between the liquid limit of the mixture and the plastic limit of the mixture, both measured in accordance with the ASTM standard test method D 4318. These limits are also known as the Atterberg limits.
  • the present inventors have found quite surprisingly that notwithstanding the granular character of the finely comminuted steel slag particles, it is possible to achieve a mixture which is at least slightly plastic (i.e. having a plasticity index between 1 and 5) which is enough for landfill cover applications.
  • a comparative test with river sand instead of the comminuted steel slag revealed that with river sand no cohesion at all could be obtained.
  • the present invention also relates to a water barrier material obtained by the method according to the present invention and also to the use of this water barrier material for producing a water barrier underneath, aside and/or on top of a landfill.
  • Figure 1 is a graph representing the particle size distribution of the fine fraction of the crushed stainless steel slag used in Experiment 1 , the particle size distribution being measured by dry sieving; and Figure 2 shows the titration curves of a stainless steel slag material and of quartz sand illustrating the buffering effect of the stainless steel slag material.
  • the present invention generally relates to a method for producing a water barrier material.
  • the water barrier material is in particular intended as landfill cover or capping or as landfill liner underneath and/or aside a landfill. When used as landfill cover, the water barrier material should preferably remain at least slightly plastic (i.e.
  • the water barrier material may become stiffer (i.e. less plastic), for example by a natural carbonation of the steel slag material contained therein.
  • the material may become immediately stiffer.
  • cementitious materials or carbonating agents such as for example carbonates like potassium and sodium carbonate or bicarbonate in combination with for example calcium or magnesium hydroxide, in order to increase the strength of the barrier material.
  • clay materials are often applied as landfill cover or lining.
  • clay materials should provide a permeability which is less than 1 .0 10 "9 m/s in the Walloon Region of Belgium.
  • the water barrier material is mainly made of waste materials instead of natural materials.
  • These materials comprise first of all a granular material that comprises a comminuted steel slag material and further a plasticizing material and a pozzolanic material.
  • the pozzolanic material should show a basicity, i.e. a ratio between its CaO content (i.e. its calcium content expressed as % CaO) and its Si0 2 content (i.e. its silicon content expressed as % Si0 2 ), which is smaller than 0.20 and preferably smaller than 0.15.
  • This pozzolanic material is activated under alkaline conditions so that a silica-gel material is produced.
  • This silica-gel material fills the pores of the mixture of comminuted steel slag material and plasticizing material at least partially to reduce the permeability, i.e. the hydraulic conductivity, of this mixture.
  • the pozzolanic material comprises solid particles which remain at least partially in the barrier material.
  • the alkaline steel slag material is incorporated in such an amount in the water barrier material that this barrier material is alkaline, and has in particular a pH higher than 8. Due to the high pH of the barrier material, the production of silica-gel material continues in-situ in this water barrier material. In this way, the low permeability of the barrier material is maintained for a very long period of time. By the in-situ gel formation, the permeability of the barrier material becomes even lower during at least the first months after having produced the barrier material.
  • the steel slag material used in the method of the present invention should be a relatively fine material. It should more particularly have a D 0 value on dry sieving which is smaller than 100 ⁇ , preferably smaller than 70 ⁇ , more preferably smaller than 40 ⁇ and most preferably even smaller than 20 ⁇ . A finer steel slag material enables to achieve a lower permeability.
  • the steel slag material may be a common steel slag material produced for example in a basic oxygen steelmaking furnace starting from pig iron.
  • This steel slag material is in particular an LD steel slag material.
  • the steel slag material used in the method of the present invention is however preferably a stainless steel slag material.
  • Stainless steel slag is produced during the production of stainless steel.
  • the stainless steel may be chromium steel or nickel-chromium steel. In general, the stainless steel has a chromium content of at least 1000 mg Cr/kg, more particularly of at least 2000 mg Cr/kg.
  • the stainless steel slag is a nickel- chromium stainless steel slag having a nickel content of at least 50 mg Ni/kg, more preferably at least 100 mg/kg.
  • the slag may be electric arc furnace (EAF) slags, converter slags such as AOD (Argon Oxygen Decarbu ration) and VOD slags (Vacuum Oxidising Decarburation) or a mixture thereof.
  • EAF electric arc furnace
  • converter slags such as AOD (Argon Oxygen Decarbu ration) and VOD slags (Vacuum Oxidising Decarburation) or a mixture thereof.
  • the steel slag material has a calcium content of at least 30%, in particular at least 40% by dry weight CaO and a silicon content of at least 15%, in particular at least 20% by dry weight SiO 2 (the calcium and silicon contents are based on the molecular weight of CaO and SiO 2 respectively but the calcium and silicon do not have to be present in their oxide form but are in particular in other amorphous or crystalline phases, in particular in silicates).
  • the hot slag material removed from the liquid steel is not quenched to produce an amorphous material but is relatively slowly cooled down so that the solidified steel slag is mainly crystalline.
  • the steel slag material used in the method of the present invention comprises preferably more than 50% by dry weight, more preferably more than 60% by dry weight and most preferably more than 70% by dry weight of crystalline phases, the remaining phases being amorphous.
  • the steel slag material preferably has substantially no hydraulic properties. In the method of the present invention it is important for the stainless steel slag material not to contain too much amorphous phases since such amorphous phases may be activated under alkaline conditions so that, due to its relatively high calcium content, too much CSH gel (calcium -silicate- hydrate) could be formed.
  • a molten stainless steel slag can be treated to recover valuable stainless steel particles and to produce aggregates or fine filler materials which can be used as secondary construction materials, is for example disclosed in EP-B-0837043 and in EP-B-21 60367.
  • the molten steel slag is poured into large pits wherein it is cooled down relatively slowly.
  • the large pieces of solidified stainless steel slag are crushed to produce for example coarse and/or fine aggregates that can be used for example in concrete or asphalt.
  • a filler material can be produced which can also be used in concrete or asphalt.
  • valuable stainless steel particles are recovered from the crushed steel slag.
  • a problem of this known recycling process is that also a fine stainless steel slag fraction is produced.
  • This fraction has in particular a particle size of less than 500 ⁇ . Due to its high water absorption property it cannot be used as such in concrete or asphalt.
  • a large portion of the small stainless steel slag particles are caused by the transition of ⁇ - dicalcium silicates into ⁇ -dicalcium silicates in the stainless steel slag. Upon this transition, an expansion of these crystalline phases occurs resulting in a pulverisation of the slag material and the formation of cracks/micro cracks therein.
  • This fine stainless steel slag fraction has a relatively high ⁇ - dicalcium silicate content, namely a ⁇ -dicalcium silicate content of at least 2 %, in particular at least 3 % and more particularly even at least 4 % by dry weight of the crystalline phases of the slag material.
  • this fine steel slag fraction has such a particle distribution, and contains such an amount of fine particles (fines) that a water barrier material can be produced therewith which has a higher cohesion than a water barrier material which is produced with river sand and which also has a lower hydraulic conductivity.
  • the fine steel slag fraction Due to this new valuable application of the fine steel slag fraction, it is also possible to produce a larger amount of fine steel slag material by finely milling the stainless steel slag material so that the milled material has a particle size distribution which shows a D-m value which is smaller than 100 ⁇ , preferably smaller than 70 ⁇ and more preferably smaller than 40 ⁇ . Milling the steel slag material to a smaller particle size enables to recover more valuable steel from the slag material, in particular stainless steel.
  • the steel slag material which is milled is a steel slag fraction which still contains a relatively high amount of stainless steel.
  • the steel slag fraction used to produce the water barrier material therefore preferably has a particle size uniformity coefficient which is larger than 2, preferably larger than 4 and more preferably larger than 6.
  • the steel slag material is incorporated in the water barrier material in an amount of at least 40% by dry weight. In a preferred embodiment, this amount comprises at least 50%, preferably at least 60% and more preferably at least 70% by dry weight of the water barrier material.
  • the steel slag material may be one single steel slag material or a mixture of two or more steel slag materials. Due to the alkaline nature of the steel slag material, this material contributes to the alkalinity of the water barrier material. In order to achieve a continuous in situ silica-gel formation by alkaline activation of the portion of the solid particles of pozzolanic material that remain in the water barrier material, this material should have a pH higher than 8.0. Preferably, it has even a higher pH, more particularly a pH higher than 8.5 and preferably higher than 9.0.
  • a silica-gel material is formed by alkaline activation of the pozzolanic material.
  • a pozzolanic material can however also react with free lime (calcium oxide and/or calcium hydroxide) contained in the mixture so that a CSH gel would be formed rather than a silica-gel.
  • free lime calcium oxide and/or calcium hydroxide
  • silica-gel in the water barrier material is however essential due to the fact that silica-gel provides a more effective water barrier than a CSH gel and that silica-gel prevents the moisture contained in the water barrier from escaping so that the sealing properties of the water barrier material are maintained.
  • a CSH gel dries more quickly out and becomes stiffer more quickly thereby losing its water sealing properties.
  • stainless steel slag compared to for example common steel slag, such as LD slag, is that stainless steel slag has a lower free lime content.
  • the steel slag material used to prepare the water barrier material contains no free lime or has a free lime content which is preferably smaller than 6% by dry weight, more preferably smaller than 4% by dry weight, most preferably smaller than 2% by dry weight and even more preferably smaller than 1 % by dry weight free lime expressed as CaO.
  • the free lime content of the steel slag material can be reduced by bringing this material in contact with carbon dioxide, in particular with gaseous carbon dioxide so that the free lime is converted to carbonate.
  • stainless steel slag material used to produce the water barrier material is preferably not carbonated, or only to a little extent, so that it contains less than 5%, preferably less than 3% and more preferably less than 1 % by dry weight of carbonates.
  • An advantage of such low carbonate contents is that the slag material still has a higher pH enabling more in situ silica-gel formation.
  • the carbonates formed during a carbonation step bind the slag particles to one another so that the resulting pieces have to be crushed or milled again to obtain the required particle size distribution (with the required amount of fine particles).
  • the silica-gel employed in the method of the present invention is produced by alkaline activation of a pozzolanic material which has a basicity, i.e. a CaO/Si0 2 ratio (both amounts in % by dry weight), which is smaller than 0.20, preferably smaller than 0.15.
  • the pozzolanic material preferably has a relatively high Si0 2 content (i.e. a silicon content expressed as % Si0 2 ), in particular an Si0 2 content of at least 45%, preferably of at least 55% and more preferably of at least 65% by dry weight.
  • the pozzolanic material may comprise silica fume.
  • Silica fume has a high Si0 2 content, more particularly an Si0 2 content of more than 85% by dry weight of Si0 2 . It contains no or nearly no CaO so that it has a very low basicity.
  • An advantage of silica fume is therefore that substantially only silica-gel is formed in case no CaO is present in the mixture.
  • the pozzolanic material may also comprise natural pozzolans, in particular natural pozzolans classified by ASTM C 618 (AASHTO M 295) as Class N pozzolans. These include calcined clay and calcined shale.
  • a more preferred pozzolanic material comprises fly ash.
  • This fly ash should be a fly ash having a basicity smaller than 0.20 and preferably smaller than 0.15.
  • the fly ash is in particular ASTM C 618 (AASHTO M 295) Class F fly ash.
  • Class F fly ash materials are low- calcium (generally less than 10% CaO) fly ashes with pozzolanic properties but without cementitious properties. They have relatively high SiO 2 contents, in particular SiO 2 contents higher than 50% by dry weight.
  • Another more preferred pozzolanic material comprises glass powder, in particular soda-lime glass powder.
  • This glass powder can be made by milling glass cullet, which is a waste product comprising industrial silicate glass and flat and hollow (container) glass that cannot be introduced in a furnace to be valorised in the production of new glass.
  • the pozzolanic material may also be a mixture of these pozzolanic materials.
  • the pozzolanic material has to produce a silica-gel by alkaline activation of the solid particles. These solid particles preferably have a large surface to increase the rate of silica-gel formation.
  • the Blaine specific surface area of the pozzolanic material should therefore preferably be equal to or higher than 1000 cm 2 /g, more preferably equal to or higher than 2000 cm 2 /g, and most preferably equal to or higher than 3000 cm 2 /g.
  • the pozzolanic material is preferably used in an amount of at least 2, preferably at least 3, more preferably at least 4 and most preferably at least 5 parts by dry weight for producing 100 parts by dry weight of the water barrier material.
  • the amount of pozzolanic material used to produce the barrier material is preferably less than 20 parts by dry weight for producing 100 parts by dry weight of the water barrier material.
  • the solid particles of the pozzolanic material are activated in situ in the barrier material itself.
  • the solid particles of the pozzolanic material dissolve very slowly in the moisture contained in the barrier material so that new silica-gel material is continuously produced therein.
  • the pozzolanic material can be activated in an alkaline aqueous solution before being mixed with the stainless steel slag material. This is especially advantageous when the steel slag material has a reduced pH by being already carbonated to some extent.
  • the alkaline solution may comprise calcium hydroxide.
  • the alkaline solution comprises however preferably sodium and/or potassium hydroxide.
  • the granular material is not only mixed with a pozzolanic material but also with a plasticizing material.
  • This plasticizing material increases the plasticity or workability of the mixture. Moreover, it improves the water retention properties of the water barrier. This is also important since the silica-gel contained in the barrier material should remain wet in order to be able to exert its water sealing function.
  • the plasticizing material may comprise sewage treatment sludge.
  • This sludge may comprise primary sludge, produced by allowing the solids contained in the waste water to settle, and also activated sludge produced during the biological treatment of waste water.
  • the primary sludge is usually digested microbiologically.
  • the sludge is preferably dewatered and can additionally be hygienised by means of calcium oxide.
  • the sludge is a colloidal material that contributes to the silica- gel formation.
  • an organo-silica-gel material is formed in the presence of the sewage sludge. It also assists in increasing the water retention of the barrier material and it especially improves the plasticity thereof.
  • the plasticizing material may also comprise a clay material.
  • the clay material preferably comprises at least 20, preferably at least 30, and more preferably at least 40 % by dry weight of clay particles having a size of less than 2 ⁇ .
  • the clay material can be a pure clay but it may also be for example a clay soil which is much cheaper than a pure clay.
  • the clay soil can be for example of type E (clay soil) or of type U (heavy clay soil) of the Belgian soil texture classification.
  • the plasticizing material may also be a mixture of different plasticizing materials. It constitutes preferably at least 1 %, more preferably at least 2%, most preferably at least 3% and even more preferably at least 4% by dry weight of the water barrier material.
  • the barrier material comprises less than 50%, preferably less than 40%, more preferably less than 30% and most preferably less than 20% by dry weight of the water barrier material.
  • the plasticizing material is in particular added in such an amount that the water barrier material has a plasticity index which is higher than 1 , preferably higher than 2, more preferably higher than 3 and most preferably higher than 4.
  • the plasticity index is the difference between the liquid limit of the mixture and the plastic limit of the mixture, both measured in accordance with the ASTM standard test method D 4318.
  • the water barrier material By compacting the water barrier material the porosity thereof is reduced and the dry density increased.
  • the water barrier material is preferably compacted to a dry density of at least 1400 kg/m 3 .
  • the method according to the present invention enables to produce a water barrier material which has a hydraulic conductivity, measured with an oedometer-permeameter in accordance with the standard NBN CEN ISO/TS 17892-1 1 , which is smaller than 1 .10 "9 m/s, in particular smaller than 1 .10 "10 m/s or even smaller than 1 .10 "11 m/s.
  • water barrier materials were made by mixing a granular stainless steel slag material with a plasticizing material and with a pozzolanic material that has been activated under alkaline conditions.
  • Sodium hydroxide was more particularly first diluted in water (to make a saturated solution) and was allowed to cool down to ambient temperature.
  • glass powder i.e. the pozzolanic material
  • the granular material was mixed with the plasticizing material (and with the calcium oxide when used) and homogenised for 5 minutes.
  • the activated glass powder was then added to that mixture, additional water was added to achieve the required water/solid ratio and the mixture was homogenised for at least 5 further minutes.
  • Specimens were made from this mixture by compacting it in a Proctor mould having an internal diameter of 10.2 cm and a height of 1 1 .7 cm according to the standard NF P 94 093 (i.e. with 6 complete rotations of the mould instead of 3 as in the standard NBN EN 13682-2).
  • the pastilles were compacted in three layers, each layer being compacted by applying 25 blows.
  • the stainless steel slag material was obtained by crushing a stainless steel slag, sieving off the smallest fraction, removing the particles larger than 0.5 mm from this smallest fraction by means of a hydrosizer and filtering the overflow to obtain the 0/0.5 mm fraction.
  • the granular stainless steel slag had thus a particle size distribution ranging from 0 to 500 ⁇ .
  • the particle size distribution is illustrated in Figure 1 .
  • the stainless steel slag material had a D 0 value of about 35 ⁇ and a D 60 value of about 1 10 ⁇ .
  • the particle size uniformity coefficient of the stainless steel slag material was thus equal to about 3.1 .
  • the stainless steel slag material was fresh so that it contained some free calcium oxide but no calcium hydroxide or calcium carbonate.
  • sewage sludge As plasticizing material two types of sewage sludge were used namely unhygienised sewage sludge and sewage sludge hygienised with calcium oxide.
  • the sewage sludge had a moisture content of about 60% and an organic matter content of 12 - 14% by wet weight.
  • the hygienised sludge contained about 7% by wet weight of calcium oxide. 10 parts of the wet sewage sludge were mixed with 90 parts of the dried stainless steel slag corresponding to a dry weight ratio of 4.8 parts by dry weight sewage sludge to 95.2 parts by dry weight of stainless steel slag material.
  • glass cullet As pozzolanic material use was made of glass cullet, having a size of 0 to 10 mm, which was finely milled with a ball mill to achieve a Blaine specific surface area of about 3000 cm 2 /g.
  • This finely milled glass cullet was first activated in an alkaline solution containing either NaOH or a combination of NaOH and Ca(OH) 2 .
  • the alkaline solution was a concentrated solution wherein the glass powder was allowed to dissolve until a gel was produced (for example after 1 hour at ambient temperature).
  • the Proctor values of the different mixtures were determined, i.e. the water content at which in a Proctor test the highest dry density is obtained. Moisture contents which were close to this Proctor value were used in the following tests:
  • Table 1 Compositions of the water barrier materials of Tests 1 to 6.
  • the dry densities measured for the pastilles of Tests 5 and 6 were respectively about 1600 kg/m 3 and 1560 kg/m 3 .
  • the compression strength of the pastilles was measured with a Controlab hydraulic press of type E0160S.
  • the pastilles of Tests 1 and 2 were so plastic that no compression strength could be measured.
  • the compression strength could be measured but comprised only 0.4 MPa. This material was thus also still plastic.
  • a possible explanation for the higher compression strength obtained in Test 3 could be that more CSH gel was produced due to the fact that not only the sewage sludge and the stainless steel slag material contained some free lime but that additionally the alkaline activation of the glass cullet was partially carried out by means of calcium oxide.
  • the permeability (or hydraulic conductivity) of the water barrier material of the first series of tests has been measured by means of an oedometer-permeameter whilst the permeability of the material of the second series of test has been measured in a triaxial cell wherein a pressure gradient of 200 kPa was applied.
  • Test 4 shows that the combination of the stainless steel slag powder and the sewage sludge enables to achieve already a quite low permeability.
  • Tests 1 , 2, 5 and 6 show that the permeability can be further reduced with a silica-gel material obtained by an alkaline activation of finely milled glass cullet powder, in particular to achieve a hydraulic conductivity which is sufficiently low for landfill cover and liner applications.
  • the glass cullet powder was activated by means of 1 % of Ca(OH) 2 (on the stainless steel slag material) whilst the sewage sludge was hygienised with about 7% by wet weight of CaO. Apparently, the amount of CSH gel produced by reaction of this free lime with the glass cullet powder may have a negative effect on the permeability as in this test the permeability was not low enough for landfill cover applications.
  • the pH of the barrier materials of Tests 4 to 6 has been measured by comminuting the compacted water barrier samples to a particle size of less than 10 mm and by immersing the samples for 24 hours in distilled water at a liquid/solid ratio of 10:1 and by measuring the pH of the water.
  • the pH's were respectively 12.6, 12.7 and 12.7.
  • the leaching values of other heavy metals were also measured, in particular of Al, Cd, Co, Cu, Pb, Sb, Ti, Zn, but only very small values were measured which were mostly even below the detection limits.
  • Tests 4 to 6 of Example 1 were repeated with the same materials. The only difference was that the pastilles were made manually instead of by means of the Proctor apparatus. Table 4: Compositions of the water barrier materials of Tests 7 to 9.
  • the permeability of the water barrier materials decreases over time. This is also the case for the stainless steel slag material that doesn't contain activated glass powder (Test 7). The decreasing permeability could possibly be explained by a natural carbonation of the material. For the water barrier materials that contain activated glass powder, a larger decrease has however been observed. This larger decrease can be explained by the fact that additional silica-gel is formed from the portion of the glass cullet particles that remained in the water barrier material.
  • Tests 8 and 9 (aged for one day) have also been subjected to mechanical tests. From triaxial shear resistance tests it appeared that these materials behaved like sand, with high values for the internal friction angle and low values for the cohesion, so that these materials are suitable for the stability of slopes. Since a water barrier layer often also comprises a plastic foil, in particular a high density polyethylene foil, the resistance against sliding has also been measured between a HDPE foil and the water barrier materials of Tests 8 and 9. The maximum sliding angle was respectively equal to about 35.2 degrees and respectively 30.5 degrees, which is much larger than the sliding angle of about 10.0 degrees obtained with natural clay. Again, the water barrier materials of the present invention are more appropriate for being applied onto slopes than natural clay water barrier materials.
  • Tests 7 to 9 have been modified by the use of a larger amount of sewage sludge.
  • An additional comparative Test 13 was done with a 33.4% sodium silicate solution instead of glass cullet.
  • Table 7 Compositions of the water barrier materials of Tests 10 to 13.
  • Test 13 2.3 23.6 (comp.)
  • the NaOH was first dissolved in water to obtain a saturated solution. After cooling this alkaline solution, which the glass powder was added thereto and was allowed to form a gel by a partial activation of this glass powder.
  • the solid materials (including any Ca(OH) 2 ) were mixed and subsequently the activated glass cullet was added thereto. The moulds were filled in different steps.
  • the dry densities of the pastilles made with the Protor apparatus were measured and also the permeabilities thereof.
  • the permeabilities were measured with an oedometer-permeameter in accordance with the standard NBN CEN ISO/TS 17892-1 1 by applying a load of 20 kg, and thus a pressure of 1 kg/cm 2 , which corresponds to a height of the material which can be estimated at about 5 m. For each test, two or three measurements were done at regular intervals.
  • Table 8 Permeabilities/hydraulic conductivities and dry densities of the water barrier materials of Tests 10 to 13.
  • a plasticity index of 0 indicates a non-plastic material, a plasticity index of 1 to 5 a slightly plastic material and a plasticity index of 5 to 10 a material with a low plasticity, such as for example a clayey sand.
  • the water barrier material made with sodium silicate had a somewhat higher plasticity than the water barrier materials made with glass powder.
  • the glass powder had a Blaine specific surface area of 3000 cm 2 /g. Tests done with a less fine glass powder, having a Blaine specific surface area of 2000 cm 2 /g, showed that the material was less subjected to deformations under a predetermined load, it was less plastic, and its permeability was slightly higher.
  • Table 10 Compositions of the water barrier materials of Tests 14 and 15.
  • the compacted mixtures of Tests 16 and 17 had respectively a dry density of about 1800 and about 1700 kg/m 3 .
  • Table 12 Heavy metal leaching values in mg/l for the water barrier material of Tests 16 to 18
  • Table 13 Permeabilities/hydraulic conductivities of the water barrier materials of Tests 16 to 18 after different aging periods.
  • Table 14 Compositions of the water barrier materials of Tests 16 and 17.
  • the fresh stainless steel slag fraction was made by sieving off the particles smaller than 75 ⁇ from a 0.0/0.5 mm stainless steel slag fraction.
  • the quartz sand mixture was made by mixing 56% of a 0.07/0.15 mm quartz sand with 44% of a 0.10/0.50 mm quartz sand so that the particle size distribution substantially fitted with the particle size distribution of the 0.075/0.5 mm stainless steel slag fraction.
  • the D 0 value of the stainless steel slag fraction was about 88 ⁇ whilst its D 6 o value was about 140 ⁇ so that its particle size uniformity coefficient, defined by it D 6 o/Di 0 ratio was about 1 .6.
  • the water barrier materials produced with the stainless steel slag fraction has a somewhat lower permeability than the water barrier materials produce with the sand mixture after 9 days of aging. This may possibly be explained by the in-situ silica-gel formation that continues in the barrier material made of the stainless steel slag fraction or by other neoformed phases that may be produced in the stainless steel slag fraction. This is not the case in quartz sand since quartz sand is inert under the conditions prevailing in the water barrier material.
  • the permeability of the materials of Tests 19 to 21 is considerably higher, notwithstanding the fact that these materials contained twice as much of the clay soil. It thus appears that the amount of fines in the steel slag fraction, and the particle size uniformity coefficient, has an important effect on the permeability of the material. It does not only affects the porosity of the material but the fines may also provide a larger specific surface area enhancing the production of neoformed phases such as for example silica-gels, CSH gels, carbonates, etc, especially when the steel slag material comprises a portion of amorphous phases and optionally portlandite.
  • the stainless steel slag material has a large buffer capacity.
  • the pH of the water barrier material containing this steel slag material will therefore remain quite high even when being exposed accidentally to an acid medium, or even after a long period of natural carbonation. Due to the high pH of the barrier material, new silica- gel will continuously be formed by the solid particles of pozzolanic material contained therein.

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Abstract

Selon l'invention, une barrière d'eau est fabriquée à partir d'un matériau à base de scories d'acier moulues granulaires alcalines qui est mélangé à un matériau pouzzolanique qui comprend des particules solides et à un matériau de plastification. Grâce à l'activation alcaline du matériau pouzzolanique, qui comprend de préférence du calcin de verre, il est produit un gel de silice qui remplit au moins partiellement les pores de la barrière d'eau afin de réduire sa conductivité hydraulique. En raison de la nature alcaline du matériau barrière d'eau, et en raison du fait que des particules solides du matériau pouzzolanique restent dedans, du gel de silice continue d'être produit dans le matériau barrière pour réduire la conductivité hydraulique et tout gel de silice qui peut être perdu dans le temps est remplacé par le gel de silice nouvellement formé. En raison de la nature cristalline du matériau à base de scories d'acier, la formation de gel de HSC, qui réduirait la plasticité du matériau barrière, est limitée.
PCT/EP2014/075991 2013-12-13 2014-11-28 Méthode de production de matériau barrière d'eau comme couverture de décharge, recouvrement ou confinement de décharge sous et/ou sur le côté d'une décharge, et matériau barrière d'eau produit ainsi WO2015086350A1 (fr)

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CN107913889A (zh) * 2017-11-20 2018-04-17 贵州欧瑞欣合环保股份有限公司 一种用于垃圾的覆盖材料及其制备方法
CN110357459A (zh) * 2019-08-15 2019-10-22 中冶南方工程技术有限公司 一种控制含铬钢渣中铬污染风险的方法
CN114229852A (zh) * 2021-12-03 2022-03-25 山西大学 一种利用钢渣脱除烟气中so2协同提取硅胶的方法

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CN107913889A (zh) * 2017-11-20 2018-04-17 贵州欧瑞欣合环保股份有限公司 一种用于垃圾的覆盖材料及其制备方法
CN110357459A (zh) * 2019-08-15 2019-10-22 中冶南方工程技术有限公司 一种控制含铬钢渣中铬污染风险的方法
CN114229852A (zh) * 2021-12-03 2022-03-25 山西大学 一种利用钢渣脱除烟气中so2协同提取硅胶的方法
CN114229852B (zh) * 2021-12-03 2024-03-22 山西大学 一种利用钢渣脱除烟气中so2协同提取硅胶的方法

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