WO2013000115A1 - Ozone treatment of wastewater - Google Patents

Ozone treatment of wastewater Download PDF

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Publication number
WO2013000115A1
WO2013000115A1 PCT/CN2011/076464 CN2011076464W WO2013000115A1 WO 2013000115 A1 WO2013000115 A1 WO 2013000115A1 CN 2011076464 W CN2011076464 W CN 2011076464W WO 2013000115 A1 WO2013000115 A1 WO 2013000115A1
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Prior art keywords
ozone
oxygen
wastewater
catalyst
reactor
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PCT/CN2011/076464
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French (fr)
Inventor
Yunhui DENG
Yaping Lu
Guohua Xiu
Yepin ZHENG
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Linde Aktiengesellschaft
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Priority to PCT/CN2011/076464 priority Critical patent/WO2013000115A1/en
Publication of WO2013000115A1 publication Critical patent/WO2013000115A1/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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • 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
    • 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
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
    • 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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/003—Downstream control, i.e. outlet monitoring, e.g. to check the treating agents, such as halogens or ozone, leaving the process
    • 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
    • C02F2209/03—Pressure
    • 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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/20—Activated sludge processes using diffusers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • Traditional methods of wastewater treatment involve bringing wastewater streams into contact with bacteria, either in an aerobic or an anaerobic type process. This is typically referred to as an activated sludge treatment.
  • the bacteria consume parts of the substrate material or the waste contained in the wastewater which are typically organic compounds containing carbon, nitrogen, phosphorus, sulfur and the like. Typically a portion of the waste is consumed to further the metabolism of the bacterial cells or to maintain the physiological functioning of the bacterial cells. In addition, a portion of the waste is also consumed as part of the process of the synthesis of new bacterial cells.
  • Some wastewaters such as those from the dyeing, chemical and pharmaceutical production facilities often cannot meet discharge standards after normal bio-treatment processes.
  • Organic compounds bring problems in industrial wastewater and the mixtures in the liquid include different contaminants and chroma or color in the wastewater. This can create difficulties in treating the wastewater.
  • ozone can be employed to treat wastewater and ozone oxidation in wastewater faces three different challenges in its treatment. The first is to transform poisonous compounds present in the wastewater; the second is to partially oxidize components in COD for biological compounds and lastly elimination of chroma.
  • Traces of ozone can be introduced too into the activated sludge system to control the amount of the activated sludge present in the wastewater treatment system.
  • Ozone destruction units can be catalytic, thermal, thermo-catalytic or activated carbon.
  • the catalytic units use either manganese dioxide or aluminum coated with palladium and destroy ozone at temperatures around 50°C.
  • Thermal destructive units typically operate at temperatures around 120°C.
  • the invention is able to overcome some of the limitations of earlier wastewater treatment methods.
  • the invention uses impregnated catalysts on ACFC (activated carbon fiber clothes) and activated AI 2 O 3 to decompose residual ozone in an ozone treatment of wastewater system.
  • the invention provides for a method of treating wastewater comprising the steps: a) Feeding wastewater to a bio-treatment reactor; b) Feeding oxygen to the bio-treatment reactor; c) Feeding the mixture of wastewater and oxygen to an ozone treatment reactor wherein ozone is fed to said mixture; d) Withdrawing the treated wastewater; and e) Recovering tail gas which contains unreacted ozone by feeding said tail gas which contains unreacted ozone to a reactor, wherein said ozone is decomposed and converted to oxygen.
  • the wastewater to be treated is typically wastewater from the dyeing, chemical or pharmaceutical production industries and will contain color and organic compounds that will need to be removed before the wastewater can be discharged into the environment or re-used in an industrial process.
  • the source of oxygen is selected from the group consisting of liquid oxygen, gaseous oxygen, air, and other oxygen-containing sources and is typically fed to the bio-treatment reactor as a liquid where it is vaporized before entering the bio-treatment reactor.
  • the wastewater is fed to the bio- treatment reactor from a separate source from the oxygen feed.
  • the ozone will be fed to the ozone treatment reactor in an amount up to about 8 to12% ozone by volume in oxygen.
  • the ozone will typically be from a source such as an ozone generator, and when fed to the ozone treatment reactor will react with the contaminants causing color and the organic compounds present in the wastewater being treated.
  • the tail gas which contains unreacted ozone (about 1 % by volume) from the ozone treatment reactor will be fed to the ozone destruction unit where a catalyst reactor is present.
  • the catalyst in said reactor is a catalyst material impregnated onto an ACFC (activated carbon fiber clothes) or other type of inert support materials such as activated Al 2 0 3 .
  • the catalyst material is typically selected from the group consisting of manganese dioxide, nickel and aluminum coated with palladium.
  • the catalyst will typically be fixed onto the support materials by a method selected from the group consisting of impregnation and cationic exchange.
  • the ozone treatment reactor will destroy the unreacted ozone in the tail gas after treatment of the wastewater.
  • One by-product of the reaction is the generation of oxygen which is captured and can be fed back to the bio- treatment reactor for use in treating the wastewater.
  • a method of treating ozone wherein wastewater and oxygen are fed to a bio-treatment reactor comprising the steps: a) Feeding the mixture of wastewater and oxygen to an ozone treatment reactor and feeding ozone into said mixture; b) Withdrawing the wastewater; and c) Recovering unreacted ozone in the tail gas and feeding the unreacted ozone to a reactor wherein said unreacted ozone is converted to oxygen.
  • the figure is a schematic of a wastewater treatment systems with ozone and oxygen recycle.
  • Liquid oxygen or another source of oxygen selected from the group consisting of gaseous oxygen, air and other oxygen- containing source from oxygen tank A passes through a vaporizer and a pressure regulation valve and is injected into the bio-treatment reactor B. This injection will typically be through a diffusion system under a particular pressure suitable for the bio-treatment reactor B.
  • the effluent from the bio- treatment reactor B will need to be further treated using ozone and is passed through line 4 to the ozone treatment reactor C.
  • Oxygen from the oxygen tank A is fed though line 3 to the ozone generator D which will produce ozone in amounts up to 8 to 12% by volume ozone in oxygen. This ozone is fed through line 8 to the ozone treatment reactor C.
  • the treated wastewater stream will exit the ozone treatment reactor C through line 5 where it can be returned or reused as being suitable for various purposes.
  • the tail gas stream will exit the ozone treatment reactor C through line 6 and is fed to the ozone destruction unit E where the
  • reactor is mounted. Typically this is a fixed-bed reactor packed with catalyst material impregnated onto an ACFC (activated carbon fiber clothes) or other inert support materials such as activated AI 2 O 3 .
  • ACFC activated carbon fiber clothes
  • the activated carbon fiber cloth is a higher efficiency adsorbent and catalyst support. It typically has high adsorption capacity and high mass transfer rate for both adsorption and desorption; has a large specific surface area and special pore structure consisting of micropores having diameters less than 2 nanometers, and a short diffusion path for adsorbents. Activated carbon fiber cloth is also advantageous as it can have the form of a felt, sheet or honeycomb.
  • the catalyst material is typically manganese dioxide or titanium dioxide or activated aluminum coated with palladium; however, other catalyst materials such as Fe 2 O 3 , NiO 2 , Co 2 O 3 , Mn0 2 may also be employed.
  • the catalyst is fixed on the ACFC or other support materials with pellets by impregnation or by cationic exchange.
  • the activated carbon fiber has pores with a mean size in the range of 0.3 nanometers to 3 nanometers; carbon content greater than 99% and a high density of functional groups per unit area which favors the dispersion of metal catalyst in the form of fine particles and which is good for highly selective catalytic reactions.
  • the ozone will be catalyzed forming oxygen in the reactor bed inside of the ozone destruction unit E.
  • the oxygen along with the oxygen in the tail gas can be captured and fed through line 7 to the bio-treatment reactor B where it can be employed in treating the wastewater.
  • Example 1 Catalyst that can be employed in destroying ozone comprises titanium dioxide impregnated onto ACFC.
  • the ACFC from the Anshan ACF plant had a specific surface area of 1230 m 2 /g and a micropore volume of 0.62 ml/g.
  • the ACFC was impregnated in 0.5 mol Ti(Ac) solution and dried at 250°C in 3 cycles in an atmosphere of nitrogen.
  • the diameter of the activated carbon bed was 50 mm and its length was 500 mm.
  • the reaction temperature was controlled by a constant temperature bath.
  • the glass-made fixed bed reactor had an inner diameter of 5 cm with effective length 50 cm for packing with catalysts, the outer layer surrounding electric heating belts. Two thermal couples were inserted in the inlet and outlet position of the reactor.
  • the conditions of the feed stream were: the oxygen to the ozone generator was 2.5 SCFH with a pressure of 1 .035 atm (0.06845 m 3 /hr); the ozone concentration was 22.4mg/L.
  • the flow rate of nitrogen for dilution was 12 standard cubic feed per hour (SCFH) with pressure of 1 .035 atm (0.3334 m 3 /hr).
  • SCFH standard cubic feed per hour
  • the concentration of ozone at the outlet was measured over time.
  • Example 2 Catalyst that can be employed in destroying ozone
  • the activated Al 2 0 3 was from Shanghai Huanqiu Molecular Sieve Plant.
  • the activated Al 2 0 3 was impregnated in 0.5 mol Ti(Ac) solution and dried at 250°C in 3 cycles.
  • the catalyst bed, packed with impregnated Ti0 2 catalyst on activated Al 2 0 3 passes 1 to 5% ozone and detects the ozone concentration in the effluent gas stream.
  • the reaction temperature was controlled by a constant temperature bath.
  • Example 2 The experimental conditions are the same as for Example 1 except the support was changed from ACFC to activated Al 2 0 3 . After continuously running for two weeks, we found that this type of catalyst is stable and suitable for decomposing ozone.
  • Example 3 Catalyst that can be employed in destroying ozone
  • Example 2 The experimental conditions were the same as Example 2 except the gas stream was saturated with water at 20° C. The experimental results showed that the catalysts had no activity unless we heated the fixed-bed reactor to over 60° C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)

Abstract

Provided is a method for treating wastewater, which comprises the following steps: separately feeding the wastewater and oxygen to a bio-treatment reactor (B), then feeding the mixture to an ozone treatment reactor (C), withdrawing the treated wastewater and recovering the tail gas which contains untreated ozone by feeding it to an ozone destruction unit (E), wherein the untreated ozone is decomposed and converted to oxygen by a suitable catalyst material.

Description

OZONE TREATMENT OF WASTEWATER
BACKGROUND OF THE INVENTION
[0001] Traditional methods of wastewater treatment involve bringing wastewater streams into contact with bacteria, either in an aerobic or an anaerobic type process. This is typically referred to as an activated sludge treatment. The bacteria consume parts of the substrate material or the waste contained in the wastewater which are typically organic compounds containing carbon, nitrogen, phosphorus, sulfur and the like. Typically a portion of the waste is consumed to further the metabolism of the bacterial cells or to maintain the physiological functioning of the bacterial cells. In addition, a portion of the waste is also consumed as part of the process of the synthesis of new bacterial cells.
[0002] Some wastewaters, such as those from the dyeing, chemical and pharmaceutical production facilities often cannot meet discharge standards after normal bio-treatment processes. Organic compounds bring problems in industrial wastewater and the mixtures in the liquid include different contaminants and chroma or color in the wastewater. This can create difficulties in treating the wastewater. However, ozone can be employed to treat wastewater and ozone oxidation in wastewater faces three different challenges in its treatment. The first is to transform poisonous compounds present in the wastewater; the second is to partially oxidize components in COD for biological compounds and lastly elimination of chroma.
[0003] All residual gases from the ozone reactor must be subjected to an ozone destruction procedure before they are emitted into the atmosphere due to the corrosive and potentially poisonous nature of ozone. Regulations in the United States require that the concentration of ozone be below 0.1 parts per million before it can be released into the atmosphere. Furthermore, pure oxygen ozone generators are often used. The off-gas from these generators contains enriched oxygen with traces of ozone. The off-gas is useful if it is reasonable and commercially practicable to recycle the oxygen by
decomposing ozone. Traces of ozone can be introduced too into the activated sludge system to control the amount of the activated sludge present in the wastewater treatment system.
[0004] Ozone destruction units can be catalytic, thermal, thermo-catalytic or activated carbon. The catalytic units use either manganese dioxide or aluminum coated with palladium and destroy ozone at temperatures around 50°C. Thermal destructive units typically operate at temperatures around 120°C.
[0005] The invention is able to overcome some of the limitations of earlier wastewater treatment methods. The invention uses impregnated catalysts on ACFC (activated carbon fiber clothes) and activated AI2O3 to decompose residual ozone in an ozone treatment of wastewater system.
SUMMARY OF THE INVENTION
[0006] The invention provides for a method of treating wastewater comprising the steps: a) Feeding wastewater to a bio-treatment reactor; b) Feeding oxygen to the bio-treatment reactor; c) Feeding the mixture of wastewater and oxygen to an ozone treatment reactor wherein ozone is fed to said mixture; d) Withdrawing the treated wastewater; and e) Recovering tail gas which contains unreacted ozone by feeding said tail gas which contains unreacted ozone to a reactor, wherein said ozone is decomposed and converted to oxygen.
[0007] The wastewater to be treated is typically wastewater from the dyeing, chemical or pharmaceutical production industries and will contain color and organic compounds that will need to be removed before the wastewater can be discharged into the environment or re-used in an industrial process.
[0008] The source of oxygen is selected from the group consisting of liquid oxygen, gaseous oxygen, air, and other oxygen-containing sources and is typically fed to the bio-treatment reactor as a liquid where it is vaporized before entering the bio-treatment reactor. The wastewater is fed to the bio- treatment reactor from a separate source from the oxygen feed.
[0009] The ozone will be fed to the ozone treatment reactor in an amount up to about 8 to12% ozone by volume in oxygen. The ozone will typically be from a source such as an ozone generator, and when fed to the ozone treatment reactor will react with the contaminants causing color and the organic compounds present in the wastewater being treated.
[0010] The tail gas which contains unreacted ozone (about 1 % by volume) from the ozone treatment reactor will be fed to the ozone destruction unit where a catalyst reactor is present. The catalyst in said reactor is a catalyst material impregnated onto an ACFC (activated carbon fiber clothes) or other type of inert support materials such as activated Al203. The catalyst material is typically selected from the group consisting of manganese dioxide, nickel and aluminum coated with palladium. The catalyst will typically be fixed onto the support materials by a method selected from the group consisting of impregnation and cationic exchange.
[0011] The ozone treatment reactor will destroy the unreacted ozone in the tail gas after treatment of the wastewater. One by-product of the reaction is the generation of oxygen which is captured and can be fed back to the bio- treatment reactor for use in treating the wastewater.
[0012] In another embodiment of the invention there is disclosed a method of treating ozone wherein wastewater and oxygen are fed to a bio-treatment reactor comprising the steps: a) Feeding the mixture of wastewater and oxygen to an ozone treatment reactor and feeding ozone into said mixture; b) Withdrawing the wastewater; and c) Recovering unreacted ozone in the tail gas and feeding the unreacted ozone to a reactor wherein said unreacted ozone is converted to oxygen.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The figure is a schematic of a wastewater treatment systems with ozone and oxygen recycle.
DETAILED DESCRIPTION OF THE INVENTION
[0014] Turning to the figure, a wastewater treatment system with ozone and oxygen recycle is presented. Liquid oxygen or another source of oxygen selected from the group consisting of gaseous oxygen, air and other oxygen- containing source from oxygen tank A passes through a vaporizer and a pressure regulation valve and is injected into the bio-treatment reactor B. This injection will typically be through a diffusion system under a particular pressure suitable for the bio-treatment reactor B. The effluent from the bio- treatment reactor B will need to be further treated using ozone and is passed through line 4 to the ozone treatment reactor C. Oxygen from the oxygen tank A is fed though line 3 to the ozone generator D which will produce ozone in amounts up to 8 to 12% by volume ozone in oxygen. This ozone is fed through line 8 to the ozone treatment reactor C.
[0015] The treated wastewater stream will exit the ozone treatment reactor C through line 5 where it can be returned or reused as being suitable for various purposes. The tail gas stream will exit the ozone treatment reactor C through line 6 and is fed to the ozone destruction unit E where the
appropriate reactor is mounted. Typically this is a fixed-bed reactor packed with catalyst material impregnated onto an ACFC (activated carbon fiber clothes) or other inert support materials such as activated AI2O3.
[0016] The activated carbon fiber cloth is a higher efficiency adsorbent and catalyst support. It typically has high adsorption capacity and high mass transfer rate for both adsorption and desorption; has a large specific surface area and special pore structure consisting of micropores having diameters less than 2 nanometers, and a short diffusion path for adsorbents. Activated carbon fiber cloth is also advantageous as it can have the form of a felt, sheet or honeycomb.
[0017] The catalyst material is typically manganese dioxide or titanium dioxide or activated aluminum coated with palladium; however, other catalyst materials such as Fe2O3, NiO2, Co2O3, Mn02 may also be employed. The catalyst is fixed on the ACFC or other support materials with pellets by impregnation or by cationic exchange. The activated carbon fiber has pores with a mean size in the range of 0.3 nanometers to 3 nanometers; carbon content greater than 99% and a high density of functional groups per unit area which favors the dispersion of metal catalyst in the form of fine particles and which is good for highly selective catalytic reactions.
[0018] The ozone will be catalyzed forming oxygen in the reactor bed inside of the ozone destruction unit E. The oxygen along with the oxygen in the tail gas can be captured and fed through line 7 to the bio-treatment reactor B where it can be employed in treating the wastewater.
Example 1 : Catalyst that can be employed in destroying ozone comprises titanium dioxide impregnated onto ACFC.
[0019] The ACFC from the Anshan ACF plant had a specific surface area of 1230 m2/g and a micropore volume of 0.62 ml/g. The ACFC was impregnated in 0.5 mol Ti(Ac) solution and dried at 250°C in 3 cycles in an atmosphere of nitrogen. The diameter of the activated carbon bed was 50 mm and its length was 500 mm. The catalyst bed, packed with impregnated Ti02 catalyst on ACFC, passes about 1 to 5% ozone and detects the ozone concentration in the effluent gas stream. The reaction temperature was controlled by a constant temperature bath.
[0020] The glass-made fixed bed reactor had an inner diameter of 5 cm with effective length 50 cm for packing with catalysts, the outer layer surrounding electric heating belts. Two thermal couples were inserted in the inlet and outlet position of the reactor.
[0021] The conditions of the feed stream were: the oxygen to the ozone generator was 2.5 SCFH with a pressure of 1 .035 atm (0.06845 m3/hr); the ozone concentration was 22.4mg/L. The flow rate of nitrogen for dilution was 12 standard cubic feed per hour (SCFH) with pressure of 1 .035 atm (0.3334 m3/hr). Thus the total ozone concentration fed to the catalyst reactor was 0.01987 m3/hr (4.9%). The concentration of ozone at the outlet was measured over time.
[0022] The experimental results showed that the temperature at the outlet of the reactor increased from room temperature (20° C) to 77° C and the color of the ACFC changed from black to grey at the outer surface of the ACFC after running 8 hours. By testing, it was found that carbon from ACFC reacts with ozone to form carbon dioxide.
Example 2: Catalyst that can be employed in destroying ozone
comprises titanium dioxide impregnated onto activated Al203 with 3 mm average diameter.
[0023] The activated Al203 was from Shanghai Huanqiu Molecular Sieve Plant. The activated Al203 was impregnated in 0.5 mol Ti(Ac) solution and dried at 250°C in 3 cycles. The catalyst bed, packed with impregnated Ti02 catalyst on activated Al203, passes 1 to 5% ozone and detects the ozone concentration in the effluent gas stream. The reaction temperature was controlled by a constant temperature bath.
[0024] The experimental conditions are the same as for Example 1 except the support was changed from ACFC to activated Al203. After continuously running for two weeks, we found that this type of catalyst is stable and suitable for decomposing ozone.
Example 3: Catalyst that can be employed in destroying ozone
comprises titanium dioxide impregnated onto activated Al203 with 3 mm averaged diameter with the stream containing steam
[0025] The experimental conditions were the same as Example 2 except the gas stream was saturated with water at 20° C. The experimental results showed that the catalysts had no activity unless we heated the fixed-bed reactor to over 60° C.
[0026] While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of the invention will be obvious to those skilled in the art. The appended claims in this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the invention.

Claims

Having thus described the invention, what we claim is:
1 . A method of treating wastewater comprising the steps: a) feeding wastewater to a bio-treatment reactor; b) feeding oxygen to the bio-treatment reactor; c) feeding the mixture of wastewater and oxygen to an ozone treatment reactor wherein ozone is fed to said mixture; d) withdrawing the treated wastewater; and e) recovering tail gas which contains unreacted ozone by feeding said tail gas which contains unreacted ozone to a reactor, wherein said ozone is decomposed and converted to oxygen.
2. The method as claimed in claim 1 wherein said wastewater contains color and organic compounds.
3. The method as claimed in claim 1 wherein said wastewater and said oxygen are separately fed to said bio-treatment reactor.
4. The method as claimed in claim 1 wherein ozone is fed up to 8 to 12% by volume ozone in oxygen.
5. The method as claimed in claim 1 wherein said ozone reacts with said color and organic compounds.
6. The method as claimed in claim 1 wherein said oxygen is selected from the group consisting of liquid oxygen, gaseous oxygen, air, and other oxygen-containing sources.
7. The method as claimed in claim 1 wherein said converted oxygen is fed to said bio-treatment reactor.
8. The method as claimed in claim 1 wherein said wastewater is wastewater selected from the group consisting of dyeing, chemical and pharmaceutical production facilities.
9. The method as claimed in claim 1 wherein said reactor contains a catalyst.
10. The method as claimed in claim 9 wherein said catalyst is selected from the group consisting of a catalyst material fixed onto an activated carbon fiber clothes and a catalyst material fixed onto activated Al203.
1 1 . The method as claimed in claim 10 wherein said catalyst is selected from the group consisting of manganese dioxide, titanium dioxide, nickel and aluminum coated with palladium.
12. The method as claimed in claim 1 1 wherein said catalyst is fixed onto the activated carbon fiber clothes and activated Al203 by a method selected from the group consisting of impregnation and cationic exchange.
13. A method of treating ozone wherein wastewater and oxygen are fed to a bio-treatment reactor comprising the steps: a) feeding the mixture of wastewater and oxygen to an ozone treatment reactor and feeding ozone into said mixture; b) withdrawing the wastewater; and c) recovering tail gas which contains unreacted ozone and feeding the tail gas containing unreacted ozone to a reactor wherein said unreacted ozone is converted to oxygen.
14. The method as claimed in claim 13 wherein said wastewater contains color and organic compounds.
15. The method as claimed in claim 13 wherein said wastewater and said oxygen are separately fed to said bio-treatment reactor.
16. The method as claimed in claim 13 wherein ozone is fed up to 8 to 12% by volume ozone in oxygen.
17. The method as claimed in claim 13 wherein said ozone reacts with said color and organic compounds.
18. The method as claimed in claim 13 wherein said oxygen is selected from the group consisting of liquid oxygen, gaseous oxygen, air, and other oxygen-containing sources.
19. The method as claimed in claim 13 wherein said converted oxygen is fed to said bio-treatment reactor.
20. The method as claimed in claim 13 wherein said wastewater is wastewater selected from the group consisting of dyeing, chemical and pharmaceutical production facilities.
21 . The method as claimed in claim 13 wherein said reactor contains a catalyst.
22. The method as claimed in claim 21 wherein said catalyst is selected from the group consisting of a catalyst material fixed onto an activated carbon fiber clothes and a catalyst material fixed onto activated Al203.
23. The method as claimed in claim 21 wherein said catalyst is selected from the group consisting of manganese dioxide, titanium dioxide, nickel and aluminum coated with palladium.
24. The method as claimed in claim 23 wherein said catalyst is fixed on the activated carbon fiber clothes and activated Al203 by a method selected from the group consisting of impregnation and cationic exchange.
PCT/CN2011/076464 2011-06-28 2011-06-28 Ozone treatment of wastewater WO2013000115A1 (en)

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CN107010783A (en) * 2017-04-20 2017-08-04 佛山市佳利达环保科技股份有限公司 A kind of processing method of sewage foul smell
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IT202100017066A1 (en) 2021-06-29 2022-12-29 Soc It Acetilene E Derivati S I A D S P A In Breve S I A D S P A WASTEWATER TREATMENT PLANT WITH REDUCTION OF HARMFUL OUTFLOWS THROUGH INTEGRATION AND RECOVERY OF GAS FLOWS RICH IN OXYGEN AND OZONE WITH LOW ENERGY CONSUMPTION SYSTEMS
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CN114314802A (en) * 2021-12-17 2022-04-12 安道麦股份有限公司 Treatment device and method for organophosphorus wastewater from production of acephate
CN114314802B (en) * 2021-12-17 2023-12-19 安道麦股份有限公司 Device and method for treating organophosphorus wastewater from production of acephate

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