WO2025061868A1 - Procédé d'élimination de substances organiques dissoutes dans des liquides au moyen d'un adsorbant ultrafin ou superfin dans des procédés d'épuration séquentielle et/ou discontinue de traitement de l'eau et des eaux usées - Google Patents

Procédé d'élimination de substances organiques dissoutes dans des liquides au moyen d'un adsorbant ultrafin ou superfin dans des procédés d'épuration séquentielle et/ou discontinue de traitement de l'eau et des eaux usées Download PDF

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WO2025061868A1
WO2025061868A1 PCT/EP2024/076309 EP2024076309W WO2025061868A1 WO 2025061868 A1 WO2025061868 A1 WO 2025061868A1 EP 2024076309 W EP2024076309 W EP 2024076309W WO 2025061868 A1 WO2025061868 A1 WO 2025061868A1
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superfine
adsorbent
ultra
mixture
liquid
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English (en)
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Thomas FUNDNEIDER
Ulrich Grabbe
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Mecana Ag
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Mecana Ag
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Priority to CN202480053175.0A priority Critical patent/CN121729390A/zh
Priority to AU2024344975A priority patent/AU2024344975A1/en
Publication of WO2025061868A1 publication Critical patent/WO2025061868A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • 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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
    • C02F2003/003—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/001—Upstream control, i.e. monitoring for predictive control
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/04—Oxidation reduction potential [ORP]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/05—Conductivity or salinity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/20—Total organic carbon [TOC]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/21—Dissolved organic carbon [DOC]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1263—Sequencing batch reactors [SBR]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems

Definitions

  • the present invention relates to a process for the removal of dissolved organic substances in liquids using ultra- or superfine adsorbent in sequential and/or discontinuous purification processes for water and wastewater treatment.
  • WO 2020/118513 A1 discloses a process for removing contaminants from water, in particular groundwater and drinking water, comprising the following steps: adding powdered submicron activated carbon (sPAC) to an inflow of water to be treated;
  • sPAC powdered submicron activated carbon
  • US 5,126,050 A relates to a periodic multi-stage process for the removal of volatile, semi-volatile and non-volatile organic contaminants from water, Wastewater or spent granular activated carbon.
  • the process includes
  • EP 0 196402 A2 describes a combination of physicochemical and biological treatment processes for the removal of dioxins, polychlorobiphenyls (PCBs), and other halogenated organic compounds from wastewater.
  • the residual dioxins and PCBs are removed after the pretreatment steps of neutralization, oxidation, and sedimentation in a sequencing batch reactor (PAC-SBR) enriched with powdered activated carbon.
  • PAC-SBR sequencing batch reactor
  • US Pat. No. 5,451,320 A discloses a process and apparatus for removing toxic volatile organic compounds (VOCs) and other organic substances from contaminated groundwater or wastewater.
  • the process comprises treating the incoming groundwater or wastewater by air stripping, biological oxidation, and adsorption of powdered activated carbon (PAC) in a closed gas-stripping bioreactor, air purification using a granular activated carbon contactor, and recirculating the PAC-purified air for further groundwater or wastewater treatment.
  • PAC powdered activated carbon
  • WO 2019/195918 A1 discloses a wastewater treatment process using aerobic granular sludge (AGS). In this process, flocculent biomass is converted into an anoxic/anaerobic/aerobic continuous flow configuration of a flow reactor.
  • AGS aerobic granular sludge
  • EP 1 627 854 A1 relates to a method for selecting an activated sludge with a predetermined, low sludge index for wastewater treatment in a sequencing Batch Reactor (SBR). The process includes the following steps:
  • US 5,354,458 A describes a sequencing batch plant for treating contaminated water.
  • the plant comprises an inlet pipe, a batch reactor, a chemical feed device, at least one mixing device, a coarse bubble distribution device, a fine bubble distribution device, a liquid discharge device, and a sludge discharge device for the required liquid treatment.
  • it further comprises a gas movement device, a gas pipe, a flow meter, a housing, and a gas purification device for air emission control if required.
  • EP 2 960214 A1 relates to a process for removing pharmaceutical products from wastewater using powdered activated carbon in a sequential bioreactor.
  • the process comprises a first reaction unit operating sequentially, to which the powdered activated carbon is added directly.
  • the effluent produced by this first unit enters an adjacent chamber containing an ultrafiltration membrane with a pore size in the range of 0.04 - 0.4 pm, which is continuously aerated and in which the permeate is produced, which represents the final effluent of the process.
  • the object of the invention is to provide an improved process for removing (dissolved) organic substances in liquids.
  • An ultra- or superfine adsorbent with a particle diameter can be added.
  • An adsorbent mixture of two or more identical adsorbents but with different particle diameters can also be added.
  • This mixture of two or more identical adsorbents but with different particle diameters has an adsorbent and an average particle diameter that corresponds to the average of the different particle diameters according to the mixing ratio.
  • the ultra- or superfine adsorbent mixture can be a mixture of different adsorbents with the same or different particle diameters.
  • An ultrafine adsorbent or an ultrafine adsorbent mixture has a particle diameter dso of less than 0.5 pm.
  • a superfine adsorbent or a superfine adsorbent mixture has a particle diameter dso of 0.5 pm to 10 pm.
  • the particle diameter dso of the ultra- or superfine adsorbent mixture is preferably between 0.1 and 10 pm.
  • Discharge or partial discharge of suspended and/or granulated biomass can take place before or after removal of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture.
  • the residence time of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture in the system corresponds to the time between the addition of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture to the liquid to be treated and the removal of the ultra- or superfine adsorbent mixture from the liquid.
  • the reaction time of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture differs from this.
  • Reaction time corresponds to the time between the start of adsorption, i.e., the first contact of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture with organic substances, and the end of adsorption, i.e., flocculation and settling of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture in the sludge or removal of the ultra- or superfine adsorbent mixture from the liquid by sedimentation and/or flotation and/or filtration.
  • the reaction time can be between 0.1 and 720 minutes, advantageously between 0.5 and 120 minutes, further advantageously between 1 and 60 minutes, and particularly advantageously between 2 and 30 minutes.
  • Sequential and/or discontinuous purification processes include, for example, water and wastewater treatment in SBR systems.
  • the reaction steps in SBR systems typically include feeding (feed), reacting/mixing with/without aeration, settling/separating, and effluent.
  • the adsorbent mixture can be added at any stage of the SBR system.
  • the adsorbent mixture can be left in the reactor for one or more reaction steps.
  • the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture can also be removed from the liquid in the same reaction step in which it was added.
  • the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture can be added during the mixing reaction step to ensure the most uniform distribution possible within the liquid to be treated.
  • the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture can be added in the reaction step of sedimentation or separation.
  • the removal of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture from the water can take place after stripping. This means that the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture remains in the water in suspended form after addition and after the reaction step of stripping.
  • the removal of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture from the water takes place by sedimentation and/or flotation and/or filtration. In this process, the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture can be Dispersants are added.
  • the ultra- or superfine adsorbent or adsorbent mixture can also be removed by discharging it with the sludge.
  • the residence time of the ultra- or superfine adsorbent or adsorbent mixture in the water and sludge can be decoupled. This allows the ultra- or superfine adsorbent or adsorbent mixture to be flocculated into the sludge and discharged via the sludge. Flocculation can be assisted by the addition of an additive.
  • the water no longer needs to be separated from the ultra- or superfine adsorbent after the removal reaction step, for example, by filtration.
  • ⁇ reactors such as fully mixed reactor systems (Continuous Stirred Tank Reactors, CSTRs for short), which are operated with continuous/discontinuous flow or continuously/batchwise (such as Sequencing Batch Reactors (SBRs for short), Membrane Aerated Biofilm Reactors (MABRs for short), Moving Bed Biofilm Reactors (MBBRs for short), Hybrid Fluidised Beds, systems with granulated biomass), Plug-flow systems or single- or multi-stage biological systems.
  • SBRs Sequencing Batch Reactors
  • MABRs Membrane Aerated Biofilm Reactors
  • MBBRs Moving Bed Biofilm Reactors
  • Hybrid Fluidised Beds systems with granulated biomass
  • Plug-flow systems or single- or multi-stage biological systems.
  • the oxygen input into the system can be advantageously improved by adding the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture. This results in (partial) oxygen adsorption
  • the addition of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture takes place in phases in which the organic background load (measured by the dissolved chemical oxygen demand (sCOD), dissolved organic carbon (DOC), spectral absorption coefficient (SAC), for example at a wavelength of 254 nm) is low and thus the competitive adsorption is minimal, with the aim of removing substances such as organic trace substances in a process.
  • the measurement can be carried out at the beginning of a reaction step or shortly before the end of the reaction step. Measurements can also be taken shortly after the start of the reaction step. Measurements can also be taken at any time within a reaction step.
  • the ultra- or superfine adsorbent or adsorbent mixture is added proportionally to the initial concentration and/or volume flow and/or based on surrogate parameters.
  • the ultra- or superfine adsorbent or adsorbent mixture can be mixed with the liquid to be treated, for example, in the form of a suspension.
  • This ultra- or superfine adsorbent or adsorbent mixture can be mixed with additives.
  • the settling properties of the biomass are not negatively influenced by the addition of ultra- or superfine adsorbent.
  • ultra- or superfine adsorbent or ultra- or superfine adsorbent mixture increases the proportion of inorganic components in the biomass to a lesser extent than adsorbent mixtures with a particle diameter dso greater than 10 pm, since smaller amounts of ultra- or superfine adsorbent or ultra- or superfine adsorbent mixture need to be used.
  • the hydraulic residence time, or cycle time, of the biological reactors remains unchanged through the use of ultra- or superfine adsorbents or ultra- or superfine adsorbent mixtures.
  • SBR systems with the reaction steps of feeding (feed), reacting/mixing with/without aeration, settling/separating, and effluent, With/without simultaneous or/and separate removal of the (excess) adsorbent with discontinuous or continuous addition of the feed, the addition of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture with/without combined, if necessary also simultaneous, addition of additives can be integrated into the existing process without requiring an increase in the cycle time/reaction time.
  • the decanter type in SBR systems can support targeted discharge or concentration of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture.
  • Another possible application of the process according to the invention can be in biological reactors for the prevention or active in-situ minimization of toxic impacts.
  • the biological systems are protected by the targeted and rapid removal of impurities, for example, from the residual depletion of dissolved oxygen. This results in no significant accumulation of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture.
  • the process can be used in anaerobic granular-based systems (such as Upflow Anearobic Sludge Blanket Digestion (UASB) or Expanded Granular Sludge Bed Digestion (EGSB) or Internal Circulation (IC) reactors).
  • UASB Upflow Anearobic Sludge Blanket Digestion
  • EVSB Expanded Granular Sludge Bed Digestion
  • IC Internal Circulation
  • the process can also be used for partially biological or non-biological and/or chemical-physical systems such as superfine adsorbent SBRs.
  • the addition of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture can take place in the reaction steps of feeding (feed), reacting/mixing with/without aeration, settling/separating, and effluent, with/without simultaneous and/or separate removal of the ultra- or superfine adsorbent or the ultra- or superfine (excess) adsorbent mixture.
  • the process can be carried out with or without biological processes as a fast adsorption reactor with reaction times of 0.5 - 120 minutes in the reaction/mixing phase, achieving targeted enrichment of the ultra- or superfine adsorbent.
  • the solids content of the (sludge) adsorbent-additive mixture is in the range of 0.005 wt.% to 20 wt.%.
  • the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture is added in the phase in which the organic background load (based on surrogate parameters such as sCOD, DOC, SAC) is low and thus the competitive adsorption is minimal, with the aim of removing the organic substances, such as organic trace substances, in one process.
  • the process can also be used in semi-biological/non-biologically active adsorptive systems, such as (continuously or discontinuously fed) fixed/fluidized bed adsorbers (with, for example, granulated activated carbon and/or ion exchange resins) for short-term or long-term increase in the adsorptive removal of organic substances.
  • semi-biological/non-biologically active adsorptive systems such as (continuously or discontinuously fed) fixed/fluidized bed adsorbers (with, for example, granulated activated carbon and/or ion exchange resins) for short-term or long-term increase in the adsorptive removal of organic substances.
  • the addition of ultra- or superfine adsorbents or ultra- or superfine adsorbent mixtures, with or without the combined, or possibly simultaneous, addition of additives, can be used to increase and/or maintain adsorptive removal.
  • the exchange of the adsorbent in biologically active/activated fixed/fluidized bed adsorbers can be delayed by the addition of ultra- or superfine adsorbents or ultra- or superfine adsorbent mixtures, so that biological processes are maintained and adsorptive processes are only enhanced/supported in phases.
  • the existing reactor volume can generally be utilized in all reaction steps, so that the integration of the addition of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture can be easily implemented.
  • sedimentation and/or flotation and/or filtration processes can be installed downstream of all systems, so that the adsorbent content in the system effluent is minimized.
  • Surface filtration processes such as cloth filtration or, more preferably, pile filtration, are particularly preferred.
  • the residual ultra- or superfine adsorbent can be discharged via the process sludge.
  • the control and/or regulation of the dosage of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture depends on the remaining dissolved organic substances (such as dissolved organic matter, or DOM) in the reaction step, or rather, the ratio of "start DOM" to "end DOM.”
  • the use of algorithms and/or machine learning and/or artificial intelligence is advantageous for the control and/or regulation of the dosage of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture and/or additives and/or the overall process.
  • UV-VIS probes and/or TOO (Total Organic Carbon)/DOC analyzers and/or COD analyzers and/or conductivity probes and/or ammonium analyzers and/or oxygen probes and/or redox probes and/or pH probes can be used. This ensures that the required addition of ultra- or superfine adsorbent or ultra- or superfine adsorbent mixture is available to ensure consistent DOM removal.
  • the dosage ( ⁇ 1 - 10,000 mg/l) varies depending on the DOM and the ultra- or superfine adsorbent or adsorbent mixture, respectively, and their interaction with each other.
  • the large specific surface area and particle diameter dso of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture leads to a faster removal of the DOM (after just a few minutes ( ⁇ 1 - 15 min)) compared to adsorbents with larger grain diameters (dso > 10 pm). This also results in a lower demand for adsorbent with the same removal of DOM.
  • the agglomeration cores serve as growth surfaces for the ultra- or superfine adsorbent mixture and/or for organisms in the existing process.
  • the agglomeration cores themselves can serve as nuclei/growth surfaces for biomass formation (e.g., aerobic granular).
  • Agglomeration cores can be added to the liquid to be treated before or after the addition of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture. They can also be added during the preparation of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture.
  • An embodiment of the invention provides that substrate for the biological process with a particle diameter d50 of 5 to 5,000 pm is added to the liquid to be treated.
  • the substrate can be added, for example, in the form of nutrient and/or trace element pellets. It can, for example, contain a carbon, nitrogen, and/or phosphorus source.
  • the substrate promotes local biological growth. This can serve as an agglomeration nucleus for the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture.
  • the substrate can be added to the liquid to be treated before or after the addition of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture. The addition can also take place together with the preparation of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture.
  • a further embodiment of the invention consists in that the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture is added in a dosage amount of 0.1 to 10,000 mg/l, preferably of 1 to 100 mg/l, particularly preferably of 2 to 20 mg/l.
  • the dosage varies depending on the dissolved organic substances and the ultra- or superfine adsorbent used, or their interaction with each other.
  • the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture has a particle diameter dso of 0.01 to 8 pm, preferably of 0.1 to 5 pm and particularly preferably of 0.8 to 3 pm.
  • the large specific surface area and particle diameter dso of the ultra- or superfine adsorbent leads to a faster removal of the dissolved organic substances after only a few minutes ( ⁇ 1 - 15 min) compared to adsorbents with larger Particle diameter (dso > 10 pm). This also results in a lower adsorbent requirement while maintaining the same removal of dissolved organic substances.
  • the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture is added in the form of a suspension, preferably with an adsorbent concentration of 2 to 50 wt.%, preferably of 5 to 25 wt.% and particularly preferably of 8 to 15 wt.%.
  • the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture can be present as a suspension.
  • the concentration of the ultra- or superfine adsorbent in the suspension can be ⁇ 40%.
  • the suspension can be added by metering.
  • the ultra- or superfine adsorbent in the suspension does not pose an explosion hazard.
  • the suspension of ultra- or superfine adsorbent can be produced in batches. Production can be carried out directly as part of the overall process or externally and thus as a standalone process. Wet grinding is usually carried out in a one- and/or two-stage process.
  • the suspension of the ultra- or superfine adsorption mixture can contain additives, which leads to better distribution and a change in the agglomeration behavior of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture in the fluid.
  • the proportion of the additive (such as dispersant) can also be used to control the separation and enrichment behavior of the ultra- or superfine adsorbent.
  • the suspension can be produced batchwise or continuously, on-site or off-site.
  • the adsorbent is ground, for example, in a ball mill.
  • finely granulated ( ⁇ 500 pm) or powdered activated carbon ( ⁇ 180 pm) can be used as the starting material, with the grinding time being ⁇ 5 - 120 min to produce superfine activated carbon with a target particle diameter of dso 0.01 - 10 pm. Grinding takes place in a single-stage process when activated carbon ( ⁇ 500 pm) is used as the adsorbent.
  • granulated activated carbon is a granular product; by convention, at least 90% by mass is retained on a 180 pm test sieve.
  • powdered activated carbon has a grain size of less than 150 pm, with a mass fraction of 95%.
  • a further embodiment of the invention is that the ratio of the agglomeration cores to the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture is less than 1:2.
  • agglomeration nuclei for example in the form of a coarse-grained adsorbent (dso > 10 - 250 pm) or a substrate, to the suspension of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture, whereby the proportion of agglomeration nuclei in the ultra- or superfine adsorbent mixture is ⁇ 50%, a targeted accumulation of adsorbent in the biological system can be achieved, thus achieving a buffering effect and/or extensive utilization of the adsorption capacity of the adsorbent.
  • the adsorbents can simultaneously serve as growth surfaces or nuclei for granules and/or be incorporated into sludge flocs.
  • activated carbon is used as an adsorbent, the positive charge of the activated carbon has a positive effect on the granulation process.
  • the granulation process can be triggered by an ultra- or superfine adsorbent or an ultra- or superfine adsorbent mixture with differently electrically charged surfaces of the adsorbents.
  • a further embodiment of the invention consists in that the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture contains activated carbon and/or bentonite and/or zeolite and/or adsorbents of polymeric origin and/or silica gel and/or ion exchange resins and mixtures thereof.
  • any adsorbent capable of adsorbing dissolved organic substances is suitable.
  • these can include, for example, anthropogenic organic trace substances (such as pharmaceutical active ingredients, X-ray contrast agents, substances from personal care and cleaning products, biocides, flame retardants, perfluorinated chemicals, polychlorinated biphenyls) and/or per- and polyfluorinated alkyl compounds (PFAS) and/or organic (refractory) carbon compounds.
  • the raw material of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture is usually in powder and/or granular form and consists of substances that are tailored to the dissolved organic substances or the water matrix.
  • a further embodiment of the invention is that the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture contains additives, in particular metal salts and/or polymers.
  • the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture can contain appropriate additives, such as metal salts, in particular divalent or trivalent iron or/and (polymeric) aluminum salts, and/or cationic, anionic or/and non-ionic polymers to improve properties such as effluent quality with regard to separation by sedimentation and/or flotation and/or filtration.
  • the additive can be a flocculant to enable the discharge of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture through the sludge.
  • the additive can also be a dispersant to prevent separation by flocculation.
  • the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture can then be removed from the water with subsequent sedimentation and/or flotation and/or filtration.
  • the dosage of additives must be adjusted depending on the process and is usually proportional to the amount of ultra- or superfine adsorbent or ultra- or superfine adsorbent mixture.
  • the suspension of the ultra- or superfine adsorbent or ultra- or superfine adsorbent mixture may already contain additives, making them possible to add them together in the process.
  • the additives are added either directly during production or subsequently.
  • the additives can also be added to the liquid to be treated separately from the ultra- or superfine adsorbent or ultra- or superfine adsorbent mixture.
  • metal salts and/or polymers are optionally possible. These are also added to the liquid feed for sedimentation and/or flotation and/or filtration and/or the upstream contact and/or reaction reactor. The addition can take place simultaneously with the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture or shortly after its addition.
  • the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture is added to the liquid feed.
  • the liquid inlet is defined here as the area in front of the reactor in which the liquid is treated. This could be, for example, the liquid feed of an SBR.
  • the reaction time for removing the organic substances corresponds to the hydraulic residence time of the process.
  • a separate contact reactor for the action of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture before their removal from the liquid can be dispensed with.
  • a further embodiment of the invention consists in removing the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture or residues of the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture and/or biomass residues with the ultra- or superfine adsorbent or the ultra- or superfine adsorbent mixture from the liquid by cloth filtration, preferably by pile filtration.
  • Cloth filtration processes, and especially pile filtration processes have proven particularly effective and economical within the scope of the invention.
  • a correspondingly fine filter cloth can be used.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Dispersion Chemistry (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

Le but de l'invention est de fournir un procédé amélioré pour éliminer les substances organiques (dissoutes) des liquides à l'aide d'un adsorbant ultrafin ou superfin. Selon l'invention, un procédé consiste à mesurer la concentration de substances organiques dissoutes à l'entrée du liquide et/ou au début ou peu avant la fin d'une étape de réaction du procédé, puis à ajouter un adsorbant ultrafin ou superfin ou un mélange d'adsorbants ultrafin ou superfin au liquide à traiter et à le mélanger à ce dernier. Après un temps de séjour suffisant, l'adsorbant ultrafin ou superfin ou le mélange adsorbant ultrafin ou superfin est retiré du liquide.
PCT/EP2024/076309 2023-09-20 2024-09-19 Procédé d'élimination de substances organiques dissoutes dans des liquides au moyen d'un adsorbant ultrafin ou superfin dans des procédés d'épuration séquentielle et/ou discontinue de traitement de l'eau et des eaux usées Pending WO2025061868A1 (fr)

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CN202480053175.0A CN121729390A (zh) 2023-09-20 2024-09-19 在用于水处理和废水处理的相继进行和/或不连续净化法中以极细或超细吸附剂去除液体中溶解的有机物质的方法
AU2024344975A AU2024344975A1 (en) 2023-09-20 2024-09-19 Method for removing dissolved organic substances from liquids using an ultra- or superfine adsorbent in sequential and/or discontinuous purification methods for treating water and wastewater

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DE102023125542.8A DE102023125542A1 (de) 2023-09-20 2023-09-20 Verfahren zur Entfernung von gelösten organischen Substanzen in Flüssigkeiten mit ultra- oder superfeinen Adsorbens in Kombination mit biologischen/chemisch-physikalischen/ adsorptiven Systemen zur Wasser- und Abwasserbehandlung

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