EP2181220A1 - Procédé d'amélioration de la performance hydraulique d'une argile - Google Patents

Procédé d'amélioration de la performance hydraulique d'une argile

Info

Publication number
EP2181220A1
EP2181220A1 EP20080782960 EP08782960A EP2181220A1 EP 2181220 A1 EP2181220 A1 EP 2181220A1 EP 20080782960 EP20080782960 EP 20080782960 EP 08782960 A EP08782960 A EP 08782960A EP 2181220 A1 EP2181220 A1 EP 2181220A1
Authority
EP
European Patent Office
Prior art keywords
clay
bentonite
silica
free silica
swelling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20080782960
Other languages
German (de)
English (en)
Inventor
Will Peter Gates
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Elco Solutions Pty Ltd
Original Assignee
Elco Solutions Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2007904474A external-priority patent/AU2007904474A0/en
Application filed by Elco Solutions Pty Ltd filed Critical Elco Solutions Pty Ltd
Publication of EP2181220A1 publication Critical patent/EP2181220A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C04B28/001—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 unburned clay
    • 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
    • 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
    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
    • E02D2300/00—Materials
    • E02D2300/0037—Clays
    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
    • E02D2300/00—Materials
    • E02D2300/0085—Geotextiles
    • 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 problems associated with containing strongly alkaline solutions within a clay-based liner system may result from the combined effect of (1 ) high ionic strength and (2) strongly reactive conditions which can result in the dissolution and loss of the smectite component of the bentonite.
  • Reaction of high ionic strength aqueous solutions (l>0.5M) with clays causes (i) colloidal clays to flocculate, (ii) collapse of gel structure and (iii) an increase in the connectivity of interparticulate pores, thereby destroying the hydraulic barrier properties of the bentonite.
  • the smectite component is the reactive ingredient necessary for barrier function, so its loss due to dissolution will result in degradation of any hydraulic barrier capability.
  • the present invention provides a method of improving hydraulic performance of clay, such as a bentonite or other clay material, comprising its modification by the addition to the clay of a silica component containing free silica or a siliceous material.
  • the free silica or siliceous material may be added in dry form, for example as a powder, or aqueous form, for example as a stable colloidal suspension.
  • the material used as a source of free silica, not native to the bentonite, that is purposefully added to the clay in accordance with the method, is preferably the powdered form of activated or fumed silica (SiO 2 ), although any siliceous mineral, powdered or otherwise, such as opal CT, cristobalite, tridamite, quartz or other silica polytypes, siliceous material such as silica glass, volcanic ash, flyash, diatomaceous earth or other forms of natural or man made SiO 2 , including organic sources of silica such as rice hulls or derivatives thereof, is suitable.
  • the silica should be added to the clay at a rate between 1 and 50 wt%, preferably between 5% and 10 wt% of the mass of the clay to achieve improved hydraulic performance and barrier resistance to alkaline solutions, especially strong alkaline solutions.
  • the swelling sodium bentonites may be themselves processed to a preferably powdered form, a granulated form or a pelletised form suitable for efficient encapsulation within a geosynthetic clay liner, or be used in their natural unprocessed state in compacted clay liners or other barrier systems. Further, the swelling sodium bentonites may be in a dry form or variously hydrated with water or other suitable solvents to contain water at a controlled saturation involving partial pressures of water vapour less than 1 atmosphere, preferably fully saturated by water, but also may be in an uncontrolled and unsaturated state, as may be expected in many field applications.
  • the swelling sodium bentonites may be alternatively activated or beneficiated to contain any suitable exchange cation such as, but not limited to H, Li, Na, K, Mg, Ca, Rb, Sr, Ba and Cs as well as transition metals and lanthanides. Improving the hydraulic performance of the clay - as represented by parameters such as lowered permeability or hydraulic conductivity to permeating solutions - may be achieved, at least in part, by protecting the active ingredient of the clay, advantageously swelling sodium bentonite, from dissolution in alkaline solution.
  • any suitable exchange cation such as, but not limited to H, Li, Na, K, Mg, Ca, Rb, Sr, Ba and Cs as well as transition metals and lanthanides.
  • Such an active ingredient may be a smectite selected from the swelling 2:1 layer silicate group consisting of montmorillonite, beidellite, nontronite (chloropal), saponite, hectorite, stevensite and synthetic analogs thereof.
  • Montmorillonite is of special interest.
  • Other suitable clays for treatment, that is modification, in accordance with the method include other swelling clay minerals such as vermiculites and non-smectite clay minerals such as kaolin, illite, palygorskite (attapulgite) and sepiolite, or synthetic analogs thereof, and natural or synthetic layer double hydroxides or hydrotalcites. Again, these clays are preferably in the natural, though possibly beneficiated, form.
  • Such protection from dissolution may be achieved whether the modified clay is used alone or as a component of a geosynthetic clay liner or material used as a component of compacted clay liners for containment of liquors, groundwaters or leachates.
  • Use of the modified clay in applications other than geosynthetic clay liners is also possible.
  • Non limiting examples are barrier systems including bunds or encasement structures made from compacted clay, slit trenches and cut-off walls formed from slurries of the modified clay, or the modified clay could be incorporated in other manufactured clay-based composite barriers.
  • free silica, or siliceous materials may be in sufficient quantity to achieve a target SiO 2 or free SiO 2 analysis at which acceptable hydraulic performance of the clay is achieved.
  • GCL geosynthetic clay liner
  • Non-limiting examples of such solutions include aqueous solutions having pH greater than or equal to 9 such as mine waste leachates, mineral ore processing liquors, light metal (e.g Mg, Al, Ti, Ni and so on) including Bayer and other Bauxite processing liquors, alkaline abattoir wastewaters and food processing wastewaters, as well as leachates from cement-based waste storage impoundments often used in radioactive waste containment (Landais and Aranyossy, 2004).
  • the present Applicant postulates that the hydraulic performance and smectite protection mechanism is related to the dissolution of native colloidal ( ⁇ 0.2 micron) free silica, which improves the swelling performance of bentonite which contains native free silica.
  • Strongly alkaline solutions are considered to be largely non-compatible with most Na-bentonites: the high salinity is expected to cause detrimental changes to the gel structure of the hydrated bentonite and cause substantial increases in void ratio (Figure 1 ).
  • High ionic strength induced flocculation and opening of pore volume within the bentonite results in large increases in saturate hydraulic conductivity, or k, by as much as 40 to 100 times (arrow labelled 1 in Figure 1 ).
  • the present invention provides a method for production of clay liners, such as, geosynthetic clay liners, containing, as the predominant active ingredient, swelling sodium bentonite, in a preferably powdered form, as a preferably natural or beneficiated material, comprising adding free silica or siliceous material in an appropriate concentration to the swelling sodium bentonite and intimately mixing the free silica or siliceous material and bentonite to form a modified clay mixture.
  • clay liners such as, geosynthetic clay liners, containing, as the predominant active ingredient, swelling sodium bentonite, in a preferably powdered form, as a preferably natural or beneficiated material, comprising adding free silica or siliceous material in an appropriate concentration to the swelling sodium bentonite and intimately mixing the free silica or siliceous material and bentonite to form a modified clay mixture.
  • the modified clay mixture may either be incorporated into a geosynthetic clay liner during its manufacture or the modified clay mixture is added subsequent to the manufacture of the geosynthetic clay liner.
  • the clay liner incorporating the modified clay need not be a geosynthetic clay liner.
  • Non limiting examples of its use are compacted clay liners, compacted clay encasements, polymer-bentonite composite liners, or as a clay suspension or slurry used to form cut-off walls or slit trenches for sub-surface containment of wastewaters, processing wastes, leachates and groundwaters.
  • the modified clay may be used in hydraulic barrier systems including those formed from compacted bentonite or from hydrated clay or bentonite slurries. Such barrier systems may include sealants composed of bentonite-cement mix or polymer-bentonite mix.
  • the silica component for example in the form of aqueous silica, may be added directly to the pre-manufactured geosynthetic clay liner.
  • the free silica or siliceous material may be added separately from, but immediately after, the addition of dry sodium bentonite to the geosynthetic clay liner (GCL), for example, being applied at, or incorporated within, the surface of the GCL furthest from initial contact with alkaline solutions.
  • GCL geosynthetic clay liner
  • the surface may be composed of synthetic woven geotextiles, non-woven geotextiles, or composite geotextiles which contain the sodium bentonite or mixture of bentonite with free silica or siliceous material.
  • the modified clay mixture may itself be applied, at or incorporated within, the surface of the GCL furthest from initial contact with alkaline solution.
  • the free silica or siliceous material may be added in desired proportion, as above described, directly to, and incorporated within, the surface of the GCL that has initial contact with alkaline solutions.
  • This surface may also be comprised of synthetic materials, such as a woven geotextile, nonwoven geotextile, or composite geotextile which can hold or otherwise contain the desired proportion of added free silica or siliceous material and bentonite.
  • the modified clay mixture may itself be applied at, or incorporated within, the surface of the GCL initially contacting alkaline solution.
  • the free silica may be alternatively added as a stable colloidal suspension in aqueous solution to a post-manufactured geosynthetic clay liner.
  • Addition may occur immediately subsequent to installation on site, but prior to the addition of geomembranes or covering with a standard drainage layer.
  • the colloidal suspension may be sprayed directly onto the surface of the geosynthetic clay liner that will have initial direct contact with the alkaline solutions.
  • Addition of the colloidal silica suspension serves additionally to establish pre-hydration of the geosynthetic clay liner to optimise the hydraulic properties of the geosynthetic clay liner prior to contact with alkaline solutions, especially strongly alkaline solutions.
  • the present invention provides a method of producing a clay barrier to alkaline solution comprising (a) analysing free silica content of the clay; (b) comparing the determined free silica content of the clay with a target value associated with alkaline resistance; (c) contacting the clay, with acceptable free silica analysis above 5-10 wt% silica, with an alkaline solution; and (d) employing the contacted clay, with acceptable free silica analysis, as a barrier to alkaline solutions.
  • the clay produced by the method may be used in a geosynthetic clay liner (GCL).
  • the following embodiment of the present invention relates to a method of manufacture of a clay, for example a bentonite clay, for use in a geosynthetic clay liner (GCL) in which the clay is modified by addition of free silica.
  • GCL geosynthetic clay liner
  • free silica is added either to the bentonite component of the GCL; to the geotextile components of the GCL; or by addition of aqueous silica directly to the GCL during manufacture, or subsequent to GCL manufacture.
  • the bentonite clay used as raw material is composed predominantly of substantially water-free swelling sodium smectite.
  • siliceous impurities such as colloidal opal CT, cristobalite, tridamite and quartz may be present in small percentages
  • bentonites suitable for barrier systems such as GCLs should be composed of >70 wt% smectite and preferably >90% smectite. Lower percentages of the smectite component may be acceptable if >90% of the smectite present has an average fundamental particle size of ⁇ 0.2 microns.
  • the bentonite is not natively in a sodium (Na) form, it should be beneficiated by suitable means, for example as described in Murray (1995).
  • bentonite Most of the bentonite (>60 wt % of the bulk) is composed of particles less than 0.5 microns in size (See Tables 1 and 2) and 97% of the ⁇ 0.2 micron fraction is montmorillonite. Montmorillonite is the predominant component of the bentonite in all particle size fractions ⁇ 2 micron, and the finer fractions ( ⁇ 0.5 micron) are essentially pure montmorillonite (See Table 2). The small amount of non- montmorillonite mineral present in the ⁇ 0.2 micron fraction is represented by native free silica (Si ⁇ 2 ) in the form of opaline silicates.
  • SiO 2 content of both the bulk and finer fractions are elevated (by about 5 - 10% of SiO 2 ) relative to a bentonite having no free silica (See Table 3).
  • the chemical analysis provided in Table 3 represents a Na form of bentonite having >80% of its exchange complex saturated by Na.
  • Table 3 Major oxides for the bulk and ⁇ 0.2 micron fractions of a bentonite suitable for providing good barrier performance to strongly alkaline solutions.
  • the following example provides an indication of the reactivity of various mineral components in bentonite with strongly alkaline pH liquids.
  • XRD X-ray diffraction
  • TGA thermal gravimetric analysis
  • Figure 2 provides XRD traces (Cu Ka radiation) of reaction products, after 6 weeks and 6 months contacting with 1 M NaOH, of bentonite containing native colloidal free silica (lower trace of each set) and bentonite containing 10% activated silica (upper trace of each set), showing loss of free silica and the formation of hydrous aluminosilicate and carbonate minerals.
  • SAS sodium aluminium silicate
  • AHC alumohydrocalcite
  • Figure 3 provides Infrared spectra of bentonite (lower trace of each pair) and bentonite with 10 wt% free silica added (upper trace of each pair) following 6 weeks reaction with 1 M NaOH.
  • Fig 3a details presence of absorbance bands near 3475, 3378, 3246 and a broad band near 2950 - cm "1 , associated with hydrous aluminosilicate phases in addition to the smectite band near 3630 cm "1 .
  • Fig 3b details appearance of absorbance bands near 1430, 1475 and 852 cm “1 as carbonates, shift of main band from 1030 to 1046 cm “1 , loss of absorbance bands near 780 - 800 cm “1 and protection of absorbance bands associated with smectite near 848, 880 and 915 cm “1 with addition of 10% activated silica. Results from Infrared Spectroscopy ( Figure 3, Table 5) for reaction with 1
  • Example 2 The following example provides an indication of the hydraulic performance of a bentonite containing native colloidal free silica when subjected to strongly alkaline and saline solutions.
  • a fluid (ore processing leachate) reported to have the following properties: density of about 1.04 g/cm 3 ; initial pH of 12.4; with dominant anions and cations of Na (12700 ppm), Cl (1070 ppm), Al (3360 ppm) and S (460 ppm) was used.
  • the following example provides further indication of the hydraulic performance of a bentonite containing native colloidal free silica when subjected to strongly alkaline and saline solutions.
  • the same geosynthetic clay liners used in Example 3 that had been permeated with water containing 0.1 M dissolved alkali chloride salts and 1 M NaOH containing 0.1 M dissolved salts were examined by scanning electron microscopy (SEM). Specimens were flash frozen in liquid nitrogen, cut polished and examined after freeze drying. Results are shown in Figures 6, 7 and 8 which respectively provide: Fig 6: Backscattered electron micrographs of geosynthetic clay liner
  • Fig 7 Backscattered electron micrographs of a geosynthetic clay liner (bentonite only) reacted with 1 M NaOH containing 0.1 M dissolved salts and EDS spectra of the regions circled indicating chemistry of montmorillonite (Fig 7a) and of a silica rich phase (Fig 7b).
  • Fig 8 Backscattered electron micrographs depicting formation of aluminosilicate phases (web-like material in Fig 8b) in a geosynthetic clay liner containing bentonite plus 10 wt% SiO 2 as activated silica (larger angular particles in Fig 8a) reacted with 1 M NaOH + 0.1 M dissolved salts. Results can be summarised as follows.
  • XRD, IR and SEM results indicate that reaction of bentonite with 1 M NaOH results in partial dissolution of the smectite component, but that 10 wt % added silica substantially protects the smectite from dissolution, and promotes the formation of new mineral phases (Example 1).
  • IR results further indicate that addition of 10 wt% additional free silica (as activated silica) provides protection for the bentonite against dissolution as, for example, the intensity of the band near 880 cm "1 , which is less affected by 1 M NaOH when 10 wt% activated silica is added to the bentonite.
  • the loss of higher order (00I) reflections (e.g d(002)) in the XRD patterns following reaction of the bentonite containing native free silica (indexed as cristobalite) indicate that significant disruption of ordered layer stacking within the bentonite occurred, due to dispersion and/or loss of ordered stacking domains associated with dissolution of silica.
  • the value of the ratio R (d(opal)/d(smectite)) for the original bentonite was 1.84, but dissolution of the opal reduced that ratio by half when no free silica was added.
  • Colloidal opalline silicas are known to be intimately associated with crystalline layers of bentonites, involved in cementation of stacking domains, and their presence in close association with montmorillonite is probably a limiting factor to the swell index (-24 ml/ 2 g) of the bentonite used (properties listed in Tables 1-3).
  • the swelling index of bentonites which contain native colloidal free silicates is increased upon the removal of the native free silicates and importantly, reaction with 1 M NaOH results in a swell index as high as the original material (Example 3).
  • the removal of the cementing silica through dissolution in strongly alkaline solutions enhances the dispersion and swelling of the bentonite.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

L'invention concerne un procédé d'amélioration de la performance hydraulique d'une argile, comprenant sa modification par l'addition à l'argile d'un composant silice contenant de la silice libre ou une matière siliceuse. L'argile est avantageusement une argile de bentonite de sodium capable de gonfler avec une teneur en smectite supérieure à 70 % en poids. L'argile modifiée peut être employée dans des revêtements d'argile géosynthétiques utilisés pour le confinement de solutions fortement alcalines, ainsi que dans d'autres systèmes de barrière.
EP20080782960 2007-08-20 2008-08-19 Procédé d'amélioration de la performance hydraulique d'une argile Withdrawn EP2181220A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2007904474A AU2007904474A0 (en) 2007-08-20 A Modified Clay and Method for its Production
PCT/AU2008/001212 WO2009023915A1 (fr) 2007-08-20 2008-08-19 Procédé d'amélioration de la performance hydraulique d'une argile

Publications (1)

Publication Number Publication Date
EP2181220A1 true EP2181220A1 (fr) 2010-05-05

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP20080782960 Withdrawn EP2181220A1 (fr) 2007-08-20 2008-08-19 Procédé d'amélioration de la performance hydraulique d'une argile

Country Status (10)

Country Link
EP (1) EP2181220A1 (fr)
AR (1) AR067984A1 (fr)
AU (1) AU2008288689B2 (fr)
BR (1) BRPI0815569A2 (fr)
CA (1) CA2696845A1 (fr)
CL (1) CL2008002455A1 (fr)
NZ (1) NZ583373A (fr)
PE (1) PE20090857A1 (fr)
WO (1) WO2009023915A1 (fr)
ZA (1) ZA201001177B (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102120587B (zh) * 2011-01-17 2013-06-12 内蒙古大学 从富含方英石钙基膨润土矿制取高纯钠基蒙脱石、白炭黑及尺寸可控的纳米二氧化硅的方法
PL3019271T3 (pl) 2013-07-12 2021-08-30 Amcol International Corporation Mieszanina glina/polimer jako bariera dla cieczy o wysokiej wartości pH lub liczbie jonowej
CN113578257B (zh) * 2021-07-20 2023-10-31 中国地质科学院矿产资源研究所 一种铁尾矿复合材料及其制备方法和应用

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FR2631954B1 (fr) * 1988-05-31 1992-10-23 Sif Entreprise Bachy Procede de realisation dans le sol d'une coupure d'etancheite resistant aux acides et beton utile a cet effet
US5501753A (en) * 1994-09-01 1996-03-26 Geosynthetics, Inc. Stabilized fluid barrier member and method for making and using same
US5915881A (en) * 1997-04-30 1999-06-29 Reclamation Technology, Inc. Method and composition of a clay slurry capping system for landfill and mineral waste areas

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009023915A1 *

Also Published As

Publication number Publication date
CL2008002455A1 (es) 2009-06-26
AR067984A1 (es) 2009-10-28
NZ583373A (en) 2011-07-29
PE20090857A1 (es) 2009-07-25
ZA201001177B (en) 2010-10-27
BRPI0815569A2 (pt) 2015-02-18
AU2008288689A1 (en) 2009-02-26
CA2696845A1 (fr) 2009-02-26
WO2009023915A1 (fr) 2009-02-26
AU2008288689B2 (en) 2012-03-01

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