WO2020114556A1 - Use of iron oxide particles in wastewater to eliminate contaminants - Google Patents

Use of iron oxide particles in wastewater to eliminate contaminants Download PDF

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Publication number
WO2020114556A1
WO2020114556A1 PCT/DE2019/101032 DE2019101032W WO2020114556A1 WO 2020114556 A1 WO2020114556 A1 WO 2020114556A1 DE 2019101032 W DE2019101032 W DE 2019101032W WO 2020114556 A1 WO2020114556 A1 WO 2020114556A1
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Prior art keywords
iron oxide
oxide particles
particles
heavy metals
cyanides
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PCT/DE2019/101032
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German (de)
French (fr)
Inventor
Rainer Meckenstock
Sadjad MOHAMMADIAN
Beate KROK
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Universitaet Duisburg-Essen
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Priority to EP19831976.6A priority Critical patent/EP3860954A1/en
Publication of WO2020114556A1 publication Critical patent/WO2020114556A1/en

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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
    • B01J20/0225—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
    • B01J20/06—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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/3028—Granulating, agglomerating or aggregating
    • 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
    • B01J20/3202—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
    • 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
    • B01J20/3242—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
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular 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
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/18—Cyanides
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • 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 use of iron oxide particles in waste water for the elimination of heavy metals and / or cyanides and / or polyfluorinated alkyl compounds, colloidal iron oxide particles suspended in waste water adsorbing the heavy metals and / or cyanides and / or polyfluorinated alkyl compounds tie.
  • the particles are subsequently agglomerated and precipitated with or without the aid of flocculants.
  • the process for adsorbing contaminants and the process of flocculation for removing heavy metals and cyanides from industrial and mining waters are already known.
  • iron chloride and polyacrylamide for example, are added to the wastewater in order to achieve good flocculation and to remove the adsorbed or bound impurities from the wastewater. It is important that the heavy metals and / or cyanides adsorbed or bound to the adsorber substances are easier to separate later, so that the adsorber substances sediment well.
  • the adsorber substances known in the prior art are generally organic chemicals which function, for example, as ion exchangers.
  • Activated carbon is also used as the adsorbent substance, but it has the disadvantage of a long contact time, which is necessary so that the pollutants can diffuse into the interior of the pore.
  • wastewater treatment plants use large amounts of activated carbon in appropriately sized treatment tanks.
  • flocculants to increase the pore sizes such as iron chloride and polyacrylamide, creates a relatively large volume of sludge, which has to be reprocessed, for example, by drying, and the substances used can only be removed with high energy input and cannot be regenerated.
  • DE 100 35 432 A1 is known from the prior art, in which a lime-clay suspension for liquid manure processing and soil improvement is described. However, adsorption of heavy details or cyanides on the suspended Kaik clay components is not mentioned in the document.
  • DE 102 10 786 A1 is known as prior art, in which a mixture of granules is described as adsorber materials for contaminated zones, in which heavy metals or cyanides can be adsorbed on iron oxides. Coating the granules with humic substances is not mentioned in the publication.
  • DE 10 2015 221 206 A1 describes a composition, in particular for immobilizing metal ions such as heavy metals from waste water, comprising at least one iron hydroxide and at least one porous carrier material such as, for example, granules. Adsorption of cyanides and entry of a suspension with subsequent agglomeration is not disclosed in the document.
  • DE 10 2018 103 952 A1 describes the use of humic oxide-coated iron oxides as agglomeration
  • the object of the present invention is therefore a method of generating contamination-free waste water, contaminations such as heavy metals and / or cyanides and / or fluorinated alkyl compounds being removed from the waste water up to the discharge limit and the contamination in the waste water being adsorbed or bound by the iron oxide particles.
  • Particles of iron oxide can have nanocrystalline constituents which enable heavy metals and / or cyanides and / or fluorinated alkyl compounds to be adsorbed or bound to the particles used.
  • iron oxide particles are introduced into areas of contaminated wastewater to which solutions of alkaline earth metal salts of variable concentration are added.
  • the aggregation of the iron oxide particles following the entry of the particles and the addition of the alkaline earth metal salt solutions can be used as a fixed component for the adsorption or binding of heavy metals and / or cyanides and / or polyfluorinated alkyl compounds.
  • alkaline earth metal solutions are added in such a way that, after the iron oxide particles have been added, the alkaline earth metal solutions are gradually added and a pH value is set which prevents the particles from aggregating and adsorbing or binding contaminants such as heavy metals and / or cyanides and / or or polyfluorinated alkyl compounds on the particles.
  • the pH is adjusted in a range from 6.0 to 9.0.
  • a concentration variable ie 5 to 10 times the amount of a solution containing alkaline earth metal, in particular a solution containing calcium or magnesium ions, is added to the iron oxide particles.
  • heavy metals and / or cyanides and / or polyfluorinated alkyl compounds can be adsorbed or bound to the particles, and the particles can then agglomerate and precipitate.
  • nano-goehtitle particles are used as iron oxide particles.
  • nano-goethite coated with humic acid is used as an adsorbent or binding partner for the contamination of waste water, the hydrodynamic diameter of which can be in a range of 100-500 nm.
  • the particles are stable in monovalent ion solutions due to an adsorbed layer of humic acids. Particle aggregation occurs quickly when calcium or magnesium is present. The reason for this is the onset of complexation, which takes place on the surface due to the interaction of divalent cations with the particle coated with humic acid. Above a limit dose of divalent cations, the particles and adsorption aggregate Heavy metals and / or cyanides and / or polyfluorinated alkyl compounds can be bound or bonded promptly to the surface of the particles.
  • Heavy metals and / or cyanides and / or polyfluorinated alkyl compounds include.
  • heavy metals are to be understood as elements which have a density> 5 g / cm 3 .
  • heavy details occur in natural material cycles.
  • trace elements and trace nutrients can also have a pollutant character.
  • Heavy metals are also used by numerous branches of industry. In contaminated sites, heavy metals occur primarily in mining waste, in smelting works, foundries, metal processing companies with electroplating, and as enrichments in combustion residues (slags). Heavy metals are also contained in commercial and household waste. Heavy metals are of particular importance in environmental toxicology. Even at relatively low concentrations, they are harmful to human and animal organisms and accumulate through the food chain.
  • the ubiquitous exposure rate often exceeds the limit of the resilience.
  • Even essential heavy metals are toxic in higher concentrations or can, such as. As copper, damage plant growth even in relatively low concentrations. Heavy metals are persistent and accumulate in the soil, so that convection, dispersion or diffusion in the soil should be prevented at a disproportionately high concentration. Heavy metals must also be removed from industrial wastewater, since industrial wastewater is often reused and must not contain any disruptive substances.
  • the heavy metal compounds are adsorbed or bound to the iron oxide particles, which subsequently agglomerate. The binding preferably takes place on the hydroxylated surfaces of the iron oxide.
  • Hydroxo complexes (MOH + ) of the heavy metals are therefore preferably adsorbed. According to the hydrolysis constant, the specific adsorption of the heavy metals increases in the following order: Cd ⁇ Ni ⁇ Co ⁇ Zn «Cu ⁇ Pb « Hg
  • the adsorbed pollutants can be mobilized again by changing the physico-chemical environment. However, whether a mobilizing effect occurs depends essentially on the structure of the iron oxides and the organic substance.
  • the water solubility of the generally weakly polar complexing agent is based on the dissociation of acidic functional groups, which increases with the pH.
  • Heavy metal humates are generally poorly soluble and can only be mobilized at higher pH values, so that the use of the agglomerated goethite particles coated with humic acid are particularly suitable for adsorbing or binding heavy metals.
  • the agglomerated particles should also be used to adsorb or bind cyanides from the waste water.
  • cyanides are known in emissions from waste water or exhaust gases from coking plants, gas plants, mineral oil refineries, hardening plants and electroplating companies.
  • the environmental behavior of the cyanides is characterized above all by high mobility due to their high water solubility and high toxicity to biosystems.
  • the free cyanide ion (CN) is characterized by a high water solubility and a low adsorbability.
  • the cyanide ion is the strongest poison in inorganic chemistry based on its lethal dose. It is therefore provided according to the invention that the property of the cyanide ions is to be used, that they are complexes stable with heavy metals (Fe, Cu, Zn and Cd) form less water solubility and toxicity.
  • heavy metals Fe, Cu, Zn and Cd
  • the agglomerated particles are intended to adsorb or bind polyfluorinated alkyl compounds, polyfluorinated alkyl compounds in particular meaning per- and polyfluorinated alkyl compounds (PFAS).
  • Perfluorinated and polyfluorinated alkyl compounds also include polyfluorinated alkyl surfactants, such as perfluorooctane sulfonate (PFOS), which in the prior art have only been able to be separated from the waste water as contamination with the addition of activated carbon and which require time-consuming and costly processing.
  • PFOS perfluorooctane sulfonate
  • FIG. 1 shows schematically that when mixed and after the addition of goethite particles 2, alkaline earth metal salt solutions 3 and / or flocculants 4 to the wastewater 1, the particles 2 are aggregated, with contaminants in the wastewater 1, for example heavy metals 5 and / or adsorb or bind cyanides 6 and / or polyfluorinated alkyl compounds 8 to the particles 2 (5, 6, 8). It is also possible without a flocculant 4

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The invention relates to the use of iron oxide particles in wastewater to eliminate heavy metals and/or cyanides. According to the invention, colloidal iron oxide particles suspended in wastewater are agglomerated by the addition of alkaline-earth metal salt solutions and/or flocculants at variable concentration, and subsequently the heavy metals and/or cyanides and/or polyfluorinated alkyl compounds are adsorbed onto or react with the iron oxide particles.

Description

VERWENDUNG VON EISENOXID-PARTIKELN IN ABWÄSSERN ZUR USE OF IRON OXIDE PARTICLES IN WASTEWATER FOR
ELIMINIERUNG VON KONTAMINATIONEN Die Erfindung betrifft die Verwendung von Eisenoxid-Partikeln in Abwässern zur Eliminierung von Schwermetallen und/oder Cyaniden und/oder polyfluorierten Alkylverbindungen, wobei kolloidale, in Abwasser suspendierte Eisenoxid-Partikel die Schwermetalle und/oder Cyanide und/oder polyfluorierte Alkylverbindungen adsorbieren oder binden. Die Partikel werden nachfolgend mit oder ohne Hilfe von Flockungsmitteln agglomerisiert und ausgefällt. ELIMINATION OF CONTAMINATIONS The invention relates to the use of iron oxide particles in waste water for the elimination of heavy metals and / or cyanides and / or polyfluorinated alkyl compounds, colloidal iron oxide particles suspended in waste water adsorbing the heavy metals and / or cyanides and / or polyfluorinated alkyl compounds tie. The particles are subsequently agglomerated and precipitated with or without the aid of flocculants.
Allgemein ist das Verfahren zur Adsorption von Verunreinigungen und das Verfahren der Flockung zur Entfernung von Schwermetallen und Cyaniden aus Industrie- und Bergbauwässem bereits bekannt. Dabei werden für die Flockung dem Abwasser zum Beispiel Eisenchlorid und Polyacrylamid zugegeben, um eine gute Flockung zu erzielen und die adsorbierten oder gebundenen Verunreinigungen aus dem Abwasser zu entfernen. Dabei ist es wichtig, dass zur spateren erleichterten Abtrennung der an die Adsorbersubstanzen adsorbierten oder gebundenen Schwermetalle und/oder Cyanide, die Adsorbersubstanzen gut sedimentieren. In general, the process for adsorbing contaminants and the process of flocculation for removing heavy metals and cyanides from industrial and mining waters are already known. For the flocculation, iron chloride and polyacrylamide, for example, are added to the wastewater in order to achieve good flocculation and to remove the adsorbed or bound impurities from the wastewater. It is important that the heavy metals and / or cyanides adsorbed or bound to the adsorber substances are easier to separate later, so that the adsorber substances sediment well.
Die im Rahmen des Stands der Technik bekannten Adsorbersubstanzen sind in der Regel organische Chemikalien, die z.B. als ionentauscher funktionieren. Ferner wird auch Aktivkohle als Adsorbersubstanz eingesetzt, die jedoch den Nachteil einer langen Kontaktzeit aufweist, die nötig ist, damit die Schadstoffe in das Poreninnere diffundieren können. Damit auch in kürzerer Zeit möglichst alle Schadstoffe abgefangen werden, setzen Kläranlagen größere Mengen Aktivkohle in entsprechend großen Behandlungsbecken ein. Durch den notwendigen Zusatz von Flockungsmitteln zur Erhöhung der Porengrößen wie Eisenchlorid und Polyacrylamid wird jedoch ein relativ großes Schlammvolumen erzeugt, was beispielsweise durch Trocknung wiederaufbereitet Werden muss und wobei die verwendeten Substanzen nur unter hohem Energieeinsatz beseitigt werden können und nicht regeneriert werden können. Problematisch ist auch, dass bestimmte Schwermetalle wie beispielsweise Zink nur schwer aus den Abwässern zurückgehalten werden. Aus dem Stand der Technik ist die DE 100 35 432 A1 bekannt, in der eine Kalk-Ton- Suspension zur Güileäufbereitung und Bodenverbesserung beschrieben ist. Jedoch wird eine Adsorption von Schwermetailen oder Cyaniden an die suspendierten Kaik- Ton-Bestandteile in der Druckschrift nicht genannt. The adsorber substances known in the prior art are generally organic chemicals which function, for example, as ion exchangers. Activated carbon is also used as the adsorbent substance, but it has the disadvantage of a long contact time, which is necessary so that the pollutants can diffuse into the interior of the pore. To ensure that all pollutants are trapped as quickly as possible, wastewater treatment plants use large amounts of activated carbon in appropriately sized treatment tanks. However, the addition of flocculants to increase the pore sizes, such as iron chloride and polyacrylamide, creates a relatively large volume of sludge, which has to be reprocessed, for example, by drying, and the substances used can only be removed with high energy input and cannot be regenerated. Another problem is that certain heavy metals, such as zinc, are difficult to retain from the waste water. DE 100 35 432 A1 is known from the prior art, in which a lime-clay suspension for liquid manure processing and soil improvement is described. However, adsorption of heavy details or cyanides on the suspended Kaik clay components is not mentioned in the document.
Ferner ist als Stand der Technik die DE 102 10 786 A1 bekannt, in der eine Mischung aus Granulaten als Adsorbermaterialien für kontaminierte Zonen beschrieben ist, bei der eine Adsorption von Schwermetallen oder Cyaniden an Eisenoxide erfolgen kann. Eine Beschichtung der Granulate mit Hum instoffen ist in der Druckschrift nicht genannt. Furthermore, DE 102 10 786 A1 is known as prior art, in which a mixture of granules is described as adsorber materials for contaminated zones, in which heavy metals or cyanides can be adsorbed on iron oxides. Coating the granules with humic substances is not mentioned in the publication.
In der DE 10 2015 221 206 A1 ist eine Zusammensetzung, insbesondere zur Immobilisierung von Metallionen wie Schwermetallen aus Abwasser beschrieben, umfassend mindestens ein Eisenhydroxid und mindestens ein poröses Trägermaterial wie beispielsweise ein Granulat. Eine Adsorption von Cyaniden und eine Eintragung einer Suspension mit nachfolgender Agglomerisation ist in der Druckschrift nicht offenbart. DE 10 2015 221 206 A1 describes a composition, in particular for immobilizing metal ions such as heavy metals from waste water, comprising at least one iron hydroxide and at least one porous carrier material such as, for example, granules. Adsorption of cyanides and entry of a suspension with subsequent agglomeration is not disclosed in the document.
Ferner ist in der DE 10 2018 103 952 A1 die Verwendung von huminstoffbeschichteten Eisenoxiden als Agglomerisations- undFurthermore, DE 10 2018 103 952 A1 describes the use of humic oxide-coated iron oxides as agglomeration and
Dekontaminationspartikel beschrieben. Allerdings enthält die nachveröffentliche Druckschrift keine Hinweise auf die Verwendung von Flockungsmitteln zur Agglomeration, sowie die Bindung von polyfluorierten Alkylverbindungen und die pH-Bedingungen für eine Adsorption oder Bindung von Schwermetallen und/oder Cyaniden. Decontamination particles described. However, the post-published publication contains no references to the use of flocculants for agglomeration, the binding of polyfluorinated alkyl compounds and the pH conditions for adsorption or binding of heavy metals and / or cyanides.
Aufgabe der vorliegenden Erfindung ist es daher ein Verfahren Generierung kontaminationsfreien Abwassers, wobei Kontaminationen wie Schwermetalle und/oder Cyanide und/öder fluorierten Alkylverbindungen bis zur Einleitungsgrenze aus den Abwässern entfernt werden und die Kontaminationen im Abwasser von den Eisenoxid-Partikeln adsorbiert oder gebunden werden. The object of the present invention is therefore a method of generating contamination-free waste water, contaminations such as heavy metals and / or cyanides and / or fluorinated alkyl compounds being removed from the waste water up to the discharge limit and the contamination in the waste water being adsorbed or bound by the iron oxide particles.
Die Aufgabe wird erfindungsgemäß durch die Merkmale des unabhängigen Anspruchs 1 gelöst. Partikel aus Eisenoxid können nanokristalline Bestandteile aufweisen, die eine Adsorption oder Bindung von Schwermetallen und/oder Cyaniden und/oder fluorierten Alkylverbindungen an die eingesetzten Partikel ermöglichen. So ist erfindungsgemäß vorgesehen, dass Eisenoxid-Partikel in Bereiche kontaminierten Abwassers eingetragen werden, denen Lösungen von Erdalkalisalzen variabler Konzentration zugesetzt werden. Die dem Eintrag der Partikel und dem Zusatz der Erdalkalisalzlösungen nachfolgende Aggregation der Eisenoxid-Partikel kann als fester Bestandteil zur Adsorption oder Bindung von Schwermetallen und/oder Cyaniden und/oder polyfluorierten Alkylverbindungen genutzt werden. Der Zusatz von Erdalkalilösungen erfolgt erfindungsgemäß derart, dass nach Zusatz der Eisenoxid-Partikel eine allmähliche Zugabe der Erdalkalilösungen erfolgt und ein pH- Wert eingestellt wird, der eine Aggregation der Partikel und eine Adsorption oder Bindung von Kontaminationen wie beispielsweise Schwermetalle und/oder Cyanide und/oder polyfluorierten Alkylverbindungen an die Partikel ermöglicht. Dabei wird der pH-Wert in einen Bereich von 6,0 bis 9,0 eingestellt. Den Eisenoxid-Partikeln wird bei der Abwasserzugabe eine konzentrationsvariable d.h. 5 bis 10-fache Menge einer erdalkalisalzhaltigen Lösung, insbesondere einer Kationenhaltigen Lösung aus Calcium- oder Magnesiumionen, zugesetzt. Dies hat zur Folge, dass eine Adsorption oder Bindung von Schwermetallen und/oder Cyaniden und/oder polyfluorierten Alkylverbindungen an die Partikel erfolgen kann die Partikel anschließend agglomerisieren und ausfallen. The object is achieved by the features of independent claim 1. Particles of iron oxide can have nanocrystalline constituents which enable heavy metals and / or cyanides and / or fluorinated alkyl compounds to be adsorbed or bound to the particles used. According to the invention, it is provided that iron oxide particles are introduced into areas of contaminated wastewater to which solutions of alkaline earth metal salts of variable concentration are added. The aggregation of the iron oxide particles following the entry of the particles and the addition of the alkaline earth metal salt solutions can be used as a fixed component for the adsorption or binding of heavy metals and / or cyanides and / or polyfluorinated alkyl compounds. According to the invention, alkaline earth metal solutions are added in such a way that, after the iron oxide particles have been added, the alkaline earth metal solutions are gradually added and a pH value is set which prevents the particles from aggregating and adsorbing or binding contaminants such as heavy metals and / or cyanides and / or or polyfluorinated alkyl compounds on the particles. The pH is adjusted in a range from 6.0 to 9.0. When the wastewater is added, a concentration variable, ie 5 to 10 times the amount of a solution containing alkaline earth metal, in particular a solution containing calcium or magnesium ions, is added to the iron oxide particles. As a result, heavy metals and / or cyanides and / or polyfluorinated alkyl compounds can be adsorbed or bound to the particles, and the particles can then agglomerate and precipitate.
In einer besonderen Ausgestaltung der Erfindung werden als Eisenoxid-Partikel Nano-Goehtit-Partikel verwendet. Ferner ist in einer weiteren Ausgestaltung der Erfindung vorgesehen, dass Huminsäure-beschichtetes Nano-Goethit als Adsorbens oder Bindungspartner für die Kontaminationen von Abwässern verwendet wird, dessen hydrodynamischer Durchmesser in einem Bereich von 100-500 nm liegen kann. Die Partikel sind in einwertigen lonenlösungen aufgrund einer adsorbierten Schicht von Huminsäuren stabil. Eine Partikelaggregation erfolgt jedoch schnell, wenn Calcium oder Magnesium vorhanden ist. Grund dafür ist eine einsetzende Komplexierung, die aufgrund der Wechselwirkung von zweiwertigen Kationen mit der mit Huminsäure beschichteten Partikel an der Oberfläche erfolgt. Oberhalb einer Grenzdosis von zweiwertigen Kationen aggregieren die Partikel und eine Adsorption öder Bindung von Schwermetallen und/oder Cyaniden und/oder polyfluorierten Alkylverbindungen kann zeitnah an der Oberfläche der Partikel erfolgen. In a particular embodiment of the invention, nano-goehtitle particles are used as iron oxide particles. Furthermore, a further embodiment of the invention provides that nano-goethite coated with humic acid is used as an adsorbent or binding partner for the contamination of waste water, the hydrodynamic diameter of which can be in a range of 100-500 nm. The particles are stable in monovalent ion solutions due to an adsorbed layer of humic acids. Particle aggregation occurs quickly when calcium or magnesium is present. The reason for this is the onset of complexation, which takes place on the surface due to the interaction of divalent cations with the particle coated with humic acid. Above a limit dose of divalent cations, the particles and adsorption aggregate Heavy metals and / or cyanides and / or polyfluorinated alkyl compounds can be bound or bonded promptly to the surface of the particles.
Ferner ist in einer besonderen Ausgestaltung der Erfindung vorgesehen, dass durch Zusätze zu den unbeschichteten oder beschichteten Eisenoxid-Partikeln Kontaminationen von den Partikeln in der Lösung schneller adsorbiert oder von den Partikeln schneller gebunden werden können. Dabei ist vorgesehen, dass den Eisenoxid-Partikeln Polyacrylamid als ein Flockungsmittel zugesetzt wird. Durch den Zusatz von Polyacrylamid wird eine stärkere und/oder schneller Agglomerisation im Abwasser erzielt Furthermore, it is provided in a special embodiment of the invention that, by adding to the uncoated or coated iron oxide particles, contamination of the particles in the solution can be adsorbed faster or the particles can bind them more quickly. It is provided that polyacrylamide is added to the iron oxide particles as a flocculant. The addition of polyacrylamide results in a stronger and / or faster agglomeration in the wastewater
Kontaminationen sollen erfindungsgemäß. Schwermetalle und/oder Cyanide und/öder polyfluorierte Alkylverbindungen umfassen. Contaminations are intended according to the invention. Heavy metals and / or cyanides and / or polyfluorinated alkyl compounds include.
Unter Schwermetallen sind erfindungsgemäß solche Elemente zu verstehen, die eine Dichte > 5 g/cm3 aufweisen. Im Gegensatz zu den meisten organischen Schadstoffen kommen Schwermetaile in natürlichen Stoffkreisläufen vor. In hohen Konzentrationen können aber auch Spurenelemente und Spurennährstoffe Schadstoffcharakter besitzen. Zudem werden Schwermetalle von zahlreichen Industriezweigen verwendet. In Altlasten treten Schwermetalle vornehmlich im Bergbauabraum, in Hüttenwerken, Gießereien, metallverarbeitenden Betrieben mit Galvanik, sowie als Anreicherungen in Verbrennungsrückständen (Schlacken) auf. Darüber hinaus sind Schwermetalle im Gewerbe- und Hausmüll enthalten. Schwermetalle sind umwelttoxikologisch von besonderer Bedeutung. Sie wirken bereits bei verhältnismäßig geringen Konzentrationen gesundheitsschädlich auf den menschlichen und den tierischen Organismus und reichem sich über die Nahrungskette an. Für einige Metalle, z.B. Blei und Cadmium, überschreitet die ubiquitäre Belastungsrate häufig schon die Grenze der Belastbarkeit Aber auch essentielle Schwermetalle wirken in höheren Konzentrationen toxisch oder können, wie z. B. Kupfer, bereits in verhältnismäßig geringen Konzentrationen das Pflanzenwachstum schädigen. Schwermetalle sind persistent und reichem sich im Boden an, sodass bei einer unverhältnismäßig hohen Konzentration eine Konvektion, Dispersion oder Diffusion im Boden verhindert werden soll. Schwermetalle müssen auch aus Industrieabwässem entfernt werden, da Industrieabwasser oft wiederverwendet wird und keine störenden Stoffe enthalten darf. Es ist erfindungsgemäß vorgesehen, dass eine Adsorption oder Bindung der Schwermetallverbindungen an die Eisenoxid-Partikel erfolgt, die anschließend agglomerisieren. Die Bindung findet bevorzugt an den hydroxylierten Oberflächen des Eisenoxids statt. Hydroxokomplexe (MOH+) der Schwermetalle werden daher bevorzugt adsorbiert. Entsprechend der Hydrolysekonstante nimmt daher die spezifische Adsorption der Schwermetalle in folgender Reihenfolge zu Cd < Ni < Co < Zn « Cu < Pb « Hg According to the invention, heavy metals are to be understood as elements which have a density> 5 g / cm 3 . In contrast to most organic pollutants, heavy details occur in natural material cycles. In high concentrations, trace elements and trace nutrients can also have a pollutant character. Heavy metals are also used by numerous branches of industry. In contaminated sites, heavy metals occur primarily in mining waste, in smelting works, foundries, metal processing companies with electroplating, and as enrichments in combustion residues (slags). Heavy metals are also contained in commercial and household waste. Heavy metals are of particular importance in environmental toxicology. Even at relatively low concentrations, they are harmful to human and animal organisms and accumulate through the food chain. For some metals, such as lead and cadmium, the ubiquitous exposure rate often exceeds the limit of the resilience. Even essential heavy metals are toxic in higher concentrations or can, such as. As copper, damage plant growth even in relatively low concentrations. Heavy metals are persistent and accumulate in the soil, so that convection, dispersion or diffusion in the soil should be prevented at a disproportionately high concentration. Heavy metals must also be removed from industrial wastewater, since industrial wastewater is often reused and must not contain any disruptive substances. According to the invention, the heavy metal compounds are adsorbed or bound to the iron oxide particles, which subsequently agglomerate. The binding preferably takes place on the hydroxylated surfaces of the iron oxide. Hydroxo complexes (MOH + ) of the heavy metals are therefore preferably adsorbed. According to the hydrolysis constant, the specific adsorption of the heavy metals increases in the following order: Cd <Ni <Co <Zn «Cu <Pb« Hg
Zwar können über Änderungen des physiko-chemischen Milieus die adsorbierten Schadstoffe wieder mobilisiert werden. Ob eine mobilisierende Wirkung jedoch auftritt, hängt dabei im Wesentlichen von der Struktur der Eisenoxide und der organischen Substanz ab. Die Wasserlöslichkeit, der in der Regel schwach polaren Komplexbildner, beruht auf der Dissoziation saurer funktioneller Gruppen, die mit dem pH-Wert ansteigt. So sind Schwermetall-Humate in der Regel schlecht löslich und können erst bei höheren pH-Werten mobilisiert werden, so dass sich die Verwendung der agglomerisierten, mit Huminsäure beschichteten Goethit-Partikel zur Adsorption oder Bindung von Schwermetallen besonders gut eignen. The adsorbed pollutants can be mobilized again by changing the physico-chemical environment. However, whether a mobilizing effect occurs depends essentially on the structure of the iron oxides and the organic substance. The water solubility of the generally weakly polar complexing agent is based on the dissociation of acidic functional groups, which increases with the pH. Heavy metal humates are generally poorly soluble and can only be mobilized at higher pH values, so that the use of the agglomerated goethite particles coated with humic acid are particularly suitable for adsorbing or binding heavy metals.
Es soll erfindungsgemäß durch die agglomerisierten Partikel weiterhin eine Adsorption oder Bindung von Cyaniden aus dem Abwasser erreicht werden. So sind Cyanide in Emissionen von Abwässern oder Abgasen von Kokereien, Gaswerke, Mineralölraffinerien, Härtereien und galvanotechnische Betriebe bekannt. Das Umweltverhalten der Cyanide zeichnet sich vor allem durch eine hohe Mobilität infolge großer Wasserlöslichkeit und hoher Toxizität gegenüber Biosystemen aus. According to the invention, the agglomerated particles should also be used to adsorb or bind cyanides from the waste water. For example, cyanides are known in emissions from waste water or exhaust gases from coking plants, gas plants, mineral oil refineries, hardening plants and electroplating companies. The environmental behavior of the cyanides is characterized above all by high mobility due to their high water solubility and high toxicity to biosystems.
Das freie Cyanid-Ion (CN ) ist gekennzeichnet durch eine starke Wasserlöslichkeit und eine geringe Adsorbierbarkeit. Das Cyanid-Ion ist bezogen auf seine letale Dosis das stärkste Gift innerhalb der anorganischen Chemie. Es ist daher erfindungsgemäß vorgesehen, dass die Eigenschaft der Cyanid-Ionen genutzt werden soll, dass sie mit Schwermetallen (Fe, Cu, Zn und Cd) stabile Komplexe geringerer Wasserlöslichkeit und Toxizität bilden. So ist es beispielsweise möglich Eisen-Cyanid-Komplexe wie Berliner Blau und Kaiium-Eisen-Cyanid Komplexe (rotes und gelbes Blutlaugensalz) zu bilden und damit die Cyanide nach erfolgter Exposition an die Eisenoxidpartikel zu binden und auszufällen. The free cyanide ion (CN) is characterized by a high water solubility and a low adsorbability. The cyanide ion is the strongest poison in inorganic chemistry based on its lethal dose. It is therefore provided according to the invention that the property of the cyanide ions is to be used, that they are complexes stable with heavy metals (Fe, Cu, Zn and Cd) form less water solubility and toxicity. For example, it is possible to form iron-cyanide complexes such as Berlin blue and kaiium-iron-cyanide complexes (red and yellow blood-lye salts) and thus to bind and precipitate the cyanides to the iron oxide particles after exposure.
Schließlich sollen durch die agglomerierten Partikel eine Adsorption oder Bindung von polyfluorierten Alkylverbindungen erfolgen, wobei unter polyfluorierten Alkylverbindungen insbesondere per- und polyfluorierte Alkylverbindungen (PFAS) zu verstehen sind. Zu per- und polyfluorierte Alkylverbindungen zählen auch polyfluorierte Alkyltenside, wie Perfluoroctansulfonat (PFOS), die im Stand der Technik bislang nur unter Zusatz von Aktivkohle aus dem Abwasser als Kontamination abgetrennt werden können und eine zeit- und kostenintensive Aufarbeitung erfordern. Die Erfindung wird anhand des nachfolgenden Beispiels in Figur 1 nochmals erklärt: Kontamination von Abwasser 1 treten häufig auf und es besteht Bedarf nach kostengünstigen Efimrnationstechniken. Es wurde gefunden, dass die Zugabe von mit Huminstoffen überzogenen Eisenoxid-Partikeln 2 eine Eliminierung von Schwermetallen 5 wie beispielsweise Arsen oder Cyaniden 6 oder fluorierten Alkylverbindungen 8 ermöglicht. Diese Technologie basiert auf der Injektion von mobilen mit Humansäure beschichteten Goethit-Partikeln 2, die anschließend durch Zugabe von Erdalkalilösungen 3 und/oder Flockungsmitteln 4 durch Aggregation in einer kontaminierten Zone abgeschieden werden. So ist insbesondere in Figur 1 schematisch dargestellt, dass bei Durchmischung und nach Zugabe von Goethit-Partikeln 2 Erdalkalisalzlösungen 3 und/oder Flockungsmitteln 4 zu dem Abwasser 1 eine Aggregation der Partikel 2 erfolgt, wobei sich im Abwasser 1 befindliche Kontaminationen beispielsweise Schwermetalle 5 und/oder Cyanide 6 und/oder polyfluorierten Alkylverbindungen 8 an die Partikel 2 (5, 6, 8) adsorbieren oder binden. Es ist auch möglich ohne Flockungsmittel 4 eineFinally, the agglomerated particles are intended to adsorb or bind polyfluorinated alkyl compounds, polyfluorinated alkyl compounds in particular meaning per- and polyfluorinated alkyl compounds (PFAS). Perfluorinated and polyfluorinated alkyl compounds also include polyfluorinated alkyl surfactants, such as perfluorooctane sulfonate (PFOS), which in the prior art have only been able to be separated from the waste water as contamination with the addition of activated carbon and which require time-consuming and costly processing. The invention is explained again with the aid of the following example in FIG. 1: Contamination of wastewater 1 occurs frequently and there is a need for inexpensive efficiency techniques. It has been found that the addition of iron oxide particles 2 coated with humic substances enables the elimination of heavy metals 5 such as arsenic or cyanides 6 or fluorinated alkyl compounds 8. This technology is based on the injection of mobile goethite particles 2 coated with human acid, which are then separated by adding alkaline earth solutions 3 and / or flocculants 4 by aggregation in a contaminated zone. In particular, FIG. 1 shows schematically that when mixed and after the addition of goethite particles 2, alkaline earth metal salt solutions 3 and / or flocculants 4 to the wastewater 1, the particles 2 are aggregated, with contaminants in the wastewater 1, for example heavy metals 5 and / or adsorb or bind cyanides 6 and / or polyfluorinated alkyl compounds 8 to the particles 2 (5, 6, 8). It is also possible without a flocculant 4
Adsorption oder Bindung der Kontaminationen durch Erdalkalisalzlösungen 3 zu initiieren, indem Erdalkalisalzlösungen 3 zur Aggregation dem kontaminierten Abwasser 1 zugesetzt werden. Nach beendeter Durchmischung und Sedimentation der agglomerierten Partikel 2 wird gereinigtes Wasser 7 als obere Schicht über dem Rest-Abwasser 1 erhalten und kann dem Prozess entnommen werden. Säulenversuche von mit Huminsäure-Goethit-Partikeln 2 (2,80 mg Goethit g-1-Sand) überzogenem Sand und schrittweiser Injektion von As (V) (1 bis 4,9 mg As L-1) zeigten eine hochwirksame Entfernung von As (V) aus der Flüssigkeit bzw. dem Abwasser 1. Die Phase als Abfluss As (V) -Konzentrationen blieb unterhalb der Trinkwassergrenze (10 mg As L-1), bis etwa 45% der Sorbenskapazität (30 mg As g-1 Goethit) erreicht waren. Initiate adsorption or binding of the contaminations by alkaline earth salt solutions 3 by adding alkaline earth salt solutions 3 to the contaminated wastewater 1 for aggregation. After the mixing and sedimentation of the agglomerated particles 2 has ended, purified water 7 becomes the upper layer above the Residual waste water 1 received and can be removed from the process. Column experiments with sand coated with humic acid goethite particles 2 (2.80 mg goethite g -1 sand) and gradual injection of As (V) (1 to 4.9 mg As L -1 ) showed a highly effective removal of As ( V) from the liquid or wastewater 1. The phase as runoff As (V) concentrations remained below the drinking water limit (10 mg As L -1 ) until about 45% of the sorbent capacity (30 mg As g- 1 goethite) was reached were.
Bezugszeichenliste Reference symbol list
1 Abwasser 1 waste water
2 Eisenoxid-Partikel 2 iron oxide particles
3 Erdalkalilösung 3 alkaline earth solution
4 Flockungsmittel 4 flocculants
5 Schwermetall 5 heavy metal
6 Cyanid 6 cyanide
7 Gereinigtes Wasser 7 Purified water
8 Polyfluorierte Alkylverbindungen 8 Polyfluorinated alkyl compounds

Claims

PATENTANSPRÜCHE PATENT CLAIMS
1. Verfahren zur Verringerung von Kontaminationen von Abwasser (1), wobei kolloidale in einer Flüssigkeit suspendierte Eisenoxid-Partikel (2) mindestens mit einer Erdalkalisalzlösung (3) versetzt werden, wobei die Eisenoxid-Partikel (2) agglomerisieren und Kontaminationen im Abwasser (1) von den Eisenoxid- Partikeln (2) adsorbiert oder von den Eisenoxid-Partikeln (2) gebunden werden. dadurch gekennzeichnet, dass die Eisenoxid-Partikel (2) vor Eintragung in das Abwasser (1) mit organischen Substanzen wie Huminstoffen oder Huminsäuren beschichtet und anschließend in einer wässrigen Suspension in das Abwasser (1) eingetragen werden und nachfpigend agglomerisieren. 1. A method for reducing contamination of waste water (1), wherein colloidal iron oxide particles (2) suspended in a liquid are mixed with at least one alkaline earth metal salt solution (3), the iron oxide particles (2) agglomerating and contamination in the waste water (1 ) adsorbed by the iron oxide particles (2) or bound by the iron oxide particles (2). characterized in that the iron oxide particles (2) are coated with organic substances such as humic acids or humic acids before being introduced into the waste water (1) and are then introduced into the waste water (1) in an aqueous suspension and agglomerate to replenish them.
2. Verfahren nach Anspruch 1, 2. The method according to claim 1,
dadurch gekennzeichnet, dass die Eisenoxid-Partikel (2) Nano-Goethit- Partikel umfassen. characterized in that the iron oxide particles (2) comprise nano-goethite particles.
3. Verfahren nach Anspruch 1 oder 2, 3. The method according to claim 1 or 2,
dadurch gekennzeichnet, dass die Eisenoxid-Partikel einen hydrodynamischen Durchmesser in einem Bereich von 100-500 nm aufweisen. characterized in that the iron oxide particles have a hydrodynamic diameter in a range of 100-500 nm.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Aggiomerisation durch konzentrationsvariable Zusätze von Erdalkalimetallsalzlösungen (3) mit Kalzium- oder Magnesiumionen erfolgt. 4. The method according to any one of claims 1 to 3, characterized in that the aggiomerization is carried out by variable-concentration additions of alkaline earth metal salt solutions (3) with calcium or magnesium ions.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass den Eisenoxid-Partikeln (2) bei der Abwasserzugabe eine 5- bis 10-fache Menge der Erdalkaiisaiz Lösung (3) zugesetzt wird. 5. The method according to any one of claims 1 to 4, characterized in that a 5 to 10 times the amount of the alkaline earth solution (3) is added to the iron oxide particles (2) when the wastewater is added.
6. Verfahren nach einem der Ansprüche 1 bis 5, 6. The method according to any one of claims 1 to 5,
dadurch gekennzeichnet, dass der wässrigen Suspension ein Flockungsmittel (4) zugesetzt wird. characterized in that a flocculant (4) is added to the aqueous suspension.
7. Verfahren nach Anspruch 6, 7. The method according to claim 6,
dadurch gekennzeichnet, dass das Flockungsmittel (4) Polyacrylamid umfasst. characterized in that the flocculant (4) comprises polyacrylamide.
8. Verfahren nach einem der Ansprüche 1 bis 7, 8. The method according to any one of claims 1 to 7,
dadurch gekennzeichnet, dass an die agglomerisierten Partikel (2) eine Adsorption oder Bindung von Schwermetallen (5) erfolgt. characterized in that heavy metals (5) are adsorbed or bound to the agglomerated particles (2).
9. Verfahren nach einem der Ansprüche 1 bis 8, 9. The method according to any one of claims 1 to 8,
dadurch gekennzeichnet, dass an die agglomerisierten Partikel (2) eine Adsorption oder Bindung von Cyaniden (6) erfolgt. characterized in that the agglomerated particles (2) are adsorbed or bound by cyanides (6).
10. Verfahren nach einem der Ansprüche 1 bis 9, 10. The method according to any one of claims 1 to 9,
dadurch gekennzeichnet, dass an die agglomerisierten Partikel (2) eine Adsorption oder Bindung von polyfluorierten Alkylverbindungen (8) erfolgt. characterized in that adsorption or binding of polyfluorinated alkyl compounds (8) takes place on the agglomerated particles (2).
11. Verfahren nach Anspruch 10, 11. The method according to claim 10,
dadurch gekennzeichnet, dass die polyfluorierte Alkylverbindungen polyfluorierte Alkyltenside umfassen. characterized in that the polyfluorinated alkyl compounds comprise polyfluorinated alkyl surfactants.
12. Verfahren nach Anspruch 10 oder 11 , 12. The method according to claim 10 or 11,
dadurch gekennzeichnet, dass die polyfluorierten Alkyltenside Perfiuoroctansulfbnate (PFOS) sind. characterized in that the polyfluorinated alkyl surfactants are perfiuorooctanesulfonates (PFOS).
13. Verfahren nach einem der Ansprüche 1 bis 12, 13. The method according to any one of claims 1 to 12,
dadurch gekennzeichnet, dass der pH-Wert zur Adsorption oder Bindung der Schwermetalle (5) und/oder Cyanide (6) und/oder polyfluorierten Alkylverbindungen (8) in einem Bereich von 6,0 bis 9,0 liegt. characterized in that the pH for adsorption or binding of the heavy metals (5) and / or cyanides (6) and / or polyfluorinated alkyl compounds (8) is in a range from 6.0 to 9.0.
14. Verfahren nach einem der Ansprüche 1 bis 13, 14. The method according to any one of claims 1 to 13,
dadurch gekennzeichnet, dass nach beendeter Eintragung der Suspension und Sedimentation der agglomerierten Partikel (2) gereinigtes Wasser (7) als obere Schicht dem Abwasser (1) entnommen wird. characterized in that after the entry of the suspension and sedimentation of the agglomerated particles (2), purified water (7) is removed from the waste water (1) as the upper layer.
15. Verwendung von in einer Flüssigkeit suspendierten Partikeln (2) In Form von Eisenoxiden, nach einem der Ansprüche 1 bis 14 zur Eliminierung von Schwermetallen (5) und/oder Cyaniden (6) und/oder polyfluorierten Alkylverbindungen (8) aus Industrie- und Bergbauabwässem. 15. Use of suspended in a liquid particles (2) in the form of iron oxides, according to one of claims 1 to 14 for the elimination of heavy metals (5) and / or cyanides (6) and / or polyfluorinated alkyl compounds (8) from industrial and Mining wastewater.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111875024A (en) * 2020-08-10 2020-11-03 紫金矿业集团股份有限公司 Iron and cyanogen removing method for mixing copper-containing wastewater and cyanogen-containing wastewater
CN113304723A (en) * 2020-09-23 2021-08-27 华南理工大学 Surfactant-loaded goethite material and preparation method thereof
WO2022117633A1 (en) 2020-12-02 2022-06-09 Haemers Technologies Societe Anonyme Combination of pollution clean-up techniques: in situ thermal desorption and immobilization

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10035432A1 (en) 2000-07-20 2002-01-31 Kalksteinwerk Vilshofen Gmbh Lime-clay suspension
DE10210786A1 (en) 2002-03-12 2003-10-02 Bayer Ag Mixtures of adsorber materials
DE102015221206A1 (en) 2015-10-29 2017-05-04 Fränkische Rohrwerke Gebr. Kirchner Gmbh & Co. Kg Composition for the immobilization of metal ions
DE102018103952A1 (en) 2018-02-21 2019-08-22 Universität Duisburg-Essen Nano-goethite as agglomeration and decontamination particles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10035432A1 (en) 2000-07-20 2002-01-31 Kalksteinwerk Vilshofen Gmbh Lime-clay suspension
DE10210786A1 (en) 2002-03-12 2003-10-02 Bayer Ag Mixtures of adsorber materials
DE102015221206A1 (en) 2015-10-29 2017-05-04 Fränkische Rohrwerke Gebr. Kirchner Gmbh & Co. Kg Composition for the immobilization of metal ions
DE102018103952A1 (en) 2018-02-21 2019-08-22 Universität Duisburg-Essen Nano-goethite as agglomeration and decontamination particles
WO2019161842A1 (en) * 2018-02-21 2019-08-29 Universität Duisburg-Essen Colloidal iron oxide as agglomeration and decontamination particles

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BIANCO ET AL: "Controlled Deposition of Particles in Porous Media for Effective Aquifer Nanoremediation", SCIENTIFIC REPORTS,, vol. 7, 11 October 2017 (2017-10-11), pages 1 - 10, XP002791030, DOI: 10.1038/S41598-017-13423-Y *
DANIELA MONTALVO ET AL: "Efficient removal of arsenate from oxic contaminated water by colloidal humic acid-coated goethite: Batch and column experiments", JOURNAL OF CLEANER PRODUCTION, vol. 189, 1 July 2018 (2018-07-01), AMSTERDAM, NL, pages 510 - 518, XP055672884, ISSN: 0959-6526, DOI: 10.1016/j.jclepro.2018.04.055 *
FU FENGLIAN ET AL: "The use of zero-valent iron for groundwater remediation and wastewater treatment: A review", JOURNAL OF HAZARDOUS MATERIALS, ELSEVIER, AMSTERDAM, NL, vol. 267, 7 January 2014 (2014-01-07), pages 194 - 205, XP028615387, ISSN: 0304-3894, DOI: 10.1016/J.JHAZMAT.2013.12.062 *
MAMUN RASHID ET AL: "Kinetic and Mechanistic Evaluation of Inorganic Arsenic Species Adsorption onto Humic Acid Grafted Magnetite Nanoparticles", JOURNAL OF PHYSICAL CHEMISTRY C, vol. 122, no. 25, 24 February 2018 (2018-02-24), US, pages 13540 - 13547, XP055672890, ISSN: 1932-7447, DOI: 10.1021/acs.jpcc.7b12438 *
TIRAFERRI ALBERTO ET AL: "Colloidal behavior of goethite nanoparticles modified with humic acid and implications for aquifer reclamation", JOURNAL OF NANOPARTICLE RESEARCH, KLUWER ACADEMIC PUBLISHERS, DORDRECHT, NL, vol. 19, no. 3, 11 March 2017 (2017-03-11), pages 1 - 11, XP036206060, ISSN: 1388-0764, [retrieved on 20170311], DOI: 10.1007/S11051-017-3814-X *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111875024A (en) * 2020-08-10 2020-11-03 紫金矿业集团股份有限公司 Iron and cyanogen removing method for mixing copper-containing wastewater and cyanogen-containing wastewater
CN113304723A (en) * 2020-09-23 2021-08-27 华南理工大学 Surfactant-loaded goethite material and preparation method thereof
WO2022117633A1 (en) 2020-12-02 2022-06-09 Haemers Technologies Societe Anonyme Combination of pollution clean-up techniques: in situ thermal desorption and immobilization
BE1028844A1 (en) 2020-12-02 2022-06-27 Haemers Tech Societe Anonyme Combination of depollution techniques: In Situ Thermal Desorption and Immobilization

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