EP3860954A1 - Verwendung von eisenoxid-partikeln in abwaessern zur eliminierung von kontaminationen - Google Patents
Verwendung von eisenoxid-partikeln in abwaessern zur eliminierung von kontaminationenInfo
- Publication number
- EP3860954A1 EP3860954A1 EP19831976.6A EP19831976A EP3860954A1 EP 3860954 A1 EP3860954 A1 EP 3860954A1 EP 19831976 A EP19831976 A EP 19831976A EP 3860954 A1 EP3860954 A1 EP 3860954A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- iron oxide
- oxide particles
- particles
- heavy metals
- cyanides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- 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)
- Water Treatment By Sorption (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102018130744.6A DE102018130744A1 (de) | 2018-12-03 | 2018-12-03 | Verwendung von Eisenoxid-Partikeln in Abwässern zur Eliminierung von Kontaminationen |
PCT/DE2019/101032 WO2020114556A1 (de) | 2018-12-03 | 2019-12-02 | Verwendung von eisenoxid-partikeln in abwaessern zur eliminierung von kontaminationen |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3860954A1 true EP3860954A1 (de) | 2021-08-11 |
Family
ID=69105665
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19831976.6A Pending EP3860954A1 (de) | 2018-12-03 | 2019-12-02 | Verwendung von eisenoxid-partikeln in abwaessern zur eliminierung von kontaminationen |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3860954A1 (de) |
DE (1) | DE102018130744A1 (de) |
WO (1) | WO2020114556A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111875024B (zh) * | 2020-08-10 | 2022-07-15 | 紫金矿业集团股份有限公司 | 一种含铜废水与含氰废水混合的除铁除氰方法 |
CN112263986A (zh) * | 2020-09-23 | 2021-01-26 | 华南理工大学 | 一种负载表面活性剂的针铁矿材料及其制备方法 |
BE1028844B1 (fr) | 2020-12-02 | 2022-07-04 | Haemers Tech Societe Anonyme | Combinaison de techniques de dépollution: Désorption thermique In Situ et Immobilisation |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10035432A1 (de) * | 2000-07-20 | 2002-01-31 | Kalksteinwerk Vilshofen Gmbh | Kalk-Ton-Suspension |
DE10210786A1 (de) * | 2002-03-12 | 2003-10-02 | Bayer Ag | Mischungen aus Adsorbermaterialien |
DE102015221206A1 (de) * | 2015-10-29 | 2017-05-04 | Fränkische Rohrwerke Gebr. Kirchner Gmbh & Co. Kg | Zusammensetzung zur Immobilisierung von Metallionen |
DE102018103952A1 (de) * | 2018-02-21 | 2019-08-22 | Universität Duisburg-Essen | Nano-Goethit als Agglomerisations- und Dekontaminationspartikel |
-
2018
- 2018-12-03 DE DE102018130744.6A patent/DE102018130744A1/de active Pending
-
2019
- 2019-12-02 WO PCT/DE2019/101032 patent/WO2020114556A1/de unknown
- 2019-12-02 EP EP19831976.6A patent/EP3860954A1/de active Pending
Also Published As
Publication number | Publication date |
---|---|
WO2020114556A1 (de) | 2020-06-11 |
DE102018130744A1 (de) | 2020-06-25 |
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