WO2010003267A1 - Système de traitement de l'eau avec un matériau adsorbant à base de grains minéraux pour éliminer l'arsenic et procédés de production, de recyclage et d'utilisation - Google Patents

Système de traitement de l'eau avec un matériau adsorbant à base de grains minéraux pour éliminer l'arsenic et procédés de production, de recyclage et d'utilisation Download PDF

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WO2010003267A1
WO2010003267A1 PCT/CH2009/000243 CH2009000243W WO2010003267A1 WO 2010003267 A1 WO2010003267 A1 WO 2010003267A1 CH 2009000243 W CH2009000243 W CH 2009000243W WO 2010003267 A1 WO2010003267 A1 WO 2010003267A1
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grains
manganese dioxide
adsorbent material
calcinated
mineral
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PCT/CH2009/000243
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English (en)
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Con Hong Tran
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Bibus Ag
Hcth Technology Inc.
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Publication of WO2010003267A1 publication Critical patent/WO2010003267A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0222—Compounds of Mn, Re
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3295—Coatings made of particles, nanoparticles, fibers, nanofibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C02F1/505—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/08—Nanoparticles or nanotubes

Definitions

  • the invention relates to the field of water treatment and more specifically to systems for water purification to remove arsenic and possibly other heavy metals, microbes and other pollutants from drinking water and it relates to adsorbent materials based on surface activated mineral grains, methods of producing and recycling them and to the use of the system.
  • the water treatment system comprises adsorbent material, of which at least a fraction is based on mineral grains and comprises manganese dioxide in a surface layer.
  • Preferred methods of producing the adsorbent material for water purification according to embodiments of the invention are based on calcinated mineral grains which are treated to comprise manganese dioxide on the grain surfaces.
  • the mineral grains can be produced from a variety of minerals, and the described embodiments described with laterite are not limiting the invention to the use of laterite but the invention extends also to the use of other minerals such as limonite or clay etc. It is generally advantageous to use a mineral which at least after calcination has good physical stability in water and is highly porous and exhibiting a large surface area per volume and weight of adsorbing material comprising inner and outer adsorbing surfaces.
  • Arsenic is present in water in a variety of forms mainly in the form of arsenate and arsenite.
  • the term arsenic used within the context of this specification means arsenic in at least one chemical form depending on the chemical context.
  • a first aspect of the invention concerns water treatment systems including highly efficient adsorbent material for arsenic based on mineral grains comprising manganese dioxide or both iron(III) oxyhydroxide and manganese dioxide on the surface. This results in a surprisingly high adsorption capacity for arsenic, compared to the adsorption capacity of calcinated mineral grains treated to comprise iron oxyhydroxide not in combination with manganese dioxide on the surface as known from prior art.
  • the water treatment systems comprises several fractions of adsorbent material for adsorption of multiple pollutants.
  • a water treatment system comprises calcinated laterite grains with iron oxyhydroxide and manganese dioxide on the surface for removal of arsenic.
  • the water treatment system additionally comprises a fraction of calcinated mineral grains in the filtration apparatus for removal of heavy metals in cationic form.
  • This fraction of mineral grains is treated with acid (then alkaline to neutralize) creating a hydroxide layer on the surface comprising iron and aluminum hydroxides. It adsorbs heavy metals in cationic form such as lead, copper, nickel and mercury.
  • such a filtration apparatus comprises fractions of laterite grains which are treated differently in separate compartments separated from each other by a permeable barrier.
  • one or more additional fractions of adsorbent material for other pollutants e.g. for removal of bacteria based on mineral grains coated with nano-silver particles are included.
  • mineral grains derived from minerals other than laterite treated such to comprise iron(III) oxyhydroxide and manganese dioxide on the surface for filtration systems or to combine mineral grains sourced from different minerals in a single water treatment system or furthermore to include grains which are not derived from minerals such as silica gel granules for removal of other pollutants than arsenic.
  • a second aspect of the invention concerns methods of production of differently treated fractions of adsorbent material for various embodiments of the water treatment system according to the invention.
  • Embodiments of the second aspect of the invention concern the production of the highly efficient arsenic adsorption material based on mineral grains which are treated to comprise manganese dioxide or a combination of iron oxyhydroxide and manganese dioxide on the surface. Further embodiments concern methods of production of adsorption material for removal of other pollutants based on calcinated mineral grains, which in special cases can be substituted by non- mineral grains such as silica granules.
  • the exploited mineral naturally has a high iron content, such as laterite.
  • the iron oxyhydroxide on the surface of the mineral grains is produced by hydrolyzing iron oxide present in the calcinated mineral by treatment with acid. For higher adsorption capacity for arsenic manganese dioxide may subsequently be introduced additionally to the surface of the acid treated grains. It is important that the surface layer is thin.
  • adsorbent material comprising iron oxyhydroxide and / or manganese dioxide on the surface
  • they are both introduced to the mineral grains' surface from an external source.
  • dried calcinated laterite grains are contacted with colloidal solutions comprising nano particles of iron(III) oxyhydroxide and / or manganese dioxide.
  • laterite grains are coated with silver nano particles for removal of bacteria.
  • Described methods include treating mineral grains such as calcinated laterite grains or silica gel granules with a solution comprising nano silver particles, or in other variants soaking the grains in a solution containing silver ions and then the nano silver particles are formed on the grains surface by reductive reaction.
  • silver is a generally safe and effective anti-microbial metal.
  • the recycling of adsorbent materials which is saturated with arsenic is disclosed. Besides recycling of the saturated laterite grains the arsenic can be precipitated from the washing solution providing for reutilization of the basic washing solution and for a safe method of disposal of calcium arsenate in concentrated form or reuse of calcium arsenate for other purposes.
  • a fourth aspect of the invention includes the use of water treatment systems with adsorbent material based on mineral grains at least a fraction of which contains manganese dioxide or manganese dioxide and iron oxyhydroxide on the surface for removal of arsenic in a centralized water treatment system e.g. in a commercial or communal setting for the removal of arsenic and other pollutants or for industrial or communal drinking water production.
  • Figure 1 shows an SEM picture of the surface of calcinated laterite grains.
  • Figure 2 shows an SEM picture of calcinated laterite surface after acid treatment according to example 1.
  • Figure 3 shows a time equilibrium curve of arsenic adsorption in example 1.
  • Figure 4 shows the Langmuir isothermal curve of example 1.
  • Figure 5 shows the Langmuir isothermal curve of example 3.
  • Figure 6 shows the break-through curve for example 3.
  • Figure 7 shows an EM of the laterite surface after calcination of example 1.
  • Figure 8 shows an EM of the laterite surface after acid treatment and coating with MnO 2 according of example 3.
  • Figure 9 shows a TEM image OfMnO 2 nano particles.
  • Figure 10 shows a SEM image of calcinated laterite surface prior to coating with MnO 2 nano particles.
  • Figure 11 shows a SEM image of calcinated laterite surface after coating with MnO 2 nano particles.
  • Figure 14 shows a TEM image of FeOOH nano particles.
  • Figure 16 shows the surface of calcinated laterite grains before (a) and after (b) coating with nano FeOOH.
  • a water treatment system for the removal of arsenic and other pollutants from water :
  • the water treatment system comprises a combination of at least two fractions of adsorbent materials based on laterite in a column of a filtration apparatus with several compartments comprising at least one compartment for the adsorption of arsenic and other pollutants present in anionic form and another compartment for the adsorption of other heavy metals in cationic form.
  • the compartments are stacked in a column within the filtration apparatus and are separated from each other by a grid or by a porous membrane e.g. a cotton cloth.
  • a receiving compartment can be at the top or at the bottom of the column and is connected with the water inlet.
  • a compartment Downstream of the receiving compartment is a compartment containing laterite grains of a larger size of approximately 3-4 mm treated with acid (and then alkaline to neutralize) to exhibit a hydroxide layer including iron hydroxide and aluminium hydroxide on the laterite grain surface.
  • cationic adsorption removes heavy metal ions.
  • a subsequent compartment further downstream contains laterite grains of a smaller size e.g. of about 0.5 - 3 mm grain size treated to exhibit a surface layer comprising a combination of iron oxhydroxide and manganese dioxide efficiently removing arsenic.
  • a discharge compartment comprises the water outlet.
  • the arrangement of compartments is not limited to a vertical arrangement and in other embodiments the water flow can be in reverse direction.
  • the laterite grain size in the compartment for adsorption of cationic heavy metal ions is approximately 1-3 mm and the compartment for the adsorption of arsenic and other anionic pollutants contains laterite grains of about 0.5-1 mm grain size.
  • additional compartments are included, or different fractions of adsorption material are not separated in different compartments but may be layered or mixed or there are no separate compartments for water inlet and outlet or there is only one fraction of adsorption material for the removal of arsenic with mineral grains comprising either manganese dioxide or a combination of iron oxyhydroxide and manganese dioxide in the surface layer.
  • adsorbent material for removal of microbes included with mineral grains or silica gel granules comprising nano silver on the surface there is also a fraction of adsorbent material for removal of microbes included with mineral grains or silica gel granules comprising nano silver on the surface.
  • the inlet compartment comprises material which may be based on ceramic material or sand for the filtration of the incoming water for removal of turbidities.
  • Such filtering columns can eliminate arsenic from drinking water at least to below 10 ⁇ g/L, which is the level that should not be exceeded in drinking water according to WHO.
  • variants of the second aspect of the invention i.e. methods of production for adsorbent material.
  • the described methods mainly concern implementations based on the use of laterite, however the invention is not limited to the use of laterite.
  • Equivalent methods of production can be applied to clay, limonite and other minerals.
  • a first preferred variant of a production method yields both a fraction of adsorbent material for arsenic and a fraction of adsorbent material for heavy metals in cationic form and comprises the following 2 or 3-steps, respectively:
  • step 1 calcinated laterite grains are produced:
  • Blocks of naturally dried laterite are calcinated at 900° to 1000°C for several hours, preferably at 950° +/- 10 °C for 4 hours in order to remove naturally adsorbed arsenic and to enhance the physical stability of the laterite by turning it into a ceramic form which is stable in water.
  • the calcinated laterite is ground to grains of a particle size between 0.5 mm and 5 mm or up to 50 mm or up to 200 mm.
  • fractions of variable grain size are separated e.g. a smaller sized fraction with a grain size between 0.5 mm and 4 mm or preferably between 1 mm and 3 mm and a larger sized fraction between 2 mm or 3 mm and 4 or 5 or 6 mm, preferably between 3 mm and 4 mm.
  • the grains are separated into a fraction of smaller sized grains between 0.5mm and lmm and a fraction of larger sized grains with a lower limit of 1 mm and an upper limit of 3 or 4 mm.
  • the calcinated laterite grains are porous mineral grains comprising inner and outer adsorbing surfaces.
  • step 2 the dried calcinated laterite grains are treated with acid to restore the arsenic adsorption capacity of the laterite surface.
  • concentration of iron (III) ions in the acidic solution is controlled to optimize the adsorption capacity of the laterite grains.
  • the grains are soaked with acid e.g. with 1.0 M HCl for a controlled time (between 10 and 30 minutes) to obtain a predetermined Fe 3+ concentration e.g. between 10 "3 and 10 '2 M e.g. by photometric measurement with sulfosalisilic acid as color indicator.
  • the laterite grains are neutralized with base, e.g.
  • Laterite grains produced by steps 1 and 2 is applicable as adsorbent material for removal of heavy metals in cationic form.
  • manganese dioxide is additionally introduced into the hydroxide surface layer of the porous laterite grains.
  • a potassium permanganate solution with a concentration of preferably 0.1 M for 30 minutes with a 1 :1 volume ratio grains to liquid.
  • the concentration of the potassium permanganate solution may be varied e.g. within 0.01 M and 0.1 M with the volume ratio and the incubation time adjusted accordingly.
  • the potassium permanganate diffuses into the iron oxyhydroxide - aluminum hydroxide layer created in step 2.
  • Laterite grains produced by steps 1, step 2 and step 3 have manganese dioxide intercalated with the iron oxyhydroxide — aluminum hydroxide layer covering the outer surface and the inner surface of the laterite grains. This is the adsorptive surface responsible for highly efficient arsenic removal from water.
  • the adsorption capacity of laterite grains treated according to steps 1 to 3 is approx. 75-140 mg, often 120 -140 mg arsenic per g adsorption material.
  • Alternative methods of step 3, which is the additional introduction of manganese dioxide into the hydroxide surface layer include treatment of laterite grains obtained in step 2 with manganese(II) sulfate and oxygen from air in neutral or slightly alkaline media or with manganese sulfate and hydrogen peroxide.
  • the yield of adsorbing material after step 1 and step 2 is applicable as adsorbing material for heavy metals in cationic form and it also exhibits some arsenic adsorbing capacity.
  • the additional treatment of step 3 produces material with much enhanced arsenic adsorbing capacity which however has lost its adsorbing capacity for cationic heavy metal ions.
  • both adsorbent material fractions treated with step 1 and 2 only and adsorbent material fractions produced with steps 1 , 2 and 3 are applicable.
  • step 2 and step 3 of the first variant are replaced with a different treatment.
  • This treatment is an alternative method to create a manganese dioxide/iron hydroxide surface layer on mineral grains. It yields adsorbent material which is highly adsorptive for arsenic(III) and arsenic(V) anions.
  • calcinated laterite grains are produced according to step 1 of the first variant described above but alternatively other mineral grains can be used. Subsequently the mineral grains, such as calcinated laterite grains are soaked in 1-3 M HCl together with manganese(II) sulfate for a suitable time.
  • the wet mass is dropped into a solution containing an equivalent amount of base to neutralize and an equivalent amount of permanganate salt to oxidize the Mn(II) sulfate to MnO 2 .
  • sulfate ions are removed by washing and the grains are dried yielding the adsorbent material.
  • the porous surface of mineral grains is coated with nano dimensional MnO 2 and FeOOH.
  • calcinated laterite grains are produced according to step 1 of the first variant described above prior to the coating. Subsequently, these calcinated laterite grains are contacted with colloidal solutions containing iron oxyhydroxide and / or manganese dioxide nano particles.
  • Production methods of nano dimensional MnO 2 and FeOOH in ethanol - water media and the fact that the concentration of ethanol in the solution plays an important role for the formation of nano-particles and anticoagulation are known from the state of the art.
  • the size of the MnO 2 particles obtained is approximately 10 run to 80 nm as determined by Transmission Electron Microscopy method; the size ofthe FeOOH particles is about 10 nm and 30 nm.
  • adsorbent material according to the third variant of the second aspect of the invention create high performance adsorption material for arsenic removal from groundwater for drinking water production by coating calcinated mineral grains with MnO 2 and FeOOH nano particles present in colloidal solution. .
  • the surface of the grains is changed as revealed by Scanning Electron Microscopy images.
  • the arsenic adsorption capacity of these adsorbent materials produced according to the third variant is even higher than the arsenic adsorption capacity of the material produced according to the first variant or the second variant described above.
  • the maximum adsorption capacity of adsorbent material coated with manganese dioxide nano particles is 195 mg arsenic per gram adsorbent material and for adsorbent material coated with iron oxyhydroxide nano particles it is 135 mg per gram. There are also good results with the combination of the two coatings to even increase the adsorption capacity further.
  • colloidal solutions of nano particles of metals' oxide or hydroxide were prepared.
  • Water or organic solvents in water media were used for creation of nano dimensional MnO 2 and FeOOH from their inorganic salts.
  • the pH of the solution, the concentration of the salts and the reaction temperature all influence the quality of the product as shown in the detailed description of the examples.
  • these colloidal solutions comprising manganese dioxide and/or iron oxyhydroxide nano particles are used for coating calcinated mineral grains such as laterite grains.
  • Further embodiments of the second aspect of the invention include methods of production of mineral grains or other granules with nano silver particles on the surface for removal of microbes.
  • mineral grains such as calcinated laterite grains or silica gel granules are soaked in a solution comprising nano particles of metallic silver particles.
  • the solution is prepared e.g. by reductive reaction of silver ions in water or water-organic solvents with formaldehyde.
  • the silver nano particles attach to the granules surface.
  • mineral grains such as laterite granules are soaked in a solution comprising silver ions and ammonia. Silver ions which are adsorbed to the grains surface are subsequently reduced to silver metal e.g. by adding formaldehyde.
  • a third variant involves soaking silica gel granules in a solution comprising silver ions, then hydrolysing silver ions to form silver oxide, which by heating e.g. at 700 °C for 30 min forms silver metal.
  • water treatment systems including highly efficient adsorbent material for arsenic based on mineral grains comprising both iron oxyhydroxide and manganese dioxide or nano dimensional manganese dioxide on the surface and additionally fractions of other adsorbent materials based on mineral or other granules to remove other pollutants in addition to arsenic.
  • Adsorption material for water treatment based on mineral grains such as laterite which is fully saturated with arsenic is recyclable by washing such adsorbent material with a basic washing solution in order to release the adsorbed arsenate from the laterite grains into the basic washing solution.
  • the base used is generally NaOH or KOH, e.g. 0.2 M NaOH.
  • the basic washing solution may be treated for precipitating the released arsenate in form of an insoluble arsenate salt.
  • precipitant hydroxides of calcium magnesium of barium can be used, preferably calcium hydroxide is used and arsenic is collected as Ca 3 (As0 4 ) 2 precipitate, ready for safe disposal.
  • This adsorbant material adsorbs heavy metal ions in cationic form also serves as starting material for example 3 and it furthermore, this material exhibits arsenic binding at a relatively low level.
  • 68,5 kg raw natural laterite after 30 days of drying at ambient temperature yielded 50 kg dried laterite.
  • Dried laterite was then calcinated at 950° ⁇ 10 0 C for 4 hours and cooled to ambient temperature for 24 h. This calcinated laterite was ground and sieved to collect the 1 - 3 mm fraction which was washed by deionized water to remove dust and then dried.
  • Dried laterite grains were soaked in 1 M hydrochloric acid solution for 30 min with the iron(III) concentration controlled to reach a concentration of 0.001 - 0.01 M.After discharging the acid the grains were neutralized by 0.5 M sodium hydroxide solution. These laterite grains were washed with deionized water until chloride ions were undetectable by a silver nitrate test. The resulting yield of dried laterite grains coated by a hydroxide layer was 19.7 kg.
  • the arsenic adsorption capacity was 6.5 g arsenic per 1 kg material which is the level of the state of the art. Depending on the use of this material either as starting material for treatment according to example 3 or as adsorbent material for heavy metals in cationic form the selection of the size of the calcinated grains can be adjusted.
  • the grains were washed with deionized water until SO 4 2" ions were undetectable by a barium chloride test and dried again.
  • the yield was about 41.5 kg.
  • the arsenic adsorption capacity was 75.5 g to 80.8 g arsenic per 1 kg adsorbent material. Approximately the same yield and adsorption quality can be achieved if the drying temperature in the above procedure is lowered to a temperature between 50°-90°, e.g. to 60°.
  • the solution comprising silver nano particles was prepared: To 100 ml of 0.1 — 0.01 M silver nitrate solution, 5 ml of concentrated (30-35%) ammonium hydroxide solution, 5 ml of 99% ethanol and 3 ml of 5% polyvinyl alcohol in water solution were added and stirred for 30 min at room temperature. Then 5 ml of concentrated formaldehyde concentrated solution were added and stirred continuously until the solution changes to yellow color (about 60 min).
  • the yellow solution is the nano silver solution i.e. comprising nano-silver particles and it is used to coat mineral grains or other granules: e.g.
  • the solution comprising silver nano particles was prepared: To 100 ml of 0.001 — 0.01 M silver nitrate solution, 5 ml of concentrated (30-35%) ammonium hydroxide solution, 5 ml of 99% ethanol and 3 ml of 5% polyvinyl alcohol in water solution were added and stirred for 30 min at room temperature. Then 100 ml of a 1 M glucose solution were added and stirred continuously until the solution changes to dark yellow color (about 60 min). The dark yellow solution is the nano silver solution i.e. comprising nano-silver particles and it is used to coat mineral grains or other granules e.g. according to the procedure described in Example 4a.
  • Example 5 Example 5:
  • the calcinated laterite grains are soaked in a solution comprising silver ions and ammonia which are adsorbed to the grains surface followed by a reduction step to silver metal by adding formaldehyde.
  • silica gel granules 500 g were exposed to open air for 90 min. and then 100 ml of a silver nitrate solution with a concentration in the range of 0.01 - 0.1 M was added, mixed up and down to submerge all granules and set aside for 30 min. Next, 100 ml of a 1.0 M sodium hydroxide solution were added to the mixture, mixed up and down to submerge all granules and set aside for 90 min at room temperature. The mixture was completely dried at 90°C. The mixture was washed with deionized water until nitrate ions were undetectable. The washed granules were then calcinated at 700°C for 30 min. After cooling they are ready as BRM for use.
  • BRM Bacterial Removal Material
  • Nano silver coated grains are filled in a column with a BRM layer thickness of 0.5; 1.0; 1.5; 2.0 and 3.0 cm.
  • a water sample prepared in the laboratory containing bacteria at an initial concentration of 280 MPN/100 ml (MPN most probable number) is loaded.
  • the water flow rate is 1.3 ml per min and cm2.
  • the flow rate is measured in the range of 1.3 to 13.6 ml / min cm 2 on the same column as before with a thickness of the BRM layer of 1.0 cm. The results are shown in table 2. With these conditions the column has the capacity to efficiently remove bacteria up to a flow rate of 10 ml / min cm 2 .
  • columns with a layer of at least 1 cm thickness with adsorbent material based on mineral grains or other granules coated with nano silver particles efficiently remove microbes from water flowing through the layer at a rate of 1.3 to 10.2 ml / min cm 2 .
  • Example 8 Preparation of colloidal solutions containing MnO 2 nano particles and their use for the coating of calcinated laterite grains. Preparation of colloidal MnO 2 nano particles solution:
  • MnSO 4 at a concentration of 3 x 10 "2 M and KMnO 4 at a concentration of 2 x 10 "2 M in solutions of different ethanol concentrations from 0% to 100% for both solutions were prepared and then the MnSO 4 and KMnO 4 solutions were combined with each other.
  • the MnO 2 nano particles were produced by the following procedure: slowly adding KMnO 4 solutions one by one with ethanol concentrations of 0, 5, 10, 25, 50, 75 and 100% into the series OfMnSO 4 solutions having the same volume and ethanol concentrations from 0 to 100%. The adding rate was 2.5 ml solution per min. During the reaction time, the mixture was intensively stirred. The dark brown colloidal solution of MnO 2 nano particles was taken for particle size analysis and for coating of denaturated laterite material.
  • the yield of nano dimensional MnO 2 formation was calculated as percentage of mass ratio between amount of nano dimensional MnO 2 and the theoretical amount based on reaction stoichiometry. Table 1. The effect of ethanol concentration in reagent solutions on nanodimensional MnO 2 formation (%)
  • EPl Percentage concentration of ethanol in MnSO4 solution
  • EP2 Percentage concentration of ethanol in KMnO4 solution
  • Table 1 shows the strong effect of the ethanol concentration in the solution of the reagents on the formation OfMnO 2 nano particles.
  • Figure 9 shows a TEM image of MnO 2 nano particles. Most of them have approximately the same size with a length of 60 nm and a width of 20 nm.
  • a suitable amount of dried calcinated laterite with size of 0.5 — 1.0 mm diameter was dropped into a colloidal solution of MnO 2 nano particles and softly shaken for 60 min. When almost all of the MnO 2 particles were adsorbed on the laterite surface, the solution became colorless and was discharged.
  • the coated grains were washed by an aqueous solution with the same ethanol concentration as in the colloidal solution and then dried at 105 0 C for 4 hours. The maximum adsorption capacity was determined to be 138.89 mg arsenic per 1 gram of adsorbent.
  • Figures 10 and 11 show the surface of denaturated laterite before and after coating of MnO 2 particles in SEM images and the difference is obvious. Before coating, the surface of laterite is quite smooth; but after coating there are nano crystals Of MnO 2 with a needle shape distributed all over the laterite surface.
  • Figure 12 shows a time equilibrium curve of arsenic adsorption by calcinated laterite grains coated with MnO 2 nano particles. 1 gram adsorbent was dropped into 250 ml arsenic solution of 1000 ppb concentration. The solution was stirred continuously. Periodically the arsenic concentration was determined and the results are shown in the figure. The equilibrium adsorption time was 8 hours.
  • Figure 13 shows the Langmuir adsorption isothermal curve for calcinated laterite grains coated with MnO 2 nano particles which was established with the initial concentrations of arsenic from 0.00 to 100 ppm and the results are shown in the figure.
  • Figure 14 shows a TEM image of FeOOH nano particles which were prepared particles as described above.
  • the TEM image reveals uniform needle shaped nano crystals of FeOOH with a size of about 40 x 10 nm.
  • Figure 15 shows the influence of ethanol concentration on the formation of FeOOH nano particles.
  • Figure 16 shows the SEM image of adsorbent surface before and after coating with FeOOH nano particles.
  • Figure 17 shows a time equilibrium curve of arsenic adsorption by calcinated laterite grains coated with FeOOH nano particles. Upon the adsorption time in for 0 to 10 hours, arsenic concentration in liquid phase was measured and 6 hours were determined to be the adsorption equilibrium time.
  • Figure 18 shows the Langmuir adsorption isothermal curve for calcinated laterite grains coated with FeOOH nano particles which was established with the initial concentrations of arsenic from 0.00 to 100 ppm and the results are shown in the figure.
  • the adsorption capacity was determined to be 92 mg arsenic per 1 g adsorbent material.
  • a filtration column with 4.2 kg laterite treated according to example 1 and 4.2 kg laterite grains treated according to example 3 is saturated with adsorbed arsenic after about 10'0OO 1 of water with an arsenic concentration in the range of 198.4 ⁇ g/L.
  • the adsorbent material can be recycled by washing with 0.25 M NaOH followed by washing with deionized water until a value of pH 6-7 of the outlet water is reached
  • the column can be refreshed at least ten times with the adsorption capacity decreasing about 20% and loss of mass of about 5%.
  • the concentrated arsenate in washing solution was precipitated to form insoluble arsenate salt such as calcium arsenate.
  • the calcium arsenate can be used for other industrial purposes or disposed of safely and the NaOH can be recycled as washing solution.

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Abstract

L'invention concerne le domaine du traitement de l'eau et plus spécifiquement des systèmes de purification d'eau visant à éliminer de l'eau potable l'arsenic et éventuellement d'autres métaux lourds, les microbes et d'autres polluants et elle concerne des matériaux adsorbants à base de grains minéraux à surface activée, des procédés de production et de recyclage des matériaux adsorbants et l'utilisation des systèmes de traitement de l'eau. Le système de traitement de l'eau selon l'invention comprend un matériau adsorbant, dont au moins une fraction est à base de grains minéraux et comprend du dioxyde de manganèse dans une couche superficielle. Le procédé de production du matériau adsorbant pour la purification de l'eau selon l'invention se base sur des grains minéraux calcinés qui sont recouverts de façon à comprendre du dioxyde de manganèse sur les surfaces des grains.
PCT/CH2009/000243 2008-07-10 2009-07-08 Système de traitement de l'eau avec un matériau adsorbant à base de grains minéraux pour éliminer l'arsenic et procédés de production, de recyclage et d'utilisation WO2010003267A1 (fr)

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WO2014132106A1 (fr) * 2013-02-27 2014-09-04 University Of Calcutta Préparation et utilisation de nanoparticules métalliques
CN104275147A (zh) * 2014-09-28 2015-01-14 云南泛亚能源科技有限公司 一种天然矿土负载纳米除砷材料及其制备方法
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WO2012140520A3 (fr) * 2011-03-25 2013-01-31 Indian Institute Of Technology Composition à libération prolongée d'argent pour la purification d'eau
CN107010702A (zh) * 2011-03-25 2017-08-04 印度理工学院 用于水净化的银持续释放组合物
AU2012241522B2 (en) * 2011-03-25 2017-06-08 Indian Institute Of Technology Sustained silver release composition for water purification
JP2014509938A (ja) * 2011-03-25 2014-04-24 インディアン インスティテュート オブ テクノロジー 浄水のための持続的な銀放出組成物
WO2012140520A2 (fr) * 2011-03-25 2012-10-18 Indian Institute Of Technology Composition à libération prolongée d'argent pour la purification d'eau
WO2012175080A3 (fr) * 2011-04-05 2013-05-23 Helmholtz-Zentrum Dresden - Rossendorf E.V. Utilisation d'un matériau composite biologique pour éliminer des pollutions à l'arsenic présentes dans l'eau ainsi que procédé
US10035131B2 (en) 2011-11-24 2018-07-31 Indian Institute Of Technology Multilayer organic-templated-boehmite-nanoarchitecture for water purification
US10041925B2 (en) 2012-04-17 2018-08-07 Indian Institute Of Technology Detection of quantity of water flow using quantum clusters
KR101393665B1 (ko) * 2012-05-21 2014-05-13 단국대학교 산학협력단 금속이온 흡착제 및 이의 제조방법
CN102923887B (zh) * 2012-11-22 2014-01-01 大连海事大学 一种处理重金属废水的方法
CN102923887A (zh) * 2012-11-22 2013-02-13 大连海事大学 一种处理重金属废水的方法
WO2014132106A1 (fr) * 2013-02-27 2014-09-04 University Of Calcutta Préparation et utilisation de nanoparticules métalliques
CN103599746A (zh) * 2013-11-04 2014-02-26 中国科学院合肥物质科学研究院 一种天然矿土负载纳米除砷剂的制备方法
CN104275147A (zh) * 2014-09-28 2015-01-14 云南泛亚能源科技有限公司 一种天然矿土负载纳米除砷材料及其制备方法
WO2016163868A1 (fr) * 2015-04-07 2016-10-13 Daflow S.A. De C.V. Mélange, filtre et procédé pour éliminer l'arsenic; système et procédé pour obtenir de l'eau potable
CN106424753A (zh) * 2016-10-14 2017-02-22 泉州师范学院 一种MnO2‑Ag纳米复合材料的制备及其应用
CN106424753B (zh) * 2016-10-14 2018-12-07 泉州师范学院 一种MnO2-Ag纳米复合材料的制备及其应用
CN108967442A (zh) * 2018-07-24 2018-12-11 广东省生态环境技术研究所 一种抑制水稻镉砷积累的亚铁改性硒溶胶及其制备方法与应用
CN110508233A (zh) * 2019-05-30 2019-11-29 中国科学院地理科学与资源研究所 一种用于治理砷污染的固化稳定化材料及其制备方法
CN110342540A (zh) * 2019-08-05 2019-10-18 云南驰宏资源综合利用有限公司 一种基于改性纳米铁的硫酸铵溶液深度除砷方法
CN110342540B (zh) * 2019-08-05 2022-07-29 云南驰宏资源综合利用有限公司 一种基于改性纳米铁的硫酸铵溶液深度除砷方法

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