WO2016107617A1 - Filter for removal of inorganic and organic substances from contaminated water - Google Patents

Filter for removal of inorganic and organic substances from contaminated water Download PDF

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Publication number
WO2016107617A1
WO2016107617A1 PCT/CZ2015/000050 CZ2015000050W WO2016107617A1 WO 2016107617 A1 WO2016107617 A1 WO 2016107617A1 CZ 2015000050 W CZ2015000050 W CZ 2015000050W WO 2016107617 A1 WO2016107617 A1 WO 2016107617A1
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WIPO (PCT)
Prior art keywords
layer
cations
adsorbent material
modified
clay mineral
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PCT/CZ2015/000050
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English (en)
French (fr)
Inventor
Daniela PLACHÁ
Gražyna SIMHA MARTYNKOVÁ
Marcel MIKESKA
Original Assignee
Vysoká Škola Báňská - Technická Universita Ostrava
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Publication of WO2016107617A1 publication Critical patent/WO2016107617A1/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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • 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
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/14—Base exchange silicates, e.g. zeolites
    • 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
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/17—Organic material containing also inorganic materials, e.g. inert material coated with an ion-exchange resin
    • 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
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C02F2101/006—Radioactive 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
    • C02F2101/101—Sulfur 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
    • C02F2101/105—Phosphorus 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
    • 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
    • C02F2101/163—Nitrates
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/306—Pesticides
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
    • 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
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic 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
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • C02F2201/006—Cartridges
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/18—Removal of treatment agents after treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/24—Separation of coarse particles, e.g. by using sieves or screens

Definitions

  • the presented invention relates to a filter with adsorbent material based on modified clay minerals, especially vermiculite and smectites, intended for treatment of water contaminated with inorganic and organic substances.
  • Patent no. US6235201 describes a device and a method for removal of oil, carbohydrates and other organic minerals from water, especially from industrial wastewater, rainwater on the shores near oil wells and production platforms, by adsorption onto the oil adsorbent, while the adsorbent condition is monitored electrically by the respective probe to determine whether the adsorbent needs to be replaced.
  • Water is distributed to the device through the U-shaped water leg from the input placed in the lower part of the sump tank. The water starts to flow through the device after reaching a certain gravity weight caused by the height of water column.
  • the sump tank comprises a float vaive and an oil supply opening on the top.
  • the float valve is arranged inside an inner housing and it is connected with a pump for pumping oil into a storage tank.
  • the lower part of the water conduit is operatively connected with the water polishing units containing oil adsorbent, particularly organophilic clay.
  • oil adsorbent particularly organophilic clay.
  • the separated water flows by gravity through the water leg conduit and is conveyed into the said polishing unit with oil adsorbent.
  • the organophilic clay adsorbs the hydrocarbons, oils and other organic materials entrained with the water flowing through the water conduit, it is suitable for complete removal of hydrocarbons, especially those with less than 10 ppm.
  • the treated water flows by gravity through water exit opening in the water refining unit to the ocean.
  • GB1517715 discloses an apparatus for separating oil from water during operation, where the effluent water is contaminated with oil, for example after tanker washings, oil refineries, etc.
  • the apparatus for oil separation comprises three oil-coalescing beds, where the oil is collected, a settling zone downstream of the beds and a filter arranged under the beds.
  • the beds may comprise anthracite, charcoal, polystyrene, polyethylene, polypropylene, vermiculite or sand.
  • the filter may comprise a cellulose acetate fibre on a polypropylene core.
  • the patent application CN103991915 discloses a water filtration device comprising two chambers, wherein at least one chamber comprises inorganic particles suitable for water filtration and at least one chamber comprises biocide.
  • inorganic particles include for example porous ceramic particles, smectite clay, perlite, vermiculite, zeolite, or a combination thereof.
  • the filtration device provides the transformation of contaminated water into drinking water.
  • the first stage of filtration comprises inorganic particles and the second stage comprises biocide. At least 95 percent of inorganic particles pass through the No. #20.000 sieve and at least 95 percent do not pass through the No. #20 sieve.
  • Inorganic particles have cation exchange capacity ranging between 1 - 200 milliequivalents per 100 grams.
  • the patent application no. JPH07310295 discloses a device related to a method for removal of inorganic compounds and oils during paper recycling process.
  • the method of treating wastepaper, oils and inorganic compounds requires the use of organoclay treating composition in the waste aqueous system.
  • the organoclay in the waste aqueous system effectively removes the above mentioned oil and inorganic compounds.
  • Ammonium salts which are used for forming organoclay in situ by reacting with cation released from wastepaper, serves for making paper pulp.
  • Organoclay is swelling for 30 min at 65 °C in water and then the surfactants are added.
  • Organoclays formed in situ consist of various ammonium salts and it is preferred to use them to collect a large proportion of oil contaminants comprised in the wastepaper.
  • the background of the invention deals only with the columns filled with one kind of adsorbent mainly suitable for removing one type of petroleum and oily substances, or other organic contaminants.
  • the Czech patent application PV 2008-462 discloses a vermiculite modification process for sorptive material which is intended to collect the undesirable compounds from wastewater or other environmentally polluted water and waste gases.
  • the adsorbent material for collecting toxic contaminants consisting of microfibrous and nanofibrous two-phase textile material comprising phyllosilicate, e.g. vermiculite, its filtration and adsorption properties and its use for adsorbing chemical and/or biological warfare compounds being disclosed in the Czech patent application PV 2013-451.
  • a protective composite system comprising the adsorbent material which is used for making clothes or covers is disclosed therein.
  • the object of the invention is to present a wide-spectrum filter for removal of various types of inorganic and organic substances from the contaminated water at the same time.
  • a filter for removal of inorganic and organic substances from contaminated water consisting of a casing provided with a lower bottom and a removable lid and further comprising water inlet and water outlet inside which a patron with adsorbent material based on modified clay minerals is arranged, characterized in that the adsorbent material is arranged in layers, which comprise at least one layer of modified clay mineral with organic cations with different chain lengths and at least one layer based on natural clay mineral or clay mineral in sodium form.
  • any clay minerals belonging to the group of smectites and vermiculites wherein the composite adsorbent material is defined by the particle size and by the amount and type of exchanged cations in the structure of the original clay mineral.
  • the size of particles is defined in the patent PV 2008-462.
  • type of cations are meant - the monoionic sodium form of vermiculite (between the layers mostly sodium cations are comprised, further organic cations with long aliphatic chain hydrocarbons, with aromatic rings, short chain hydrocarbons, and the like).
  • the adsorbent material comprises a layer of clay mineral modified with aliphatic organic cations with at least one long carbon chain C12-C18, wherein ammonium, phosphonium and sulfonium as well as pyridinium or piperidinium cations may be used, having at least one long hydrocarbon chain.
  • the adsorbent material comprises a layer of clay mineral modified with organic cations, especially ammonium, phosphonium and sulfonium ones, cations with long carbon chains (methyl, ethyl, propyl, butyl cations).
  • the invention is based on an assumption that one of the characteristic features of absorbent materials based on clay minerals including vermiculite and smectite is their cation exchange capacity, which indicates the amount of cations between the layers (interlayer) in layered structures of clay minerals.
  • Clay minerals belong to inexpensive natural materials which are easily accessible and harmless, their modification being a very simple and undemanding process, as the modifiers are also inexpensive. Moreover, waste material can be processed and reused after the elimination depending on the level of contamination.
  • Clay minerals modification can be performed in various ways using various organic cations and exchange of inorganic cations.
  • the exchange of cations can be performed to various degrees, however, an optimum exchange is only to a certain extent, otherwise the effectiveness of the adsorbent decreases and resistance to the flow of contaminated water is formed. Modification ranging from at least 10-50 % of the cation exchange capacity value of the used clay mineral is preferred.
  • Modifiers are organic cations and various kinds of modifiers can be used for the modification, such as ammonium, pyridinium, piperidinium, phosphonium or sulfonium cations with various lengths of hydrocarbon chains. They have an effect on organoclay adsorbent properties, such as sorption capacity and sorption mechanism. The resulting sorption and organophilic clays look the same at the first sight, however, they differ in the nature of interaction. It is known that organic cations with short hydrocarbon chains (tetramethylammonium or trimethylbezylammonium) form so called adsorbent organoclays, which are characterized by their high sorption capacity and competitive adsorption of substances according to Langmuir or Freilich isotherm.
  • Organic cations with long hydrocarbon chains form organophilic organoclays and the sorption of organic substance is defined by linear isotherm in wide range of concentrations, they are characterized by high sorption effectiveness and non-competitive sorption.
  • the sorption corresponds to the distribution process, in which the organic cations form a quasi-lipophilic phase, in which the organic substances accumulate.
  • Organic cations with short hydrocarbon chains are isolated from each other in interlayer and are surrounded by a siloxan surface. Siloxan surface between organic cations forms the primary adsorbent points for aromatic hydrocarbons.
  • Organic cations with long hydrocarbon chains (e.g. hexadecyitrimethylammonium) fill the interlayer area and this hydrophobic area fulfils the function of a separating medium for non-polar organic substances.
  • Adsorbent organoclays with short hydrocarbon chains are effective adsorbents for substances with lower Kow value, while the organophilic organoclays with long carbon chains are effective adsorbent for organic substances with higher Kow values.
  • the method for treatment of wastewater by removing organic as well as inorganic substances using modified clay minerals comprises the following steps.
  • the contaminated water is directed through at least one column, in which at least one adsorbent layer based on organoclay and at least one layer based on natural clay mineral in sodium form are arranged, in the next step it is guided through a membrane permeable for water but not for organoclays and clay minerals, to be deprived of clay material and suitable for further harmless use.
  • the filter consists of a casing preferably made of plastic or metal material suitable for industrial applicability, into which a patron filled with adsorbent material according to the desirable effect may be placed.
  • the size of the filter is determined by the area of application, such as household, industry, etc.
  • the filter consists of a sieve, which eliminates rough contaminants and impurities, wherein it has to be easily removable and cleanable, further it consists of a ceramic filter, for example cordierite ceramic based one, collecting solid particles, wherein the pore size is max. 1 pm, further followed by layers of modified clay material, the last layer consisting of natural clay material or clay material in sodium form to collect possible released organic cations, and with another ceramic filter, e.g. cordierite ceramic based one, collecting the particles of clay material with pore size of 0.2-0.8 pm on the end of filtration filling.
  • the flow of purified water might be directed from above or by countercurrent, however, the particular filling layers have to be arranged according to this, wherein at the end there is always a layer of pure clay mineral, in this case of vermiculite, for the further purification.
  • the filter casing is preferable made of such material and in such shape, so as to fill the fiction of a membrane and be impermeable to organoclay and clay mineral particles, only permeable to water particles.
  • the method of implementation and removal of organoclay from contaminated water is facilitated by a removable cover.
  • the organoclay particles and clay mineral in natural or sodium form particles stay at the same place, while the flow of liquid, in this case the flow of contaminated water, is guided through all layers of organoclay and non-modified clay mineral.
  • Such an arrangement prevents clogging and pressure drop problem.
  • Fig. 1 illustrates a view on the filter
  • Fig. 2 illustrates a patron filled with adsorbent consisting of a mixture of differently modified vermiculites and supplemented by natural vermiculite of vermiculite in sodium form
  • Fig. 3 illustrates a patron comprising absorbent arranged in the filter
  • Fig. 4 illustrates the filter with the casing designed in a form of a membrane, in which the adsorbent filling is arranged
  • the Fig. 6 illustrates one of the possible filter connections.
  • the invention solves a filter consisting of a casing 2 provided with a lower bottom 4 and a removable lid 6, as it is apparent from the Fig. 1 and Fig. 2,
  • the bottom 4 provided with a water outlet 8 and the removable lid 6 provided with a water inlet 7 through which water, organic and inorganic substances enter the filter ⁇ ⁇ fit tightly to the casing 2, wherein the separated water is withdrawn through the water outlet 8.
  • the inlet 7 in the casing 2 is preferably placed on the lid 6 and the outlet 8 is preferably placed on the lower bottom 4 of the casing, what allows a natural flow of water down by gravity.
  • adsorbent material 10 is arranged according to the desired effect.
  • a material may for example be a mixture of variously modified vermiculites, supplemented with natural vermiculite, which is defined by the particle size and the amount and type of exchangable cations in the structure of the initial vermiculite.
  • the filter further consists of a sieve 9, which eliminates rough contaminants and impurities and which has to be easily removed and cleanable, further it consists of a ceramic filter 13, for example one based on cordierite ceramics, collecting the solid particles, wherein the pore size is max. 1 pm. inside the patron 3 the particular layers of modified clay mineral, particularly vermiculite, with various organic cations are arranged, while the last layer consists of pure vermiculite In order to collect possible released organic cations.
  • the ceramic filter 13 is arranged (e.g. based on cordierite ceramics) collecting the particles of vermiculite with a pore size 0.2-0.8 ⁇ .
  • the flow of treated water may be controlled from above or with countercurrent, however, the layers have to be arranged accordingly, wherein a layer of pure clay mineral, in this case vermiculite, is arranged at the outlet 8 for further water treatment.
  • the patron 3 may be replaced with a cover 3J. which is freely placed in the casing 2.
  • the cover 31 may be of any shape, which is either perforated or porous in a shape of a sieve or the like.
  • the adsorbent material 10 comprising a certain amount of organoclay, thus also a reaction product after the modification of clay mineral, particularly vermiculite, is placed.
  • the above mentioned adsorbent material 10 is arranged in at least one cover 31 , which is permeable for liquids but not for organoclay particles allowing the flow of water.
  • the said cover 31 as it is illustrated in the Fig. 4, may be designed in a shape of an elongated sack, which is arranged inside the outside casing 2, for example in a shape of a cylinder.
  • a space is created between the organoclay filling 10 and the casing 2, which allows organoclay to swell and provides a way for the mixture of water with organic or inorganic particles to enter the cover 31 by means of external and internal generated surfaces.
  • the patron 3 is further provided with an input/output 12 for the intake of contaminated water and outlet of purified water, which is in this case connected to the outlet 8, wherein the outlet 8 may be connected to a waste pipe or another casing inlet 7 of another filter 1, as it is illustrated in the Fig. 6.
  • the function of the filter according to the invention is simple and the method of purification is performed as follows. Contaminated water is guided through the inlet 8 into the casing 2, in which a substantial part of contaminants is adsorbed when in contact with the adsorbent material placed in the cover 3J. or the patron 3, in which the adsorbent material 1j) is arranged and through which the contaminated water flows.
  • the patron 3 After the elimination of organic substances, those with low molecular and high molecular weight- the type of chlorinated hydrocarbons - chlorinated ethanes and ethenes, persistent organic pollutants, is the patron 3 filled with an adsorbent containing vermiculite modified with organic cations with short carbon chains and long carbon chains.
  • the mixed adsorbent may be arranged in the patron 3 or a cover 31 , as it is apparent in the Fig. 3.
  • adsorbent material 10 for removal of organic substances and metals the patron 3 is provided with adsorbent material 10 based on modified vermiculite with organic cations with various lengths of chains and non-modified vermiculite.
  • adsorbent material 10 containing modified vermiculite with organic cations with various lengths of chains and non- modified vermiculite.
  • Adsorbent material 10 used as filling in the patron 3 may consist of following layers:
  • Layer 101 - vermiculite modified with organic cations (ammonium, phosphonium, sulfonium) having at least one long carbon chain (the number of carbon atoms is at least 12 to 18 - C12-C18), the modification ranging between at least 10-50 % of cation exchange capacity, eventually more, in case of higher cation exchange it is preferable to use a mixture of modified clay mineral and inert material (e.g. Liapor expanded clay) to allow the flow of contaminated water, because the modified clay has a hydrophobic surface.
  • modified clay mineral and inert material e.g. Liapor expanded clay
  • the layer 102 - comprises vermiculite modified with organic cations having at least one long carbon chain C12-C18 and at least one aromatic ring, particularly pyridinium or piperidinium cations, but also ammonium, phosphonium and sulfonium cations may be used, which contain at least one hydrocarbon chain comprising aromatic benzene ring (tetraphenylphosphonium, benzyltrimethylammonium) of the modification rating between at least 10-50 % of cation exchange capacity, eventually even more. In case of higher exchange capacity it is preferable to use a mixture of modified clay mineral and inert material, e.g.
  • Liapor expanded clay to provide the flow of contaminated water, due to the hydrophobic surface of the modified clay. Collected are particularly the more complex polycyclic aromatic compounds - hydrocarbons, or their derivatives comprising various heteroatoms having free electron pair, and lower hydrocarbon aliphatic derivatives carrying various heteroatoms. it is effective also for removal of nitrate, perchlorate, chloride, sulfate, chromium, phosphate, and other anions and for removal of pharmaceuticals, dyes and pesticides from waste or surface water, as well as for removal of anionic radionucleotides (Tc and iodine). The effectiveness of this layer is determined by the presence of aromatic ring in the structure of organic cation.
  • Layer 103 comprises - vermiculite modified with organic cations (ammonium, phosphonium and sulfonium cations) having short hydrocarbon chains (methyl, ethyl, propylene and butyiene), e.g. tetramethylammonium, tetraethyiammonium and the like, and for removal of more polar organic substances (lower chlorinated hydrocarbons, phenol derivatives, and the like) with Kow values around 2-4. It is also suitable for pharmaceuticals, pesticides, and the like.
  • organic cations ammonium, phosphonium and sulfonium cations
  • short hydrocarbon chains methyl, ethyl, propylene and butyiene
  • polar organic substances lower chlorinated hydrocarbons, phenol derivatives, and the like
  • Layer 104 - vermiculite in sodium or natural form particularly intended for removal of inorganic cations. Due to the fact that the effectiveness of vermiculite for inorganic anions is low because of its negative charge on layers inside its structure, the effectiveness of this layer may be increased by using layer of vermiculite in sodium form mixed with clay minerals characterized by the positive charge on layers, such as hydrotalcites, which may be modified using respective organic anions (dodecyl sulfates, and the like).
  • the removed substances are specifically inorganic cations Cu, Ni, Zn, Cd, Pb, As, Ba, Co, Cr, Cu, Ni, Pb, Sr, V and radionuclides Ni, Eu, Th, U, Csa Sr and hydrophilic substances without a charge, further polar pharmaceuticals, pesticides and surfactants.
  • Layer 105 comprises a layer of active charcoal. It is possible to use this layer for further purification to collect possible leakages of low molecular weight substances and released organic cations.
  • Layer 106 comprises inert material, by means of which the particular layers are separated from each other.
  • the inert material may be diatomaceous earth, Liapor, and the like.
  • the adsorbent material 10 comprises inert material and following layers: layer 101 of vermiculite modified with organic cations (ammonium, phosphonium and sulfonium cations) having at least one long carbon chain, layer 102 of vermiculite modified with organic cations having at least one long carbon chain C12-C18 with at least one aromatic ring, layer 103 of vermiculite modified with organic cations (ammonium, phosphonium and sulfonium cations) with short hydrocarbon chains (methyl, ethyl, propylene and butylene), layer 104 of vermiculite in sodium or natural form, intended particularly for removal of inorganic cations, layer 105 of active charcoal and layer 106 of inert material;
  • the adsorbent material 10 comprises following layers: layer 102 of vermiculite modified with organic cations having at least one long carbon chain C12-C18 and at least one aromatic ring, layer 103 of vermiculite modified with organic cations (ammonium, phosphonium and sulfonium cations) with short hydrocarbon chains (methyl, ethyl, propylene and butylene) and layer 104 of vermiculite in sodium or natural form intended particularly for removal of inorganic cations;
  • the adsorbent material 10 comprises following layers: layer 102 of vermiculite modified with organic cations having at least one long carbon chain C12-C18 and at least one aromatic ring, layer 03 of vermiculite modified with organic cations (ammonium, phosphonium and sulfonium cations) with short hydrocarbon chains (methyl, ethyl, propyl and butyl), layer 104 of vermiculite in sodium or natural form intended particularly for the removal of inorganic cations and layer 105 of active charcoal;
  • the adsorbent material 10 comprises following layers: layer 102 of vermiculite modified with organic cations with at least one long carbon chain C12-C18 and at least one aromatic ring, layer 103 of vermiculite modified with organic cations (ammonium, phosphonium and sulfonium cations) having short hydrocarbon chains (methyl, ethyl, propyl and butyl), layer 104 of vermiculite in sodium or natural form intended particularly for removal of inorganic cations; •
  • the adsorbent material 10 comprises following layers: layer 101 of vermiculite modified with organic cations (ammonium, phosphonium and sulfonium cations) having at least one long carbon chain, layer 102 of vermiculite modified with organic cations having at least one long carbon chain C12-C18 and at least one aromatic ring, layer 103 of vermiculite modified with organic cations (ammonium, phosphonium and
  • the adsorbent material 10 comprises following layers: layer 102 of vermiculite modified with organic cations having at least one long carbon chain C12-C18 and at least one aromatic ring, layer 103 of vermiculite modified with organic cations (ammonium, phosphonium and sulfonium cations) with short hydrocarbon chains (methyl, ethyl, propyl and butyl) and layer 104 of vermiculite in sodium or natural form intended particularly for removal of inorganic cations;
  • the adsorbent materia! 10 comprises following layers: layer 101 of vermiculite modified with organic cations (ammonium, phosphonium and sulfonium ones) having at least one long carbon chain, layer 102 of vermiculite modified with organic cations having at least one long carbon chain C12-C18 and at least one aromatic ring, layer 103 of vermiculite modified with organic cations (ammonium, phosphonium and sulfonium ones) and short hydrocarbon chains (methyl, ethyl, propyl and butyl) and layer 104 of vermiculite in sodium or natural form intended particularly for removal of inorganic cations;
  • the adsorbent material 10 comprises following layers: layer 101 of vermiculite modified with organic cations (ammonium, phosphonium and sulfonium ones) having at least one long carbon chain, layer 102 of vermiculite modified with organic cations having at least one long carbon chain C12-C18 and at least one aromatic ring, layer 103 of vermiculite modified with organic cations (ammonium, phosphonium and sulfonium ones) with short hydrocarbon chains (methyl, ethyl, propyl and butyl) and layer 104 of vermiculite in sodium or natural form intended particularly for removal of inorganic cations.
  • Antibacterial effects may be observed mainly in layers 101 and 102, wherein in general, the layer 102 has a stronger effect.
  • Modified vermiculites are resistant to pH 2-12 depending on the used organic cation.
  • ammonium cations are resistant to almost entire pH range
  • pyridinium cations only to pH ranging between 4-10, this is important to take into account when treating wastewater with low pH.
  • the sorption capacity is determined in the order of tens to hundreds g per kg of sorption material.
  • the flow rate of water approximately 0,1 l/s, with minimum cleaning ability 155 m 3 per 70 kg of material.
  • Filter is suitable for purification of surface water, groundwater, or wastewater contaminated with organic as well as inorganic contaminants, for elimination of ecological burdens and also for depriving water of pathogenic microorganisms.
  • the purification of water may be performed in households as well as on industrial scale.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
PCT/CZ2015/000050 2014-12-31 2015-05-21 Filter for removal of inorganic and organic substances from contaminated water WO2016107617A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001004057A1 (en) * 1999-07-13 2001-01-18 Amcol International Corporation Method and apparatus for removing oil from water including monitoring of adsorbent saturation
WO2006077583A1 (en) * 2005-01-18 2006-07-27 Yissum Research Development Company Of The Hebrew University Of Jerusalem Removal of organic pollutants from contaminated water
CN101125718A (zh) * 2007-07-13 2008-02-20 北京大学 一种处理中晚期垃圾渗滤液的方法
CN103214054B (zh) * 2013-01-04 2014-08-06 太原理工大学 一种去除水中硫氰酸根离子的方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1517715A (en) * 1974-11-26 1978-07-12 British Petroleum Co Apparatus for oil separation
US5268109A (en) * 1990-08-31 1993-12-07 Boyd Stephen A Method of removing hydrocarbon contaminants from air and water with organophilic, quaternary ammonium ion-exchanged smectite clay
US5389200A (en) * 1993-04-26 1995-02-14 Rheox, Inc. Process for removing inorganic components that form ash on ignition and oily waste from paper during recycling
NL9301919A (nl) * 1993-05-27 1994-12-16 Pelt & Hooykaas Werkwijze voor het afvangen van milieuschadelijke stoffen uit met dergelijke stoffen verontreinigd materiaal.
US5401417A (en) * 1993-07-30 1995-03-28 University Of Delaware Selective adsorption of organic material from water by modified clays
CZ302813B6 (cs) * 2008-07-28 2011-11-23 Vysoká škola bánská - Technická univerzita Ostrava Zpusob modifikace vermikulitu, zejména na sorpcní materiál
CA2746067C (en) * 2008-12-09 2017-07-25 Crc Care Pty Ltd Modified clay sorbents
CN103991915B (zh) * 2010-09-03 2016-10-12 专业净化有限公司 水过滤装置及水过滤包
CZ2013451A3 (cs) * 2013-06-13 2014-07-30 Vysoká Škola Báňská - Technická Univerzita Adsorpční materiál pro zadržení toxických škodlivin, jeho použití a ochranný kompozitní systém, který absorpční materiál obsahuje a jeho použití

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001004057A1 (en) * 1999-07-13 2001-01-18 Amcol International Corporation Method and apparatus for removing oil from water including monitoring of adsorbent saturation
WO2006077583A1 (en) * 2005-01-18 2006-07-27 Yissum Research Development Company Of The Hebrew University Of Jerusalem Removal of organic pollutants from contaminated water
CN101125718A (zh) * 2007-07-13 2008-02-20 北京大学 一种处理中晚期垃圾渗滤液的方法
CN103214054B (zh) * 2013-01-04 2014-08-06 太原理工大学 一种去除水中硫氰酸根离子的方法

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