WO2023223058A1 - Procédé d'élimination de micropolluants de l'eau par ozonation catalytique hétérogène - Google Patents

Procédé d'élimination de micropolluants de l'eau par ozonation catalytique hétérogène Download PDF

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WO2023223058A1
WO2023223058A1 PCT/GR2023/000019 GR2023000019W WO2023223058A1 WO 2023223058 A1 WO2023223058 A1 WO 2023223058A1 GR 2023000019 W GR2023000019 W GR 2023000019W WO 2023223058 A1 WO2023223058 A1 WO 2023223058A1
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water
catalyst
ozone
removal
concentration
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PCT/GR2023/000019
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Panagiotis DIAMANTOPOULOS
Panagiota-Aikaterini PALASANTZA
Georgios GERMANIDIS
Manassis Mitrakas
Anastasios Zoumpoulis
Savvina Psaltou
Efthymia KAPRARA
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Aristotle University Of Thessaloniki-E.L.K.E.
Aktor Anonymi Techniki Etaireia
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Publication of WO2023223058A1 publication Critical patent/WO2023223058A1/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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40—Static mixers
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F2101/301—Detergents, surfactants
    • 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
    • C02F2101/305—Endocrine disruptive 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
    • C02F2101/306—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
    • C02F2101/36—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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/005—Processes using a programmable logic controller [PLC]
    • 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
    • C02F2301/00—General aspects of water treatment
    • C02F2301/02—Fluid flow conditions
    • C02F2301/022—Laminar
    • 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
    • C02F2301/02—Fluid flow conditions
    • C02F2301/028—Tortuous
    • 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
    • C02F2301/04—Flow arrangements
    • C02F2301/046—Recirculation with an external loop
    • 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
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

Definitions

  • the invention belongs to the field of chemical engineering and specifically refers to the technology of heterogeneous catalytic ozonation for the removal of organic pollutants of low concentration ( ⁇ g/L - ng/L), the so-called micropollutants, from groundwater and surface water for human consumption.
  • Micropollutants removal processes can be divided into three categories: phase change technologies, biological treatment, and advanced oxidation techniques.
  • Phase change technologies have the ability to transfer the contaminant from one phase (e.g., aqueous) to another (e.g., solid).
  • This category includes the adsorption process and membrane technology (O.M. Rodriguez-Narvaez et. al, Chem. Eng. J. 323 (2017) 361-380).
  • the most widely used adsorbent material is activated carbon, with the use of which a large fraction of micropollutants are removed at rates greater than 90% in distilled water environments (R. Baccar et. al., Chem. Eng. J. 211-212 (2012) 310-317; D.P. Grover et.
  • ultrafiltration, nanofiltration and reverse osmosis are mainly used for the removal of micropollutants.
  • the removal depends on the type of membrane and the type of micropollutant.
  • a polysulfone ultrafiltration membrane can remove bisphenol A by 75% from distilled/pure water, while with a polyvinylidene membrane the removal reaches 98% (J. Heo et. al., Sep. Purif. Technol. 90 (2012) 39-52; A. Melo- Guimaraes et. al. Water Sci. Technol. 67 (2013)).
  • Membrane technology can be effective in removing some priority pollutants, but in this case, the challenge is the final disposal of the pollutants, as the treatment creates two different effluent streams, the treated flow, and the concentrated discharge-waste phase. Moreover, in the case of drinking water, membranes degrade its quality characteristics by removing nutrients (Ca - Mg - HCO 3 - - SiO 2 ) .
  • the pollutants removed end up either in the solid phase during the adsorption process or in the discharge effluent during membrane separation. Therefore, by using this type of technologies the pollutants are not destroyed, they just change phase, continuing to be a problem for the environment (O.M. Rodriguez-Narvaez et. al., Chem. Eng. J. 323 (2017) 361-380).
  • Biodegradable compounds such as caffeine, diclofenac, trimethoprim, while they fail to remove the more difficult to biodegrade compounds such as bezafibrate, metaprolol, sulpiride (Q. Sui et. al., Environ. Sci. Technol. 45 (2011) 3341-3348).
  • the micropollutants degradation efficiency is significantly related to the treatment conditions: aerobic or anaerobic. Removal rates range from zero (e.g., carbamazepine) during aerobic treatment to almost complete removal (97-100%) of naproxen by either aerobic or anaerobic biological treatment (J. Simpa et. al., Desalination 250 (2010) 653-659; J.L.
  • AOPs Advanced Oxidation Processes
  • AOPs are the best alternative - synergistic processes, due to their ability to show higher organic compound removal efficiencies than both "phase change" technologies and conventional biological processes. It should be clarified here that AOPs are generally applied: to the biological treatment effluent of urban wastewater as tertiary treatment, as well as to the primary treatment of groundwater and surface water mainly intended for drinking. The high rates of the process are related to the production of hydroxyl radicals with an oxidation potential of 2.8 V, which is their main characteristic (E. M. Cuerda-Correa et. al., Water 12 (2020) 102). Processes belonging to AOPs have different free radical production pathways and specific conditions determined by different materials (J. L. Wang & L.
  • Ozone gas is produced on site from pure oxygen or atmospheric air by transforming oxygen in an electric field into ozone and introduced into the aqueous phase in the form of bubbles, resulting in a utilisation of less than 40%.
  • Ozone is an effective disinfectant and oxidant in water and liquid waste treatment, as it can be driven to produce hydroxyl radicals ( ⁇ OH) either by direct or indirect oxidation. Reactions of soluble ozone with organic matter leads to the formation of aldehydes and carboxylic acids, which do not react with ozone. This is a major disadvantage of ozonation, as it cannot achieve complete mineralisation.
  • oxidation reactions are relatively slow and selective, whereas the reactions of hydroxyl radicals with inorganic and organic matter are rapid and non-selective.
  • the contact of soluble ozone with the catalyst surface allows efficient production of hydroxyl radicals even at low pH.
  • the catalysts used for the controlled decomposition of ozone and the formation of hydroxyl radicals are typically metal oxides and hydroxy-oxides, metals in substrates, minerals, and carbons (J. Nawrocki & B. Kasprzyk-Hordern, Appl. Catal. B-Environ. 99 (2010) 27-42).
  • Catalytic ozonation is a promising technology for the efficient removal of micropollutants from water and wastewater, which are resistant to conventional treatment methods. Its main advantages compared to non-catalytic methods are the optimisation of ozone use, the increase in micropollutants removal efficiency and a higher degree of mineralization (P.M. Alvarez et. al., Carbon 44 (2006) 3102-3112). However, both in the process of single ozonation and in that of catalytic ozonation, the formation of bromides (BrO 3 -), which are carcinogenic ions for humans, is an important drawback. The production of bromates is related to the high ozone concentrations and contact time used for efficient removal of organic micropollutants from water (R.
  • the present invention focuses on the full utilization of ozone by membrane diffusion and high efficiency of micropollutants removal by a catalytic process to minimize BrO 3 - formation.
  • Ozone decomposes into the oxidised/reduced form of a metal deposited on the surface of a solid catalyst.
  • Ozone decomposition takes place in the hydroxy groups of oxides and hydroxy oxides of metals.
  • the catalyst dose is in the range of 1 - 100 mg/L, while using a micropollutant concentration of the same order of magnitude as the catalyst.
  • micropollutants are called the compounds found in the environment at concentrations of ng/L- ⁇ g/L. Therefore, a heterogeneous catalytic ozonation unit for micropollutants removal should focus on micropollutants concentrations in the ng/L- ⁇ g/L range.
  • micropollutants at ⁇ g/L concentrations and of these, few are those that study the effect of catalyst dose on the continuous flow process, and there are no studies of micropollutants removal at ⁇ g/L concentrations using a continuous flow process.
  • Document WO 97/14657 presents a heterogeneous catalytic ozonation process in which the waste is first contacted with ozone to oxidise the easily degradable pollutants and dissolve the ozone in water, and then the pollutant-ozone solution is contacted with a solid catalyst, which has been activated by ozone, to oxidise the hardly degradable compounds.
  • the effluent from the column can be recirculated for further contact with the catalyst.
  • the originality of this patent for its time was the dissolution of the ozone gas in the liquid, so that the phases during catalytic ozonation are 2 (liquid-solid) rather than three (gas-liquid-solid).
  • Document CN203625105 presents a fixed bed reactor for the treatment of refinery waste.
  • This process like the previous one, includes a reactor for initial ozonation of the waste to degrade easily degradable compounds and then the pre-treated waste goes to the catalytic column to degrade the difficultly biodegradable organic molecules.
  • the process was designed to enhance the utilisation of ozone and reduce its consumption. Excess ozone gas is recirculated and reused in the pre-treatment of fresh waste.
  • the catalyst in this case is activated carbon and the waste, as well as the ozone, enter the column from the bottom of the column in an upward flow.
  • the treated waste from the top of the column is then fed into a 2 nd activated carbon column for biological stabilization treatment of the waste.
  • a two fixed-bed reactor system is also presented in document CN 104710002. Each reactor differs both in the catalyst it contains and in the way it feeds the ozone. In the first column the ozone is fed to the waste in the form of microbubbles (5-10 ⁇ m) and the catalyst is two elements and contains iron and manganese in its structure, while in the second column the catalyst consists of 3 metals and the ozone is fed in the form of nano-bubbles (100-400 nm).
  • the two chambers are separated by a vertical wall, which is open at both ends and allows the waste to be recirculated.
  • the amount of catalyst to be used is 100 g/L. In both cases the ozone gas is added to the system in the form of bubbles.
  • Document CN104529001A also describes a catalytic ozonation system with a fluidized bed reactor, which includes catalyst recirculation.
  • This system is designed for the treatment of waste, mainly industrial waste, and focuses on COD reduction.
  • the dissolution of ozone in the liquid is done through bubble diffusers thus increasing the energy requirements of the system by not fully utilising the ozone. Excess ozone can lead to the formation of bromine, which are products of secondary pollution.
  • Document ES2265728 deals with the removal of SDBS (sodium dodecylbenzene sulfonate) through the process of heterogeneous catalytic ozonation using activated carbon (PAC) as a catalyst.
  • SDBS sodium dodecylbenzene sulfonate
  • PAC activated carbon
  • a 1 L reactor with agitation was set up, in which the pH and temperature conditions were controlled and remained constant, with the catalyst concentration ranging between 2.5 and 100 mg/L.
  • this process did not involve either recycling of the catalyst or control of the ozone transport efficiency in the liquid, and therefore does not achieve the process optimisation and reduction of treatment costs as brought about by the application of the present invention discussed below.
  • the removal of the micropollutants was due 60% to the adsorption process and 40% to the oxidation process.
  • the performance of the system was tested with respect to a specific micropollutant rather than over a range of micropollutants with different physicochemical properties.
  • ozone is added to the system in the form of bubbles. All attempts to optimise its use have been based on recirculating the excess ozone. Another way to achieve full utilisation of ozone is to use membranes to diffuse the ozone gas into the liquid without creating bubbles (bubble-less).
  • Document EP3202721A1 describes a system to remove micropollutants using ozone and hydrogen peroxide (H 2 O 2 ), which describes the removal of micropollutants from water. Ozone is introduced into the reactor at a controlled concentration through a PVDF hollow fibre membrane without the formation of gaseous bubbles. Another patent combining ozone with membranes is CN105060458.
  • the membranes used are hybrid PVDF membranes with nanoparticles in their structure that promote ozone decomposition. Hydroxyl radicals inhibit the growth and reproduction of microorganisms on the membrane surface resulting in reduced fouling to increase the lifetime of the membrane, but PVDF membranes do not have a long lifetime when using ozone.
  • a different way for controlled ozone channelling and reduction of bromine production was proposed in document US6024882. The researchers designed a pressurized plug-flow reactor where ozone and H 2 O 2 are injected into the system in small amounts at different points in the reactor. However, this system is quite complex, large, with many valves and requires close monitoring during operation.
  • Patent CN101050036A focuses on the control of bromine production through the catalytic ozonation process.
  • Materials containing cerium oxide (CeO 2 ) in their structure are proposed as catalysts.
  • Such catalysts have the ability to reduce the production of hydroxyl radicals, which are responsible for the formation of bromine.
  • the reduced production of hydroxyl radicals makes the process inefficient in terms of micropollutants removal, as this is largely dependent on the strong oxidising action of hydroxyl radicals.
  • Step 1 Removal of suspended particles for non-clogging of membranes and optimisation of hydroxyl radical production.
  • Step 3 Full utilization of ozone by diffusion into water through a hollow fibre membrane.
  • Step 4 Use of a plug-flow reactor airtightly closed creating low back-pressure gravity pressure based on the overlying level above the ozone diffusion membrane, to prevent ozone loss by diffusion into the removed gas phase and thus total utilisation (full consumption) of the added ozone, reducing fixed and energy costs.
  • the rapid reaction kinetics which implies a micropollutant destruction efficiency of more than 90% in up to 2 min, also implies a corresponding reduction in ozone concentration, resulting in the prevention of BrO 3 - formation, as the catalytic oxidation of micropollutants is completed using a plug-flow reactor in less than 10 min.
  • Step 5 Reuse of the catalyst by recirculating in the context of the circular economy, reducing the operational cost of processing.
  • Step 6 Biological filtration for optimal removal of the molecules resulting from the breakdown of the micropollutants.
  • Figure 1 shows the flowchart of the organic micropollutant degradation/decomposition process proposed in the present invention by the application of heterogeneous catalytic ozonation.
  • Figure 2 shows the diagram of the activity coefficients of ions in aqueous solutions, calculated from the Debye-Huckel and Guntelberg equations.
  • Figure 3 shows the flow diagram of the plug-flow catalytic ozonation reactor, which generates low back- pressure, gravity pressure and contributes to the total dissolution of ozone.
  • Figure 4 shows the correlation diagram of the pH value with the concentration of CO 2 .
  • the present invention relates to the method of catalytic ozonation with high efficiency of degradation of micropollutants from water intended for human consumption. In particular, it achieves the reduction of the concentration of a micropollutant, typically not exceeding 10 ⁇ g/L, with the following technical characteristics.
  • the present catalytic ozonation process includes the following equipment ( Figure 1):
  • pre-treatment of the water is required to remove suspended particles either by the classical flocculation-agglomeration-filtration process, or by simple filter filtration, which additionally removes partly natural humic components, improving the efficiency of catalytic ozonation.
  • Step 2 Adjust the pH of the water before starting the catalytic ozonation process.
  • Figure 4 specifies the determination of CO 2 addition dose with in-line mixer in the range of 20 ⁇ 10 g/m 3 to adjust the pH in the range pH s ⁇ pH ⁇ pH s +0.2.
  • pH s pK ⁇ ,2 - pK sp + p[Ca 2+ ] + p[HCO 3 ] - log ⁇ Ca 2+ - log ⁇ HCO3-
  • the values of the equilibrium constants of carbonate ionic forms with respect to temperature are selected to determine the saturation pH of CaCO 3 (pH s ) in order to adjust the pH of water for CaCO 3 nucleation.
  • STEP 3 Adding ozone by diffusion to a hollow fibre membrane, which:
  • the ozone diffusion hollow fibre membrane also acts as a plug-flow catalytic ozonation reactor, increasing the micropollutants decomposition efficiency up to 80%, while in the absence of CaCO 3 cores the efficiency with single ozonation does not exceed 25%, as the retention time of water in the hollow fibre membrane does not exceed 1 min.
  • STEP 4 Catalytic ozonation in a plug-flow reactor.
  • the decomposition efficiency of micropollutants is affected by the type and concentration of catalyst, as well as by the ozone concentration.
  • the most efficient catalysts are perlite, zeolite, talc and SiO 2 , especially after thermal treatment to remove crystalline waters and hydroxyls, as well as iron hydroxy- oxide in the form of goethite.
  • the catalyst application requires:
  • the optimum catalyst concentration is related to the type of micropollutant and water temperature.
  • the reactor will have 10 consecutive chambers ( Figure 3) with a depth of 2 - 6 m and a retention time in each chamber of 0.5 -1 min, with water being introduced into the first chamber at the bottom and overflowing from the last chamber.
  • the present method uses a plug-flow reactor without continuous stirring and full utilization of ozone.
  • the advantage of applying plug-flow reactor is the high efficiency of micropollutants degradation in a short retention time.
  • the retention time in a complete mixing reactor (CSTR) to reduce the initial concentration (CAO) of the micropollutant to a residual concentration (C AE ) is:
  • the catalyst remains in the storage tank in suspension form in communication with the membrane tank, which is returned by recirculation and mixed with the ozonated water at the outlet of the ozone addition hollow fibre membrane by diffusion.
  • the catalyst concentration in the storage tank ranges from 3 to 10 g/L with an optimum concentration of 5 ⁇ 2 g/L.
  • the recirculation (Q r ) will vary with respect to the treatment flow rate (Q) in the range 0.02 Q ⁇ Qr ⁇ 0.2Q.
  • the present method involves the reuse of the catalyst, which includes 2 important advantages: The use of a catalyst that is pre-ozonated resulting in maximum efficiency, as well as the continuous reuse of the catalyst meeting the criteria of circular economy, while reducing the operational cost of treatment.
  • STEP 6 Biological filtration process of the treated water with catalytic ozonation.
  • Groundwater and surface water micropollutants are generally not biodegradable.
  • Catalytic ozonation disorganises a proportion of organic micropollutants and a proportion breaks them down into smaller molecules that are largely biodegradable.
  • This method involves the removal of organic micropollutants belonging to the following categories: pharmaceutical compounds, personal care products, steroid hormones, pesticides/insecticides, surfactants, and super-fluorinated compounds at a concentration of less than 10 ⁇ g/L.
  • membranes with a total surface area of 1.7x10 3 m 2 are selected so that the ozone diffusion parameter is 60 L/m 2 h.
  • the ozone concentration, using an oxygen content of O 2 > 98%, in the gas phase is 180 g/m 3 .
  • the ozone supply will be:
  • the volume of the 10-chamber reactor is:
  • the blocks are placed in a row, with a distance between them of 0.5 m and 1 m distance from the wall then:
  • a power pump will be used to suck the treated water from the membrane blocks:
  • a power pump will be used to backwash each membrane block sequentially for 1 min:
  • a tank LxWxH 2.5 x 2.5 x 4 m, with a net volume of 20 m 3 , is constructed in communication with the membrane tank.
  • a power stirrer (Drawing 1 - number 13) will be installed to maintain the catalyst suspension in homogeneity:
  • the power of the catalyst recirculation pump will be:
  • the pH s saturation of calcium carbonate in the water is 7.25. > Selection of processing parameters:
  • thermally treated SiO 2 at 800 °C and in a particle size range of 5 - 50 ⁇ m will be used as a catalyst. Also, due to the relatively low water temperature and low kinetic reaction of ATZ with hydroxyl radicals and ozone, a catalyst concentration of 750 ⁇ 50 mg/L, a retention time in the plug-flow reactor of 10 min and an ozone concentration requirement of 1 mg/L due to low TOC concentration are selected. Control of LOD removal without changing the pH of the water.
  • membranes with a total surface area of 10 3 m 2 are selected so that the ozone diffusion parameter is 50 L/m 2 h.
  • the ozone concentration, using an oxygen content of O 2 > 98%, in the gas phase is 180 g/m 3 .
  • the volume of the 10-chamber reactor is:
  • the blocks are lined up in a row, with a distance between them of 0.5 m and 1 m distance from the wall then:
  • a power pump will be used to suck the treated water from the membrane blocks:
  • a power pump will be used to backwash each membrane block sequentially for 1 min:
  • a power stirrer (Drawing 1 - number 13) will be installed to maintain the catalyst suspension in homogeneity:
  • the power of the catalyst recirculation pump will be:
  • the pH s saturation of calcium carbonate in the water is 7.25.
  • thermally treated SiO 2 at 800 °C and in a particle size range of 5 - 50 ⁇ m will be used as a catalyst.
  • a catalyst concentration of 750 ⁇ 50 mg/L, a retention time in the plug-flow reactor of 10 min and an ozone concentration requirement of 1 mg/L due to low TOC concentration are selected. Control of ATZ removal by changing the pH of the water to pH s + 0,2.
  • a filtration treatment with 1 ⁇ m bag filters shall be performed prior to filtration, due to the low concentration of suspended solids.
  • the pH 7.4 ⁇ 0.5 pre-treated water significantly favours the production of hydroxyl radicals resulting in high removal efficiency of ATZ during the passage through the ozone addition by diffusion PTFE hollow fibre membranes.
  • membranes with a total surface area of 10 3 m 2 are selected so that the ozone diffusion parameter is 50 L/m 2 h.
  • the ozone concentration, using an oxygen content of O 2 > 98%, in the gas phase is 180 g/m 3 .
  • the volume of the 10-chamber reactor is:
  • the blocks are lined up in a row, with a distance between them of 0.5 m and 1 m distance from the wall then:
  • a power pump will be used to suck the treated water from the membrane blocks:
  • a power pump will be used to backwash each membrane block sequentially for 1 min:
  • a tank LxWxH 2.5 x 2.5 x 4 m, with a net volume of 20 m 3 , is constructed in communication with the membrane tank.
  • the power of the catalyst recirculation pump will be:

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  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

La présente invention concerne la mise au point d'un procédé d'ozonation catalytique hétérogène pour l'élimination à haut rendement des micropolluants organiques de l'eau destinée à la consommation humaine. L'invention concerne l'utilisation d'une membrane à fibres creuses, qui agit comme un réacteur à écoulement piston pour l'ozonation catalytique, en raison de la présence (génération in situ) de noyaux de CaCO3, ce qui entraîne une augmentation exponentielle de l'efficacité du processus en 1 minute et une utilisation complète de l'ozone par le biais de sa diffusion dans l'eau. La cinétique de réaction rapide combinée au réacteur à écoulement piston réduit rapidement la concentration d'ozone, ce qui permet de prévenir la formation de BrO3- (< 10 μg/l). Parallèlement, l'utilisation du réacteur à écoulement piston contribue à l'utilisation globale (consommation totale) de l'ozone. L'invention est conçue dans le contexte de l'économie circulaire, car elle comprend une étape de réutilisation du catalyseur avec recirculation de son alimentation en suspension, maximisant l'efficacité d'élimination des micropolluants organiques grâce à la préozonation du catalyseur, tout en réduisant le coût opérationnel du processus.
PCT/GR2023/000019 2022-05-20 2023-05-16 Procédé d'élimination de micropolluants de l'eau par ozonation catalytique hétérogène WO2023223058A1 (fr)

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