WO2012175080A2 - Utilisation d'un matériau composite biologique pour éliminer des pollutions à l'arsenic présentes dans l'eau ainsi que procédé - Google Patents

Utilisation d'un matériau composite biologique pour éliminer des pollutions à l'arsenic présentes dans l'eau ainsi que procédé Download PDF

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WO2012175080A2
WO2012175080A2 PCT/DE2012/200022 DE2012200022W WO2012175080A2 WO 2012175080 A2 WO2012175080 A2 WO 2012175080A2 DE 2012200022 W DE2012200022 W DE 2012200022W WO 2012175080 A2 WO2012175080 A2 WO 2012175080A2
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arsenic
nanoparticles
water
use according
layer
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WO2012175080A3 (fr
Inventor
Johannes Raff
Katrin Pollmann
Tobias Günther
André MARQUARD
Beate Katzschner
Sabine Matys
Wolfgang Pompe
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Technische Universitaet Dresden
Helmholtz Zentrum Dresden Rossendorf eV
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Technische Universitaet Dresden
Helmholtz Zentrum Dresden Rossendorf eV
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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    • B01J20/3234—Inorganic material layers
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    • 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
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    • B01J20/0277—Carbonates of compounds other than those provided for in B01J20/043
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    • 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
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    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
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    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
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    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B01J20/3274—Proteins, nucleic acids, polysaccharides, antibodies or antigens
    • 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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/04—Aerobic processes using trickle filters
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4856—Proteins, DNA
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2220/4868—Cells, spores, bacteria
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • 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
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the present invention relates to the use of a biocomposite material and to a method of removing arsenic impurities from water.
  • the use according to the invention or the method according to the invention are suitable for use in groundwater, drinking, service and wastewater treatment.
  • arsenic is the most important contaminant in seepage and surface water in the legacies of the former uranium ore mining in Saxony and Thuringia.
  • Arsenic contaminates as arsenite ([As0 3 ] 3- ) and arsenate ([As0 4 ] 3- ) the drinking, surface and groundwater.
  • Arsenic because of its chemical similarity to phosphorus, can substitute for it and, accordingly, disrupt biochemical processes such as DNA repair, cellular energy metabolism, receptor-mediated transport, and signal transduction.
  • the toxic and carcinogenic properties of arsenic are well documented (1).
  • Iron salts such as. As iron chloride are more effective than the corresponding aluminum salts. In waters with a natural iron content, it is also possible to oxidize this by intensive aeration and precipitate as iron hydroxide. This can then serve directly for the adsorption of the arsenic compounds and in turn be separated off via a filtration (eg sand filter). The reduced arsenic (III) compounds always show a significantly poorer binding behavior than the arsenic (V) compounds.
  • corresponding granules can be used in fixed bed or fluidized bed reactors.
  • the granules are usually also aluminum or Iron oxides in which the binding mechanisms are comparable to those of flocculation. So z.
  • active clay a calcination-enabled modification of the alumina
  • granulated iron hydroxide is also suitable (eg Driehaus, W. et al. (1998) J. Water SRT-Aqua (47), 30-35).
  • iron hydroxide materials have a higher loading capacity and longer life, but can be regenerated compared to the alumina-based materials only with great effort.
  • Inorganic adsorber materials with high active surface area such as nanoscale titanium dioxide and magnetic iron oxide nanoparticles are able to bind arsenic.
  • arsenic can also be bound by a number of organic, sulfur-containing compounds or complex biomolecules, such as keratin, bacterial cellulose or hyperaccumulative plants. Also demonstrated are co-complexations of iron and arsenic by iron-oxidizing bacteria or iron-containing alginate capsules.
  • the patent DE 198 1 1 763 A1 describes a method for arsenic removal from contaminated waters and sludges, in which nascent hydrogen is used. This is formed by the reaction of hydrochloric acid with iron or aluminum powder. Nascent hydrogen can reduce the presence of arsenic (III and V) to arsine, which in turn can be driven off with nitrogen. The arsenic compound is then subsequently either re-deposited as a mirror on cold surfaces after thermal decomposition or removed absorptively or adsorptively.
  • the operational and technical effort the care required and the space required must be taken into account.
  • the proven flocculation methods quickly reach their limits when these criteria are applied. Although these can basically be implemented simply and cost-effectively, they require a high degree of qualification and a high degree of commitment from operators and users to ensure smooth operation.
  • the object of the present invention is therefore to provide a suitable ab- or adsorbent material available, with the help of various arsenic species can be separated easily, inexpensively and at the same time highly efficient.
  • the object is achieved by the use of a biocomposite material which comprises S-layer proteins and nanoparticles for removing arsenic from water.
  • a biocomposite material according to the invention contains at least S-layer proteins and nanoparticles, i. H. z. B. S-layer layers, suspensions or tubes coated with nanoparticles.
  • Such biocomposite materials can be used in particular as flocculation aids.
  • the biocomposite material may also contain an additional carrier.
  • solid support materials such as filter materials, plastic, metal, ceramic or glass
  • the biocomposite material contains organic or inorganic carrier matrices (such as polysaccharides, silica gel, bentonite) into which the S-layer proteins and nanoparticles, for. B. by a sol-gel method embedded.
  • the S-layer proteins are preferably derived from microorganisms, in particular metal-binding microorganisms, which have been isolated from a heavy metal-containing environment or from extreme habitats.
  • the nanoparticles are preferably metal oxide and / or metal carbonate nanoparticles.
  • the metal in the metal oxide and / or carbonate of which the nanoparticles according to the invention are composed is selected from iron, titanium, zinc, tin, yttrium, mixtures thereof and mixtures of said metals with other metals.
  • the other metals are preferably selected from La, Zr, Mn, Y, Cr and Al.
  • the metal oxides used for the nanoparticles contained in the biocomposite material according to the invention selected from iron oxide, titanium dioxide, zinc oxide, tin oxide, and their mixed oxides.
  • Arsenic in the context of the invention both elemental arsenic and arsenic oxides such as arsenic (III) oxide (As 2 0 3 ), arsenic (V) oxide (As 2 0 5 ), arsenic (III, V ) - oxide (As 2 0 4 ) or the corresponding acids arsenic acid (arsenic (V) acid) H 3 As0 4 and Arsenic acid H 3 As0 3, arsenic (111) hydride, arsenic (III) sulfide and various arsenic salts such as AsCl 3 , AsCl 5 understood.
  • arsenic-binding surface proteins of bacteria so-called S-layers
  • arsenic-binding nanoparticles iron and titanium oxides
  • Ferrosorp® is a commercially available adsorbent granulate, which is produced by a patented process from iron (III) hydroxide.
  • the principle of the invention lies in the combination of arsenic-binding nanoscale organic and inorganic materials.
  • the newly used composite material is characterized by a surprisingly increased binding capacity for arsenic (V) compared to the binding values of the individual components.
  • This synergistic effect is based on a spatially highly symmetric, template-directed arrangement of the nanoparticles on a two-dimensional crystalline protein surface, through which a defined cluster size of the nanoparticles is achieved and the nanoparticles are simultaneously immobilized in a stable manner.
  • the defined particle size and highly ordered fixation on a solid substrate - the protein with unique arsenic binding sites - maximizes the available surface area for arsenic binding, thus enabling the removal of arsenic over a wide concentration range.
  • pentavalent arsenic in the concentration range between 0.1 and 10 mg / l is bound more effectively by the novel composite material than by the conventional adsorbent material Ferrosorp® or the individual components S-layer protein, nanoscale titanium dioxide or magnetic iron oxide.
  • the binding capacity also goes beyond what was expected in the combination of these materials.
  • arsenic-binding biological material leads to an increase in the binding capacity for pentavalent arsenic. Separation performances of up to 5.3 mg / g could be achieved in experiments of the inventors. This is almost double that of the commercial arsenic adsorbent Ferrosorp®, an iron hydroxide granulate.
  • the biocomposite material according to the invention preferably has an arsenic-binding capacity of 0.6 to 5.3 mg As / g of biocomposite material, particularly preferably over 3 mg of As / g biocomposite material, in particular in aqueous solutions with an arsenic concentration of 0.1 to 10 mg arsenic per liter ,
  • Nanoparticles in the sense of the invention are particles having a predominantly homogeneous chemical composition, the extent of which in all three dimensions ranges from 1 to 100 nm, preferably up to 50 nm.
  • the nanoparticles of the invention are preferably predominantly crystalline in composition. However, they can also have amorphous portions or be completely amorphous.
  • the nanoparticles are preferably metal oxide or metal carbonate nanoparticles, preferably the metals selected from calcium, iron, titanium, zinc, tin, yttrium, mixtures thereof and mixtures of said metals with other metals.
  • the metal oxides of the metal oxide nanoparticles are preferably selected from iron oxide, titanium dioxide, zinc oxide, tin oxide, yttrium oxide and mixed oxides thereof.
  • the metal carbonates of the metal carbonate nanoparticles are preferably selected from calcium carbonate, zinc carbonate and yttrium carbonate and mixed carbonates.
  • the iron oxide nanoparticles according to the invention are preferably selected from Fe "(Fe") 204 (magnetite), Y-Fe 2 O 3 (maghemite) Fe 2 O 3 (hematite) and a-FeO (OH) (goethite).
  • the tin oxide nanoparticles according to the invention are preferably SnO 2 .
  • these mixed oxides are preferably selected from MnTi0 3 , ZnFe 2 0 4 , ZnAl 2 0 4 , ZnCo 2 0 4 , ZnCr 2 0 4 , ZnGa 2 0 4 , ZnMn 2 0 4 , ZnV 2 0 4 , CoFe 2 0 4 , NiFe 2 0 4 , ZnFe 2 0 4 , CdFe 2 0 4 and FeTi0 3 , preferably ZnFe 2 0 4 .
  • the nanoparticles used in the biocomposite according to the invention preferably have a size of from 1 to 50 nm, preferably from 2 to 20 nm, particularly preferably from 5 to 16 nm.
  • Iron oxide nanoparticles preferably have a size of from 1 to 25 nm, particularly preferably from 1 to 10 nm. Titanium dioxide nanoparticles preferably have a size of from 5 to 20 nm, particularly preferably from 7 to 16 nm. Zinc oxide nanoparticles preferably have one Size of 5-20 nm, more preferably 7-17 nm. Zinc oxide nanoparticles and tin dioxide nanoparticles preferably have a size of 5-80 nm, more preferably 12-60 nm.
  • the use of S-layer-supported nanoparticles allows the prevention of agglomeration of the nanoparticles and thus improved accessibility with a large surface area, and the reliable immobilization of the nanoparticles.
  • the S-layer proteins contained in the biocomposite material used according to the invention are bacterial or archaeal envelope proteins which, by self-organization, can form a regular, closed, highly porous lattice structure with different symmetry properties. So far, several hundred S-layer-bearing strains are known.
  • S-layer proteins prepared from living microorganisms isolated and cultured from a heavy metal-containing environment or other extreme habitats.
  • S-layer proteins biomass is obtained from such microorganisms in sufficient quantity and by the mechanical destruction of the cell walls and an enzymatic and chemical purification according to the known protocol (for example, Engelhardt et al., J. Bacteriol 168 (1): 309 (1986) or Raff et al. (2003) Chem. Mater. 15 (1): 240-244).
  • S-layer proteins have proven to be particularly suitable, which both bind arsenic well, can be isolated to different degrees and form stable layers.
  • Preferred S-layer proteins are derived from the bacteria Geobacillus stearothermophilus ATCC 12980, Lysinibacillus sphaericus NCTC 9602, Bacillus sp. JG-B62 and Bacillus sp. JG-B5T.
  • the first mentioned two bacteria are reference strains, the latter two strains are isolates from the bottom of a uranium waste dump (Haberlandhalde near Johanngeorgenstadt, Germany).
  • Particularly preferred are S-layer proteins from the strains Geobacillus stearothermophilus ATCC 12980, Bacillus sp.
  • S-layer protein sequences are selected from SEQ ID no. 1 to 4 and homologous sequences with 70% sequence identity, preferably 80% sequence identity, particularly preferably 90% sequence identity, in particular 95% sequence identity.
  • the S-layer proteins are characterized by the ability to self-assemble, to form regular lattice structures on solid supports, and by the ability to crystallize at the air / water interface on Langmuir lipid films in the form of large-area, monomolecular assemblies.
  • These paracrystalline lattice structures comprise regularly arranged pores of uniform size. This particular arrangement results in regular spacing relationships between molecular groups of the monomer and the metal clusters that have been attached to the monomer.
  • the pore size and thus the size of the resulting metal clusters can be specifically influenced and tailored to the desired product.
  • the size of the pores defines the distance between the particles. The smaller the distance of the pores, the more densely distributed the deposited nanoparticles are expected. The size of the nanoparticles, in turn, determines the size of the available surface. The smaller the particles, the larger the surface available, which in turn should favor the binding capacity.
  • the S-layer proteins preferably have a pore size of 2 to 8 nm and are used to prepare nanoparticles having a size of 1 nm to 50 nm.
  • the S-layer proteins are used as templates for the preparation of regularly arranged active nanoparticles of a defined size.
  • the binding ability of the biocomposite material according to the invention for arsenic (V) clearly exceeds the sum of the binding values of the individual components (S-layer and nanoparticles).
  • the biocomposite material used according to the invention is very sensitive and capable of binding the existing arsenic even at very low arsenic concentrations and removing it from the water.
  • the biocomposite material used according to the invention is added directly to the water from which arsenic is to be removed, in the form of dried flakes as flocculation aid, preferably thoroughly mixed with the water and then separated again from the water by sedimentation.
  • the isolated S-layers are used directly to deposit corresponding nanoparticles in aqueous solution or suspension thereon. After cleaning and drying, these flakes can be added to a contaminated water and separated either by sedimentation or a magnetic field in the case of ferromagnetic nanoparticles.
  • biocomposite material used according to the invention is additionally introduced into a nanosol in order to obtain materials which are suitable as bulk material. This advantageously allows the use of the material in columns and flat bed reactors.
  • the nanoparticles are synthesized in aqueous solution on the S-layers and added as a nanoparticle S-layer construct in a certain volume ratio of a silicon-containing aqueous acidic or basic nanosol from tetramethoxysilane (TMOS) or tetraethoxysilane (TEOS) and neutralized.
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • the hybrid sol for example, by immersion, vacuum or spray coating on carriers such.
  • the hybrid sol is first poured into molds and then goes from a sol to a gel state by the incipient condensation process. The gel can be divided accordingly and sieved after drying and classified.
  • carriers such as. As ceramics, glass, metal, technical textiles and plastics, by means of a layer-by-layer technique (Decher, G. et al. (1997) Science 277, 1232-1237) coated with a multilayer polyelectrolyte layer, to be very defined to deposit a closed monolayer of an S-layer quickly and reproducibly.
  • the protein coating produced in this way is used for the synthesis of defined and regularly arranged nanoparticles.
  • the property of S-layer proteins is exploited in that they form monolayers at interfaces and are suitable for coating surfaces.
  • a monomer solution is first prepared from S-layers obtained in a known manner. This is preferably done by using 6 M guanidine hydrochloride, 8 M urea or by titration to a pH of 3.
  • the protein solution thus prepared is either used directly or dialyzed several times against ultrapure water to remove the reagents and finally centrifuged for preferably 30 minutes at 40,000 g to separate impurities.
  • the protein solution has a concentration of up to 20 mg / ml or in the second case, the recovered supernatant preferably has a protein concentration of 0.1 to 5 mg / ml.
  • the surface of the technical carrier is preferably cleaned before coating.
  • this is done by means of the RCA method known from the prior art.
  • the carriers are successively with two RCA solutions (1st solution: 25% ammonium hydroxide, 30% hydrogen peroxide, DI water in the ratio 1: 1: 5 to 1: 2: 7, 2nd solution: 37% hydrochloric acid, 30% hydrogen peroxide, DI water in the ratio 1: 1: 5 to 1: 2: 8) for each 10 to 20 minutes at 70 to 80 ° C incubated and then with highly pure Water rinsed.
  • sensitive supports are cleaned with another suitable method for the material used.
  • the carriers thus treated are activated by means of layer-by-layer technology with a plurality, preferably at least three, layers of polyelectrolyte.
  • the polyelectrolyte is preferably polystyrene sulfonate (PSS) combined with polyethyleneimine (PEI), polyallylamine hydrochloride (PAH) or polydiallyldimethylammonium chloride.
  • PES polystyrene sulfonate
  • PEI polyethyleneimine
  • PAH polyallylamine hydrochloride
  • the last layer used is preferably a positively charged polyelectrolyte, preferably PAH.
  • the activation is preferably carried out by immersing the carrier in the corresponding polyelectrolyte solution at a concentration of 3 g / l for 10 minutes, followed by rinsing and transfer to the next solution. These steps are repeated accordingly.
  • the carrier activated in this way is immersed in a protein-monomer solution and incubated for at least 30 minutes, preferably at least 1 hour.
  • the protein-monomer solution preferably has a concentration of 0.1 to 5 mg / ml.
  • the preferred solvent used is 0.5-15 mM TRIS buffer, 10 mM CaCl 2 pH 7.5-9.
  • a component of the invention is also a process for the removal of arsenic from water using the biocomposite material according to the invention.
  • the binding of arsenic to the biocomposite material according to the invention is preferably carried out at a pH of 5 to 9.
  • the water contaminated with arsenic is brought into contact with the biocomposite material according to the invention as a flocculation aid.
  • the dried flakes are added to the contaminated water in a continuous process and thoroughly mixed with the water.
  • the arsenic-laden flakes can be separated by conventional flotation, sedimentation or filtration. Alternatively, by using ferromagnetic materials, the flakes can be separated by means of a magnetic field.
  • the biocomposite material in the form of bulk material is preferably used in continuous processes, wherein it is usually in tower-like or columnar reactors as solid or fluidized bed, through which the water to be treated flows.
  • the adsorption processes take place on the outer and inner surface of the granules.
  • Figure 1 shows the arsenic binding to bacterial S-layer called reference strains or stock isolates (A) and bound to free and S-layer of L. sphaericus JG-A12 nanoparticles (B), in each case compared to arsenic binding to the reference material Ferrosorp® and
  • a monomer solution is prepared, which is dialyzed several times to remove the reagents against ultrapure water and finally centrifuged for 30 min at 40,000 g to remove impurities. From the supernatant thus obtained, a working solution having a protein concentration of 0.1-5 mg / ml is prepared.
  • Acid- and base-insensitive carriers are first purified by RCA method.
  • the carriers are successively with two RCA solutions (1st solution: 25% ammonium hydroxide, 30% hydrogen peroxide, DI water in the ratio 1: 1: 5 to 1: 2: 7, 2nd solution: 37% hydrochloric acid, 30% Hydrogen peroxide, DI water in the ratio 1: 1: 5 to 1: 2: 8) for each 10-20 min at 70-80 ° C incubated and then rinsed with ultrapure water.
  • Metal surfaces are first cleaned with acetone. This is followed by rinsing with EtOH and purification using solution 1 of the RCA method; purification with solution 2 is omitted. Other sensitive surfaces must also be cleaned in a suitable manner.
  • the thus treated supports are activated by layer-by-layer technique with 3 (negative surface charge) or 4 layers (positive surface charge) of polystyrene sulfonate (PSS) alternating with polyethyleneimine (PEI) or (polyallylamine hydrochloride) PAH.
  • PSS polystyrene sulfonate
  • PEI polyethyleneimine
  • PAH polyallylamine hydrochloride
  • the support is alternately immersed for 10 min in the solution with a 3 g / l concentration of polystyrene sulfonate (PSS) combined with polyethyleneimine (PEI) or (polyallylamine hydrochloride) PAH, rinsed with water, transferred to the next solution and repeated this often ,
  • PPS polystyrene sulfonate
  • PEI polyethyleneimine
  • PAH polyallylamine hydrochloride
  • Aqueous suspensions of the S-layer bound nanoparticles are mixed in different concentrations with the Nanosol B with mechanical stirring, neutralized with 0.1 N sodium hydroxide solution and coated by dip coating on z. B. glass slides produced.
  • the aqueous gel formed is stored for 3 days at 4 ° C., then comminuted, dried in a suitable manner and classified to a size of 355-500 ⁇ m.
  • either 20 mM ZnCl 2 are initially introduced into 50 ml ultrapure water or 20 mM ZnCl 2 with 10 mg protein suspended in suspension to 50 ml with ultrapure water.
  • Zn (OH) 2 is precipitated, centrifuged at 8000 g, washed twice with ultrapure water and resuspended in 20 ml ultrapure water.
  • both suspensions are incubated at 37 ° C for 24 h.
  • the unsupported material thus prepared can be used as a flocculant aid by adding it to the arsenic-containing water and re-separating by filtration, sedimentation or centrifugation or, alternatively, using the supported material as a column material in a fixed bed or fluidized bed reactor.

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Abstract

La présente invention concerne l'utilisation d'un matériau composite biologique comprenant des protéines de couche S et des nanoparticules, ainsi qu'un procédé destiné à éliminer des pollutions à l'arsenic présentes dans l'eau. L'utilisation selon l'invention et le procédé selon l'invention conviennent pour une utilisation dans le traitement des eaux souterraines, de l'eau potable, des eaux industrielles ou agricoles et des eaux usées. Les inventeurs ont réalisé des essais permettant d'atteindre une performance de 5,3 mg d'arsenic / g de matériau composite biologique. Cela correspond à une quantité quasiment deux fois supérieure par rapport à l'agent d'adsorption d'arsenic Ferrosorp®, s'agissant de granulés d'hydroxyde de fer disponibles dans le commerce. Ainsi la capacité d'adsorption d'arsenic (V) du matériau composite biologique utilisé selon l'invention dépasse sensiblement la somme des valeurs d'absorption de ses composants pris seuls (couche S et nanoparticules).
PCT/DE2012/200022 2011-04-05 2012-04-05 Utilisation d'un matériau composite biologique pour éliminer des pollutions à l'arsenic présentes dans l'eau ainsi que procédé Ceased WO2012175080A2 (fr)

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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
CN114985446A (zh) * 2022-06-16 2022-09-02 中山大学 一种同步降低酸性镉砷复合污染稻田稻米镉砷含量的方法
CN115432716A (zh) * 2022-08-18 2022-12-06 浙江鸿盛化工有限公司 一种间双废水制备硫酸铵的生产工艺
CN115432716B (zh) * 2022-08-18 2023-10-03 浙江鸿盛化工有限公司 一种间双废水制备硫酸铵的生产工艺

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