EP0859746A1 - Oxydation poussee de l'eau par ozonisation catalytique - Google Patents

Oxydation poussee de l'eau par ozonisation catalytique

Info

Publication number
EP0859746A1
EP0859746A1 EP96935002A EP96935002A EP0859746A1 EP 0859746 A1 EP0859746 A1 EP 0859746A1 EP 96935002 A EP96935002 A EP 96935002A EP 96935002 A EP96935002 A EP 96935002A EP 0859746 A1 EP0859746 A1 EP 0859746A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
ozone
water
contaminants
waste water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP96935002A
Other languages
German (de)
English (en)
Inventor
Peter Barratt
Feng Xiong
John Nelson Armor
Vincent Louis Magnotta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Products and Chemicals Inc
Original Assignee
Air Products and Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Products and Chemicals Inc filed Critical Air Products and Chemicals Inc
Publication of EP0859746A1 publication Critical patent/EP0859746A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—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
    • 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

Definitions

  • the present invention relates to the treatment of surface water or aqueous effluent to remove organic impurities therefrom.
  • COD Chemical Oxygen Demand
  • BOD Bio Oxygen Demand
  • hard COD the amount of oxygen required to oxidize the non-biodegradable contaminants
  • catalysts have been used in the Zimmerman process . These catalysts include noble or heavy metals such as palladium, platinum, cobalt or iron deposited on a carrier of, for example, alumina, silica-alumina, silica gel, activated carbon, titania or zirconia (see JP-A-49- 44556 (1974) ; JP-A-49-94157 (1974) ; and JP-A-58-64188 (1983) ) .
  • alumina silica-alumina, silica gel, activated carbon, titania or zirconia
  • Ozone is the strongest molecular oxidant for water treatment and it has been used since the beginning of this century in drinking water treatment to provide disinfection, removal of colour, taste and odour, and destruction of organic compounds.
  • ozone is very selective in its reactions; it predominantly reacts with compounds containing unsaturated bonds such as olefins, aromatic compounds and/or compounds containing electron rich groups such as sulfur and nitrogen.
  • unsaturated bonds such as olefins, aromatic compounds and/or compounds containing electron rich groups such as sulfur and nitrogen.
  • saturated alkanes and chlorinated organics most of pesticides and priority pollutants
  • these ozone refractory contaminants can be oxidized by hydroxyl radicals which are usually formed by activating ozone with hydrogen peroxide or ultraviolet light ("advanced oxidation”) .
  • Hydrogen peroxide has an operation cost higher than ozone and ultraviolet light requires capital and operational costs at least equal to that of ozone generation. Accordingly, the activation of ozone to hydroxyl radicals by these two methods results in a large increase (50 - 200%) in the cost of water treatment. Moreover, since hydroxyl radical reactions are much less specific than those involving ozone alone, the hydroxyl radicals generated in solution by hydrogen peroxide or ultraviolet light activation of ozone can be wasted by reaction with non-target inhibitors or scavengers, such as carbonate and bicarbonate ions, which do not require oxidation. Thus, a more cost effective method of ozone activation is needed.
  • PL-A-56775 (1969) reported that ozone-containing gas had been used in a continuous oxidation process to purify waste water from coke ovens but that the treatment was uneconomic for industrial use. It was proposed in PL-A- 56775 that the waste water should be continuously treated with ozone-containing gas in a froth phase by blowing the gas countercurrent to the waste water in a scrubber packed with Rashig rings, slag and/or oxides of silver, copper, aluminium, zinc, magnesium, tin, lead, iron, or manganese as catalysts.
  • US-A-4007118 (1977) discloses the ozonation of waste water using a transition metal catalyst, such as manganese trioxide, ferric oxide, copper oxide or nickel oxide, which is present as a powder contained in fabric bags, disposed on a substrate or dispersed within the waste water
  • US-A-4040982 (1977) discloses a method of removing contaminants from waste water by treatment with ozone- containing gas in the presence of a catalyst comprising ferric oxide supported on catalytically active alumina and having a surface area of 150 to 450 m 2 /g and a pore volume of at least 0.3 cm 3 .
  • the exemplified alumina is gamma alumina but reference is made to eta alumina, amorphous alumina and activated alumina.
  • JP-A-58-37039 (1983) discloses a method of removal of an aromatic organic compound from waste water by mixing first with a surfactant, then with a transition metal or alkaline earth metal compound, and contacting the resultant mixture with ozone-containing gas to oxidatively decompose the organic compound.
  • NL-A-9001721 (1991) discloses the treatment of iron- containing waste water by forming and removing precipitated Fe(III) by mixing with hydrogen peroxide,- then forming and removing precipitated carbonate by adding, for example, calcium hydroxide, calcium chloride and/or alkali metal hydroxide; and subsequently oxidation with, for example, ozone-containing gas alone or with a solid catalyst, to remove residual organic compounds.
  • Specified catalysts are activated carbon, alumina or silica. It is stated that the catalyst must have a surface area of at least 50 m 2 /g and a pore volume cf greater than C.l cm 3 /g and that its activity can be improved by addition of a transition metal such as copper, iron, molybdenum or cobalt.
  • ozone-containing gas is passed through a bubble reactor countercurrently to liquid effluent from a catalyst bed and the gas exiting the bubble reactor is passed through that catalyst bed cocurrently with the partially treated waste water. If required, additional ozone- containing gas can be added to supplement the ozone content of the gas exiting the bubble reactor.
  • US-A-5, 145,587 (1992) discloses the treatment of waste water by wet oxidation with a molecular oxygen-containing gas in the presence of a solid catalyst comprising (i) titanium dioxide; (ii) an oxide of a lanthanide element; and (iii) at least one metal selected from manganese, iron, cobalt, nickel, tungsten, copper, silver, gold, platinum, palladium, rhodium, ruthenium and iridium or a water insoluble or sparingly soluble compound thereof.
  • the catalyst is formed by adding component (iii) to a calcined mixture of (i) and (ii) and preferably is in the form of an integral or monolithical structure, such as an extruded honeycomb (having straight through channels) , of (i) and (ii) impregnated with (iii) .
  • the preferred oxidants are oxygen, ozone, hydrogen peroxide or mixtures of oxygen with ozone or hydrogen peroxide.
  • US-A-5352369 (1994) discloses a method of treating water to kill bacteria therein by contact with a silver catalyst in the presence of oxygen to form an active oxidizer in the water.
  • the silver catalyst is formed by depositing elemental silver on an alumina matrix and heating to a temperature of at least 300°C.
  • ozone-containing gas is used as the source of oxygen but it is required that the water be exposed to the silver catalyst as soon as the ozone- containing gas has been added to the water.
  • a process for the removal of contaminants from water which comprises contacting the water with ozone in the absence of a catalyst to oxidize ozone-oxidizable contaminants and to dissolve ozone in the water, and contacting the resultant ozone-containing water with a solid ozone activation catalyst to oxidize ozone refractory contaminants in the water.
  • the process of the invention permits the use of some relatively inexpensive solid catalysts which are widely used in the chemical industry for chemical synthesis.
  • the waste water first reacts with ozone in a gas-liquid contactor and the easily oxidisable contaminants are removed.
  • the thus treated waste water (free from gas bubbles but with residual dissolved ozone) passes through the ozone activation catalyst where the residual ozone is activated to secondary oxidants more reactive than ozone and which decompose contaminants remaining after treatment in the gas-liquid contactor.
  • the effluent from the catalyst treatment can be re-injected to the gas-liquid contactor to absorb more ozone for reaction if the concentration of contaminants is too high to reduce in a single pass through the catalyst (i.e. the oxidant demand of the waste water is higher than the maximum ozone solubility in water under the operational conditions) .
  • the waste water treated by the process of the invention usually will have a COD of at most 5000 mg/l.
  • the extent of the advanced oxidation by the process will be determined mainly by environmental requirements, which presently require the COD of waste water to be reduce to at most 125 mg/l before discharge.
  • the use of a two phase catalysis (liquid/solid) instead of the conventional three phases (gas/liquid/solid) used in prior art advanced oxidation catalysis improves the reaction rate and reduces catalyst erosion.
  • the ozone-containing gas will be an ozone/oxygen or ozone/air mixture but pure ozone or ozone in admixture with any inert carrier gas can be used.
  • the catalyst can be in any solid form but usually will be in the form of granules, pellets or an integral or monolithic structure especially having a three dimensional continous pore phase.
  • the catalyst will be monolithic having a low surface area ( ⁇ 20 m 2 /g) and/or high porosity ( ⁇ 5 pores per linear inch,- ⁇ 2 pores per cm) . It is especially preferred that the catalyst is in the form of foamed monolithic structure with high porosity and low pressure drop ( ⁇ 0.1 bar g; ⁇ 10 kPa in a cylindrical reactor of 1000 mm high and 24 mm ID at a water flow rate of 7 litre/min) .
  • the catalyst can be any of those conventionally employed in advanced oxidation catalysis of water.
  • it can be a transition metal oxide, such as cobalt oxide, copper oxide, ferric oxide, manganese trioxide or nickel oxide, optionally on a carrier of, for example, alumina, silica-alumina, silica gel, activated carbon, titania or zirconia.
  • the catalyst preferably is a gamma-alumina catalyst, especially undoped gamma alumina optionally on a carrier, especially alpha alumina.
  • Figure 1 is a graph of percentage COD removal (ordinate) against ozone consumed (abscissa) for a process of the invention using a gamma alumina catalyst (Catalyst C3 ,- see Example 1 infra) and for a conventional (0 3 /UV) advanced oxidation process
  • Figure 2 is a graph of percentage COD removal (ordinate) against ozone consumed (abscissa) for a process of the invention using a monolithic catalyst of gamma alumina on an alpha alumina carrier (see Example 2 infra) and for a conventional (0 3 /UV) advanced oxidation process,-
  • Figure 3 is a diagrammatic representation of apparatus for the removal of organic contaminants from high strength waste water using a process of the present invention,- and
  • Figure 4 is a diagrammatic representation of apparatus for the removal of organic contaminants from low strength waste water using a process of the present invention.
  • a stream (1) of waste water which has been treated by conventional microbiological or chemical processes to reduce the COD to 5000 mg/l or less is mixed with a recycle stream (2) of water containing dissolved ozone.
  • the resultant mixed stream (3) is pumped (4) upwardly through a fixed catalyst bed (5) and the bed effluent (6) is passed to a gas-liquid contactor (7) in which it is thoroughly mixed with an ozone-containing gas (8) from an ozone generator (not shown) .
  • the bulk of the ozonated water is removed in recycle stream (2) but a smaller portion is removed (9) for discharge or further treatment. Undissolved gas is removed in a gaseous discharge stream (10) for reuse and/or return to the ozone generator.
  • the process of Figure 4 differs from that of Figure 3 in that the waste water stream (1) is pumped (14) to the gas-liquid contactor (17) where it is mixed with ozone- containing gas (8) . All of the ozonated waste water from the gas-liquid contactor (17) is passed upwardly through the catalyst bed (5) . In this process, the spent ozone containing gas is removed (10) from the gas-liquid contactor (17) but the treated waste water discharge (19) is from the catalvst bed (5) .
  • the combination of ozone with Catalyst C3 offers advantages over the current 0 3 /UV advanced oxidation process in the destruction of COD as indicated by the comparative results in Figure 1.
  • the removal of COD was much higher with the Catalyst C3 catalytic ozonation than the 0 3 /UV process at the same ozone dosages.
  • the ozone required for the same degree of COD removal by the Catalyst C3 catalytic ozonation is less than 50% of that by the 0 3 /UV process, representing a significant reduction in treatment cost.
  • Catalyst C3 maintained its catalytic activity after 100 hours operation. Municipal secondary effluent, landfill leachate, and waste water from a hospital sewer were all satisfactorily treated using this catalyst.
  • Example 1 The procedure of Example 1 was repeated using, as catalyst, a foamed monolithic material of 92% alpha alumina (low surface area) and coated with 5% gamma alumina (RETICEL TM HPA washcoat reticulated ceramic) sold as a filter media.
  • the base material has a pore density of 10 pores per linear inch (4 pores per cm) and a calculated surface area of 2290 m 2 /m 3 ( ⁇ 5xl0 "3 ⁇ r/g) .
  • the 5% washcoat increases the surface area to 15 m 2 /g.
  • This material achieved similar COD removal rate as the 0 3 /UV process with little back-pressure (see Figure 2 ) .
  • a pressure drop of 0.02 bar g (2 kPa) was recorded at a water flow rate of 7 litre/min compared with 0.8 bar g (80 kPa) for Catalyst 3 (in granular form) under the same conditions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

On supprime des contaminants des eaux usées (1) au moyen d'un procédé d'oxydation poussée, qui consiste à mettre ces eaux usées en contact (7) avec de l'ozone (8), en l'absence d'un catalyseur, afin que les contaminants pouvant être oxydés à l'ozone s'oxydent et que l'ozone se dissolve dans l'eau, puis à mettre l'eau obtenue contenant de l'ozone (3) en contact avec un catalyseur solide (5) d'activation d'ozone, afin que les contaminants réfractaires à l'ozone contenus dans l'eau s'oxydent. On peut mettre en contact avec de l'ozone (7) l'effluent (6) provenant du traitement catalytique (5) et le recycler (2) dans le but de le remettre en contact avec le catalyseur (5). Le catalyseur préféré est une structure monolithique non dopée constituée d'alumine gamma, présentant une faible surface, une porosité élevée et une faible chute de pression.
EP96935002A 1995-10-17 1996-10-16 Oxydation poussee de l'eau par ozonisation catalytique Ceased EP0859746A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9521359.1A GB9521359D0 (en) 1995-10-17 1995-10-17 Advanced oxidation of water using catalytic ozonation
GB9521359 1995-10-17
PCT/GB1996/002525 WO1997014657A1 (fr) 1995-10-17 1996-10-16 Oxydation poussee de l'eau par ozonisation catalytique

Publications (1)

Publication Number Publication Date
EP0859746A1 true EP0859746A1 (fr) 1998-08-26

Family

ID=10782519

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96935002A Ceased EP0859746A1 (fr) 1995-10-17 1996-10-16 Oxydation poussee de l'eau par ozonisation catalytique

Country Status (5)

Country Link
EP (1) EP0859746A1 (fr)
CA (1) CA2231193A1 (fr)
GB (1) GB9521359D0 (fr)
TW (1) TW414783B (fr)
WO (1) WO1997014657A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6780223B2 (en) 2001-09-14 2004-08-24 Industrial Technology Research Institute Method and apparatus for treating an exhaust gas containing volatile organic compounds
CN105712466A (zh) * 2014-12-01 2016-06-29 抚顺环科石油化工技术开发有限公司 一种含酚废水的臭氧催化湿式氧化方法
CN110639491A (zh) * 2018-06-26 2020-01-03 宁波市雨辰环保科技有限公司 一种用于剧毒废水无害化处理的催化剂及其制备方法和应用

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69815787D1 (de) * 1997-10-21 2003-07-31 Karsten Pedersen Silkeborg Katalytisches Verfahren zur Beseitigung von organischen Schadstoffe in Gewässer
US6129849A (en) * 1998-10-23 2000-10-10 Kansai Electric Power Co., Inc. Process for accelerating reaction of ozone with AM catalyst
US8808550B2 (en) 2010-03-18 2014-08-19 Air Products And Chemicals, Inc. Apparatus and method for dissolution of ozone in water and catalytic oxidation
US8871098B2 (en) 2011-09-22 2014-10-28 Air Products And Chemicals, Inc. Gas dispersion apparatus for improved gas-liquid mass transfer
CN104986848A (zh) * 2015-07-24 2015-10-21 天津万峰环保科技有限公司 一种电磁(em)高级催化氧化污水深度处理工艺
CA3005075A1 (fr) * 2015-12-07 2017-06-15 The University Of North Carolina At Charlotte Dispositifs, systemes et procedes destines au trempage catalytique heterogene de peroxyde d'hydrogene dans une source d'eau
US11084744B2 (en) 2018-03-28 2021-08-10 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Method for mixing gas-free liquid oxidant with process liquid
US10858271B2 (en) 2018-03-28 2020-12-08 L'Air Liquide, SociétéAnonyme pour l'Etude et l'Exploitation des Procédés Claude Methods for producing high-concentration of dissolved ozone in liquid media
US11434153B2 (en) 2018-03-28 2022-09-06 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés George Claude Separation of ozone oxidation in liquid media into three unit operations for process optimization
CN111646561A (zh) * 2020-06-13 2020-09-11 深圳市创飞格环保技术有限公司 一种污水处理的臭氧催化氧化反应器及污水循环处理方法
CN111792751A (zh) * 2020-06-18 2020-10-20 神马实业股份有限公司 一种己内酰胺生产废水的处理方法
CN112569946A (zh) * 2020-12-28 2021-03-30 广西柳钢环保股份有限公司 一种有机废水处理臭氧催化剂及其制备方法
CN112919616A (zh) * 2021-02-18 2021-06-08 科盛环保科技股份有限公司 一种深度处理化工园污水尾水的高效臭氧催化氧化反应器
CN113289614B (zh) * 2021-06-03 2023-03-17 上海庞科环境技术有限公司 一种用于抗生素废水的三维氧化铝涂层臭氧催化剂的制备方法
CN113184975A (zh) * 2021-06-10 2021-07-30 青岛派尼尔环保技术有限公司 一种臭氧高级催化氧化工艺
GR1010508B (el) * 2022-05-20 2023-07-20 Αριστοτελειο Πανεπιστημιο Θεσσαλονικης-Ειδικος Λογαριασμος Κονδυλιων Ερευνας, Μεθοδος απομακρυνσης μικρορυπων με την εφαρμογη του ετερογενους καταλυτικου οζονισμου απο νερα
CN115228482B (zh) * 2022-08-15 2023-09-12 广州桑尼环保科技有限公司 一种铝泥渣为原料的臭氧催化剂及其制备方法和应用

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FR2655641B1 (fr) * 1989-12-07 1992-04-24 Anjou Rech Procede d'ozonation de l'eau avec activation par catalyse heterogene.
NL9200508A (nl) * 1992-03-19 1993-10-18 E M Engineering F T S B V Werkwijze en inrichting voor het reinigen van water.
JPH06335690A (ja) * 1993-05-31 1994-12-06 Kubota Corp オゾン接触反応槽

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6780223B2 (en) 2001-09-14 2004-08-24 Industrial Technology Research Institute Method and apparatus for treating an exhaust gas containing volatile organic compounds
CN105712466A (zh) * 2014-12-01 2016-06-29 抚顺环科石油化工技术开发有限公司 一种含酚废水的臭氧催化湿式氧化方法
CN105712466B (zh) * 2014-12-01 2018-11-06 大连福瑞普科技有限公司 一种含酚废水的臭氧催化湿式氧化方法
CN110639491A (zh) * 2018-06-26 2020-01-03 宁波市雨辰环保科技有限公司 一种用于剧毒废水无害化处理的催化剂及其制备方法和应用
CN110639491B (zh) * 2018-06-26 2022-09-16 宁波市雨辰环保科技有限公司 一种用于剧毒废水无害化处理的催化剂及其制备方法和应用

Also Published As

Publication number Publication date
GB9521359D0 (en) 1995-12-20
CA2231193A1 (fr) 1997-04-24
WO1997014657A1 (fr) 1997-04-24
TW414783B (en) 2000-12-11

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