WO2010000798A1 - Traitement d'eaux usées - Google Patents

Traitement d'eaux usées Download PDF

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Publication number
WO2010000798A1
WO2010000798A1 PCT/EP2009/058321 EP2009058321W WO2010000798A1 WO 2010000798 A1 WO2010000798 A1 WO 2010000798A1 EP 2009058321 W EP2009058321 W EP 2009058321W WO 2010000798 A1 WO2010000798 A1 WO 2010000798A1
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WIPO (PCT)
Prior art keywords
transition metal
metal catalyst
hydrogen peroxide
industrial waste
aqueous
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PCT/EP2009/058321
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English (en)
Inventor
Johannes Wietse De Boer
Stephen John Flowers
Ronald Hage
Tristan Conway Soh
Alan William Wakeling
Original Assignee
Unilever Plc
Unilever N.V.
Hindustan Unilever Limited
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Publication of WO2010000798A1 publication Critical patent/WO2010000798A1/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
    • C02F1/72—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
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • 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
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • 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
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose 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
    • C02F2103/30—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
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • 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
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Definitions

  • the present invention relates to the catalytic treatment of waste water with hydrogen peroxide.
  • AOP Advanced Oxidation Processes
  • Fenton reactors based on Fe salts and hydrogen peroxide giving rise to hydroxyl radicals that are extremely powerful to destroy any organic matter
  • Disadvantages include low selectivity, and therefore high levels of hydrogen peroxide and iron salts are needed to furnish complete breakdown of the organic matter. This leads then to high chemical costs.
  • UV/H2O2 also generates hydroxyl radicals efficiently and this method is also widely applied. Often large molecules can be then degraded into smaller, biodegradable molecules. Using this technique in conjunction with a biological treatment unit, can be very advantageous. A disadvantage may be in the high electricity costs when a full degradation of the organic waste molecules need to be obtained. Also TiO2/H2O2/UV is sometimes employed to destroy organic matter. Further, high- energy E-beam reactors can be used to generate selected radicals, such as hydroxyl radicals.
  • Ozone dissociates in water to generate hydroxyl radicals. Whilst ozone itself is also reactive, often the benefits are seen upon hydroxyl radical formation. For example direct oxidation of ethers by ozone is slow, the hydroxyl radicals react diffusion limited with substrates. Often mixtures of ozone and hydrogen peroxide are employed to generate hydroxyl radicals efficiently.
  • WO98/39098 discloses that X-bridged macrocycles may be used for the oxidative destruction of waste materials or effluents .
  • the macrocyclic triazacyclic molecules have been known for several decades, and their complexation chemistry with a large variety of metal ions has been studied thoroughly.
  • the azacyclic molecules often lead to complexes with enhanced thermodynamic and kinetic stability with respect to metal ion dissociation, compared to their open-chain analogues.
  • EP 0458397 discloses the use manganese 1, 4, 7-Trimethyl-
  • 1, 4, 7-Trimethyl-l, 4, 7- triazacyclononane (Me 3 -TACN) has been used in dishwashing for automatic dishwashers, SUNTM, and has also been used in a laundry detergent composition, OMO PowerTM.
  • the ligand (Me 3 - TACN) is used in the form of its manganese transition metal complex, the complex having a counter ion that prevents deliquescence of the complex.
  • United States Application 2002/010120 discloses the bleaching of substrates in an aqueous medium, the aqueous medium comprising a transition metal catalyst and hydrogen peroxide .
  • WO 2006/125517 discloses a method of catalytically treating a cellulose or starch substrate with a Mn(III) or Mn(IV) preformed transition metal catalyst salt and hydrogen peroxide in an aqueous solution.
  • the preformed transition metal catalyst salt is described as having a non- coordinating counter ion and having a water solubility of at least 30 g/1 at 20 0 C.
  • Exemplified ligands of the catalysts described in WO 2006/125517 are 1, 4, 7-Trimethyl-l, 4, 7- triazacyclononane (Me 3 ⁇ TACN) and 1, 2, -bis- (4, 7, -dimethyl- 1, 4, 7, -triazacyclonon-1-yl) -ethane (Me 4 -DTNE).
  • EP 0733594 discloses the use of a transition metal catalyst for removing noxious compounds in water or gas.
  • the present invention provides a method of treating aqueous industrial waste comprising the following steps : (i) storing the aqueous industrial waste in a holding vessel, the holding vessel a batch or a continuous vessel; (ii) adding to the aqueous industrial waste in the holding vessel a transition metal catalyst of a tridentate, tetradentate, pentadentate or hexadentate nitrogen donor ligand or precursor thereof and hydrogen peroxide to provide a concentration of the transition metal catalyst in a concentration from 0.1 to 100 micromolar and a concentration of the hydrogen peroxide from 1 to 1500 mM; and, (iii) releasing the effluent after treatment for further processing or directly into the environment, wherein the aqueous industrial waste is subjected to a hydroxylation step during or prior to step (ii) .
  • the method is other than that of a cleaning or bleaching process.
  • the method is other than that applied in a laundry washing machine or dishwasher.
  • industrial waste is other than that of laundry or dish water. That is to say, most preferably the process is other than that applied by default to an effluent stream arising from treating a solid or particulate substrate with a preformed transition metal catalyst or ligand thereof together with hydrogen peroxide.
  • Hydroxylation is any chemical process that introduces one or more hydroxyl groups (-OH) into a compound (or radical) thereby oxidizing it.
  • hydroxylation reactions are often facilitated by enzymes called hydroxylases .
  • the hydroxylation step is most preferably provided in an aqueous environment.
  • the hydroxylation step may be provided by enzymatic, chemical reagents or electrochemical means.
  • Examples of chemical oxidisers that may also provide hydroxylation processes are permanganate, ammonium cerium (IV) nitrate, chromic acid, dichromic acid, chromyl chloride, chromium trioxide, pyridinium chlorochromate and chromate salts, dichromate salts, hypohalite, chlorate, chlorine dioxide, perchlorate, osmium tetraoxide, potassium osmate dihydrate (K 2 Os ⁇ 2 (OH) 4 ) , ruthenium tetroxide, nitric acid, alkyl peroxide (particularly in combination with transition metal complexes), Co(OAc) 2 , Pb(OAc) 4 , SeO 2 .
  • permanganate ammonium cerium (IV) nitrate
  • chromic acid dichromic acid
  • chromyl chloride chromium trioxide
  • pyridinium chlorochromate and chromate salts dichromate salts
  • the hydroxylation step is most preferably provided by hydroxyl radicals.
  • the treatment of the aqueous industrial waste with hydroxyl radicals is stopped before treatment with the transition metal catalyst. This is to reduce degradation of the transition metal catalyst by hydroxyl radical attack.
  • the aqueous industrial waste is subjected to a hydroxylation step prior to step (ii) and not during step (ii) .
  • a carbonate buffer may also be used reduce degradation of the transition metal catalyst.
  • the transition metal catalyst is added to the aqueous industrial waste in a carbonate buffer to trap hydroxyl radicals. This mode is particularly advantageous where the hydroxyl radicals are generated chemically rather than by physical processes such as UV irradiation and electrolysis which may simply be turned off.
  • UV-irradation hydrogen peroxide is homolytically split into hydroxyl radicals.
  • hydrogen peroxide absorbs UV-light only at wavelengths less than 300 nm, only lamps generating UV-light between 200 and 300 nm can be used.
  • a wavelength of typically 254 nm is used.
  • a typically UV-light exposure dose is 1-10 J/cm 2 , although much higher values can be obtained in large-scale commercial applications. For example a large reactor may contain twelve 20 kW UV lamps.
  • a typical residence time of a flow system within the cell containing the UV-lamp is less than 1 minute.
  • Hydrogen peroxide can be applied via a single-dose unit or at various points into the system.
  • UV disinfection or units include, but are not limited to, Calgon Carbon Inc., US Filter, Berson-UV, Wedeco, and Trojan Technologies. See for example Photochemical Purification of Water and Air, T. Oppenlaender, Wiley, VCH, 2003.
  • UV is provided to the aqueous environment via a UV transmissive - 1 . ⁇ v > ⁇ to irradiate the aqueous environment.
  • the UV transmissive ⁇ ::. ⁇ may be a finger insert into which a UV source is inserted or a window which forms part of the vessel in which the aqueous environment is travelling or is held.
  • the UV transmissive V 1 ⁇ S ⁇ is a quartz window.
  • UV-irradiation to enhance the formation of hydroxyl radicals using ozone or ozone in the presence of hydrogen peroxide.
  • Ozone is generated using compressed dried air or oxygen. Usually 0.5-2.0% of ozone is generated this way. If air is used, then complete dehumidification is needed, which makes the process more costly. Therefore often pure oxygen is used to generate ozone. Ozone gas is then transferred into the liquid phase using spargers, porous pipes or plates, or Venturi-type injection at dosages of about 1-2 mg/1 ozone per mg/1 dissolved COD.
  • E-beam reactors generate high-energy electrons that irradiate contaminated water.
  • the electrons are generated by a hot cathode and are accelerated by a voltage differential.
  • these electrons react with water to form reactive species, such as hydroxyl radicals, hydrated electrons, and hydrogen atoms.
  • the high-energy electrons do not penetrate the water for more than one centimeter.
  • An advantage of this method is that when compounds react relatively slowly with hydroxyl radicals (like acetone) ; the reaction with the hydrated electrons may be much higher, leading to efficient removal of such substrate. See for example M. B. Ray, Advanced Physicochemical Treatment Processes, Humana Press, 2006.
  • Electrolytic treatment of wastewater is known in the art; see for example: US 4,014,766; US 4,399,020; US 4,308,122; US 4,839,007; and US 5,160,417.
  • Electrodes include platinum, ruthenium dioxide, lead dioxide, tin dioxide.
  • Other frequently-employed electrodes are titanium coated with mixed metal oxides such as ruthenium and iridium, especially suitable for ammonia removal. ⁇ .. ; x , fouling of the electrode may be a problem during electrolytic oxidation of substrates (like phenols) .
  • a considerable improvement has been made by using crystalline diamond electrodes that have been doped with boron to increase electrically conductivity. The conductivity should be 100 ohm cm or less, whilst the optimal current level is between 50 and 600 mA/cm 2 .
  • the electrode used is a boron-doped diamond electrode.
  • Boron-doped diamond electrodes work particularly well, due to good conductivity properties, good stability and efficiency.
  • BDD electrodes are made of polycrystalline diamond formed by Chemical Vapour Deposition
  • each carbon atom is covalently bonded to its neighbours forming an extremely robust crystalline structure.
  • Some carbon atoms in the lattice are substituted with boron to provide electrical conductivity. Boron acts as an electron acceptor due to its electron deficiency in its outer shell.
  • Most suitable levels of B in the diamond lattice are in the range 10 19 to 10 21 atoms/cm 3 (up to 8000 ppm) .
  • the current per surface area is at least 500 A/m 2 , more preferabbly at least 1000 A/m 2 and most preferably at least 2000 A/m 2 .
  • the voltage applied to the electrode is at least 5 V, more preferably at least 10 V and most preferably at least 15 V.
  • Recirculation is preferably in the range from 5 to 30 m 3 per hour .
  • Fenton reactor Fenton chemistry may also used to generate hydroxyl radicals.
  • a typical Fenton reactor contains 50-500 mM hydrogen peroxide and an iron level of 5-100 mM.
  • the pH of the system is between 2 and 5.
  • Fe salts react with hydrogen peroxide to generate hydroxyl radicals.
  • sacrificial steel electrodes can be employed, wherein the electrodes slowly release the ferric ions. Often this system is also employed in combination with UV-irradiation to enhance the flux of hydroxyl radicals.
  • the temperature of the Fenton reactor may be between ambient conditions and more than 100 0 C, when a pressured vessel is used, see for example M.J. Fesse et al . , J. Hazardous Materials, 147, 167 (2007) for a description of the Fenton processes without and with UV- irradiation .
  • the Fenton derived hydroxyl radicals are preferably provided when the pH of the aqueous environment is in the range 2 to 5. It is then preferred that the pH of the aqueous environment pH is then increased to 7.5 to 11.5; aqueous sodium hydroxide is particularly suitable to provide this pH change .
  • Pulse radiolysis or sonolysis may also used to generate hydroxyl radicals and other reactive species. In pulse radiolysis apart from hydroxyl radicals also H atoms and hydrated electrons are formed. See M. G. Gonzales, et al . ,
  • the preformed transition metal catalyst or precursor thereof is formed from or provided by a tridentate, tetradentate, pentadentate or hexadentate nitrogen donor ligand.
  • the transition metal catalyst is preferably provided as a preformed transition metal catalyst.
  • the ligand is added to sequester adventitious transition metals or transition metals salts are added.
  • the addition of a particular transition metal salt, with respect to the transition metal is preferably employed.
  • the tridentate, tetradentate, pentadentate or hexadentate nitrogen donor ligand may be built up within any organic structure which will support coordinating nitrogen atoms.
  • a basic tridentate ligand such as 1 , 4 , 7-triazacyclononane and have further nitrogen coordination groups, e.g., -CH2-CH2-NH2, -CH2-Py, covalently bound to one or more of the cyclic nitrogens or aliphatic groups .
  • the iron ion is selected from Fe(II) and Fe(III) and the manganese ion is selected from Mn(II), Mn(III), and Mn (IV) .
  • the ligand is present in one or more of the forms [MnLCl 2 ]; [FeLCl 2 ]; [FeLCl]Cl; [FeL(H 2 O)] (PFg) 2 ; [FeL]Cl 2 ,
  • the length of any alkyl chain is preferably Cl to C8-alkyl chain and preferably linear. If unspecified the aryl group is a phenyl group.
  • the bispidon class are preferably in the form of an iron transition metal catalyst.
  • the bispidon ligand is preferably of the form:
  • each R is independently selected from: hydrogen, F, Cl, Br, hydroxyl, Cl-C4-alkylO-, -NH-CO-H, -NH-CO-C1-C4- alkyl, -NH2, -NH-Cl-C4-alkyl, and Cl-C4-alkyl;
  • Rl and R2 are independently selected from: Cl-C24-alkyl, C6-C10-aryl, and, a group containing a heteroatom capable of coordinating to a transition metal;
  • R3 R4 and selected from -C(O)-O-CH3, -C(O)-O- CH2CH3, -C (0) -O-CH2C6H5 and CH2OH.
  • the heteroatom capable of coordinating to a transition metal is pyridin-2-ylmethyl optionally substituted by -C0-C4-alkyl .
  • Rl and R2 are CH3, -C2H5, -C3H7, benzyl, -C4H9, -C6H13, -C8H17, -C12H25, and -C18H37 and pyridin-2-yl .
  • a preferred class of bispidon is one in which at least one of Rl or R2 is pyridin-2-ylmethyl or benzyl, preferably pyridin-2-ylmethyl.
  • a preferred bispidon is dimethyl 2, 4-di- (2-pyridyl) -3- methyl-7- (pyridin-2-ylmethyl) -3,7-diaza-bicyclo[3.3.1]nonan- 9-one-l, 5-dicarboxylate (N2py3o-Cl) and the iron complex thereof FeN2py3o-Cl which was prepared as described in W002/48301.
  • methyl group (Cl) at the 3 position have longer alkyl chains, namely isobutyl, (n-hexyl) C6, (n- octyl) C8, (n-dodecyl) C12, (n-tetradecyl) C14, (n- octadecyl) C18, which were prepared in an analogous manner.
  • Preferred tetradentate bispidons are also illustrated in WO00/60045 and preferred pentadentate bispidons are illustrated in WO02/48301 and WO03/104379.
  • the N4py are preferably in the form of an iron transition metal catalyst.
  • N4py type ligands are preferably of the form:
  • each R 1 , R 2 independently represents -R 4 -R 5 ,
  • R 3 represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or -R 4 -R 5 , each R 4 independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and each R 5 independently represents an optionally N- substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl.
  • R 1 represents pyridin-2-yl or R 2 represents pyridin-2-yl-methyl .
  • R 2 or R 1 represents 2-amino- ethyl, 2- (N- (m) ethyl) amino-ethyl or 2- (N, N-di (m) ethyl) amino- ethyl .
  • R 5 preferably represents 3-methyl pyridin-2-yl.
  • R 3 preferably represents hydrogen, benzyl or methyl .
  • the preferred ligands are N4Py (i.e. N, N-bis (pyridin-2-yl- methyl) -bis (pyridin-2-yl) methylamine) which is disclosed in WO95/34628 and MeN4py (i.e. N, N-bis (pyridin-2-yl-methyl-l, 1- bis (pyridin-2-yl) - 1- aminoethane, as disclosed in EP0909809.
  • the TACN-Nx are preferably in the form of an iron transition metal catalyst.
  • the ligands possess the basic 1, 4, 7-triazacyclononane structure but have one or more pendent nitrogen groups that complex with the transition metal to provide a tetradentate, pentadentate or hexadentate ligand.
  • the basic 1, 4, 7-triazacyclononane structure has two pendent nitrogen groups that complex with the transition metal (TACN-N2) .
  • the TACN-Nx is preferably of the form:
  • each R20 is selected from: an alkyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N + (R2i; , wherein R21 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY2-R22, in which Y is independently selected from H, CH3, C2H5, C3H7 and R22 is independently selected from an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazo
  • R22 is selected from optionally substituted pyridin-2-yl, imidazol-4-yl, pyrazol-1-yl, quinolin-2-yl groups. Most preferably R22 is either a pyridin-2-yl or a quinolin-2-yl .
  • the cyclam and cross bridged ligands are preferably in the form of a manganese transition metal catalyst.
  • the cyclam ligand is preferably of the form:
  • R is independently selected from: hydrogen, Cl-C6-alkyl, CH2CH2OH, pyridin-2-ylmethyl, and CH2COOH, or one of R is linked to the N of another Q via an ethylene bridge;
  • Rl, R2 , R3, R4, R5 and R6 are independently selected from: H, Cl-C4-alkyl, and Cl-C4-alkylhydroxy .
  • Preferred non-cross-bridged ligands are 1,4,8,11- tetraazacyclotetradecane (cyclam) , 1, 4, 8, 11-tetramethyl- 1, 4, 8, 11-tetraazacyclotetradecane (Me4cyclam) , 1,4,7,10- tetraazacyclododecane (cyclen) , 1, 4, 7, 10-tetramethyl- 1, 4, 7, 10-tetraazacyclododecane (Me4cyclen) , and 1,4,7,10- tetrakis (pyridine-2ylmethyl) -1,4,7, 10-tetraazacyclododecane (Py4cyclen) . With Py4cyclen the iron complex is preferred.
  • a preferred cross-bridged ligand is of the form:
  • R 1 is independently selected from H, and linear or branched, substituted or unsubstituted Cl to C20 alkyl, alkylaryl, alkenyl or alkynyl; and all nitrogen atoms in the macropolycyclic rings are coordinated with the transition metal .
  • Rl Me, which is the ligand 5, 12-dimethyl- 1, 5, 8, 12-tetraaza-bicyclo [ 6.6.2] hexadecane of which the complex [Mn (Bcyclam) Cl 2 ] may be synthesised according to WO98/39098.
  • Other suitable crossed bridged ligands are also found in WO98/39098.
  • TRIDENTATE LIGANDS WITH MANGANESE A suitable class of tridentate ligands is based on terpyridine-type ligands, depicted below.
  • terpyridine derivatives could be employed, such as bispyridylpyrimidine or bispyridyltriazine .
  • Preferred classes include the ones disclosed in WO2002088289; WO2004007657; WO2004039933 ; WO2004039934 ; WO2005068075 ; and WO2005068074; WO2005105303.
  • the trispicens are preferably in the form of an iron transition metal catalyst.
  • the trispicen type ligands are preferably of the form: R17R17N-X-NR17R17 (VI),
  • X is selected from -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 C(OH)HCH 2 -;
  • R17 independently represents a group selected from: R17 and alkyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N + (R19)3 , wherein R19 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY 2 -R18, in which Y is independently selected from H, CH3, C2H5, C3H7 and R18 is independently selected from an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl,
  • the heteroatom donor group is preferably pyridinyl optionally substituted by -C0-C4-alkyl .
  • heteroatom donor groups are imidazol-2-yl, l-methyl-imidazol-2-yl, 4-methyl-imidazol-2-yl, imidazol-4- yl, 2-methyl-imidazol-4-yl, l-methyl-imidazol-4-yl, benzimidazol-2-yl and l-methyl-benzimidazol-2-yl .
  • R17 are CY 2 -R18.
  • the ligand Tpen i.e. N, N, N', N' -tetra (pyridin-2-yl- methyl) ethylenediamine
  • WO97/48787 is disclosed in WO97/48787.
  • a more preferred transition metal catalyst for the method is as described in EP 0458397 and WO06/125517; both of these patents disclose the use of manganese 1, 4, 7-Trimethyl-l, 4, 7- triazacyclononane (Me3-TACN) as related compounds as complexes.
  • the PF 6 ⁇ ligand of Me3-TACN has been commercialised in laundry detergent powders and dish wash tablets. It is preferred that a preformed transition metal of Me3-TACN and related compounds is in the form of a salt such that it has a water solubility of at least 50 g/1 at 20 0 C.
  • Preferred salts are those of chloride, acetate, sulphate, and nitrate. Most preferred are the acetate and sulphate salts.
  • the catalyst is most preferably a mononuclear or dinuclear complex of a Mn H-V transition metal catalyst, the ligand of the transition metal catalyst of formula (I) :
  • R is independently selected from: hydrogen, Cl-C6-alkyl,
  • Rl, R2 , R3, and R4 are independently selected from: H, Cl-
  • R is preferably independently selected from: hydrogen, CH3, C2H5, CH2CH2OH and CH2COOH.
  • R, Rl, R2, R3, and R4 are preferably independently selected from: H and Me.
  • the aqueous industrial waste is stored during treatment as a batch or a continuous process for treating waste water.
  • material is placed in the vessel at the start and removed at the end of the process.
  • material flows into and out of the process during the duration of the process.
  • the holding vessel may be a conduit or discreet vessel.
  • the catalytic degradation solution may be used in combination with such a biological treatment unit.
  • the vessel may be located before or after a biological treating system. When located before the biological treatment system, one can destroy most of the undesired molecules from the effluent in a more concentrated form, i.e. just after the process where it has been formed (e.g. dyeing bath or chemical reactor) . This will lead to an increased selectivity of destruction, as there are less or no components other than the component that needs to be degraded. Further, the volumes to treat the solutions are much lower, which leads to a reduced chemical (catalyst and hydrogen peroxide) demand.
  • catalase enzymes may be added to destroy hydrogen peroxide before it enters the biological treatment unit (excessive hydrogen peroxide may lead to reduced biological activity) .
  • the catalytic oxidation treatment unit may be placed after the biological treatment tank.
  • the extent of degradation of the pollutant by the catalyst and hydrogen peroxide depends on many factors, including time, pH of the reaction, optionally addition of sequestrant, temperature of the reaction, type of pollutant, level of pollutant, level of other organic materials, level of transition-metal ions, like Fe or Cu, which could give hydrogen peroxide decomposition, and presence of catalase enzyme, which gives hydrogen peroxide decomposition. For each application these optimal conditions need to be assessed.
  • the solvent is not necessarily limited to water; also organic solvents may be employed to degrade the pollutant, such as methanol, ethanol, or acetone. This could be the case where industrial processes to produce fine or bulk chemicals. In the case where an organic solvent is used, it is desired to use the same solvent (s) for the oxidative degradation process as used in the industrial processes. After the treatment with the catalyst and hydrogen peroxide, the organic solvent is preferably removed.
  • the preformed transition metal catalyst or precursor thereof may be added in one batch, multiple additions, or as a continuous flow.
  • the use of a continuous flow is particularly applicable to continuous processes.
  • the hydrogen peroxide may also be generated electrochemically or using oxidase enzymes, including glucose oxidase, methanol oxidase and the like.
  • the aqueous industrial waste is preferably monitored during treatment by UV or UV-visible spectroscopy.
  • the wavelength of monitoring depends upon the nature of the waste. When coloured dyes or lignin residues are being treated it is preferred that monitoring is conducted with UV-visible spectroscopy.
  • the absorption of the aqueous industrial waste is preferably linked to a set threshold value that when met results in an automated step taking place. This step may be step (iii) or the addition of further actives to the aqueous industrial waste.
  • the monitoring device may include HPLC or other chromatographic methods to analyse the degradation of the undesired product. This may include an automatic feedback loop as described above.
  • BDD electrodes are made of polycrystalline diamond formed by Chemical Vapour Deposition (CVD) in a high temperature microwave process.
  • CVD Chemical Vapour Deposition
  • each carbon atom is covalently bonded to its neighbours forming an extremely robust crystalline structure.
  • Some carbon atoms in the lattice are substituted with boron to provide electrical conductivity. Boron acts as an electron acceptor due to its electron deficiency in its outer shell.
  • Boron doping levels are in the range 10 19 to 10 21 atoms/cm 3 (up to 8000 ppm) .
  • the temperature was set at around 5O 0 C, the voltage set on the electrode was 31.5 V and the current was between 42 and 45 A.
  • the amount of formaldehyde was determined using a MBTH Method 8110 (Hach) set up, using a colour blue colour upon reaction with 3-methyl-2-benzothiazoline hydrazone.
  • a solution of industrial waste containing hydraulic cutting and cooling oil was treated.
  • the COD level of this system was 159.6 g/1.
  • the temperature was set at around 40 0 C, the voltage set on the electrode was around 30 V and the current was between 25 and 30 A between 0 and 4 h and at 52.5 A between 4 and 10 h.
  • the COD level was determined using a Hach Reactor Digestion Method 8000 set up, using a Mn-based COD determination.
  • the COD level was determined using a Hach Reactor Digestion Method 8000 set up, using a Mn-based COD determination.
  • the progress of the bleaching was followed by UV-Vis spectroscopy using a Hewlett-Packard 8453 UV-Vis diode array spectrophotometer following the absorbance at around 540 nm in time.
  • the dye solution was contained in a reactor consisting of a 10 mm quartz cuvette.
  • Sequestrant 60 ⁇ M Dequest 2066
  • hydrogen peroxide 10 mM at the start
  • [Mn 2 O 3 (Me 3 tacn) 2 ] (PF 6 ) 2 (10 ⁇ M) The solution was irradiated with 254 nm light (a Vilber VL-8.LC power 400-520 ⁇ W/cm 2 ) . After 15 min, nearly complete bleaching (98%) was observed.
  • MeN4Py N,N-bis (pyridin-2-yl-methyl-l, 1-bis (pyridin-2-yl) - 1- aminoethane , hereafter referred to as MeN4Py, and the corresponding iron (II) complex, [Fe (MeN4py) Cl] Cl, were prepared as described in EP0909809.
  • the progress of dye bleaching was followed as described in example 4.
  • the setup is as described as example 5.
  • a solution containing the dye Reactive Orange 16 and 5OmM carbonate buffer was treated at around 60 0 C.
  • the initial concentration of the dye was such that the initial absorbance at 50OnM was around 1.
  • Sequestrant (60 ⁇ M Dequest 2066) and hydrogen peroxide (1OmM at the start) were added together with [Fe (MeN4py) Cl] Cl (20 ⁇ M) .
  • the solution was irradiated as described above. After 40 min, a high level of bleaching (75%) is obtained, reaching 90% in 60 min.

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  • 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)
  • Catalysts (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

La présente invention concerne le traitement de déchets industriels avec des catalyseurs de type métaux de transition, du peroxyde d'hydrogène et un radical réactif.
PCT/EP2009/058321 2008-07-04 2009-07-02 Traitement d'eaux usées WO2010000798A1 (fr)

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WO2011098597A1 (fr) * 2010-02-12 2011-08-18 A.C.K. Aqua Concept Gmbh Karlsruhe Procédé de traitement d'eaux usées contenant des vernis photosensibles
CN102849876A (zh) * 2012-09-25 2013-01-02 科迈化工股份有限公司 一种处理橡胶防老剂rd生产废水的方法
CN104495972A (zh) * 2014-12-08 2015-04-08 湖南科技大学 硫化亚砷的应用
CN104773888A (zh) * 2015-04-23 2015-07-15 东南大学 铁碳内电解-Fenton氧化-电解电催化氧化法联合处理废水的方法及装置
CN105776681A (zh) * 2016-04-13 2016-07-20 东莞市联洲知识产权运营管理有限公司 一种高效环保的医药废水处理方法
CN105923859A (zh) * 2016-06-28 2016-09-07 扬州大学 一种高浓度苯酸酯类工业污水循环再利用处理方法
CN107298500A (zh) * 2017-06-26 2017-10-27 招金矿业股份有限公司 一种废水处理方法
CN107640861A (zh) * 2017-10-09 2018-01-30 北京中科康仑环境科技研究院有限公司 一种臭氧、电化学和芬顿氧化耦合联用深度处理系统及其处理工艺
CN108585304A (zh) * 2018-05-04 2018-09-28 山东默锐环境产业股份有限公司 一种bdp废水预处理方法
CN109399856A (zh) * 2017-08-18 2019-03-01 中国科学院大连化学物理研究所 一种基于臭氧催化氧化的兰炭废水零排放处理方法
CN110143698A (zh) * 2019-06-14 2019-08-20 乐清市荣禹污水处理有限公司 一种电镀污水处理方法
JP2019531875A (ja) * 2016-08-10 2019-11-07 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ 塩化物含有プロセス溶液の電気化学的浄化のためのプロセス
CN111039511A (zh) * 2019-12-30 2020-04-21 何亚婷 一种化工回收废水处理的模块化集成工艺方法
WO2020223366A1 (fr) * 2019-04-29 2020-11-05 Zero Discharge, LLC Appareil et procédé de traitement des eaux à rejet nul
CN112777716A (zh) * 2020-12-09 2021-05-11 北京理工大学 一种光催化降解地表水微量有机大分子方法
CN113044953A (zh) * 2021-04-21 2021-06-29 华东理工大学 经单质硼强化的芬顿体系及去除地下水中1,2-dca的方法

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WO2011098597A1 (fr) * 2010-02-12 2011-08-18 A.C.K. Aqua Concept Gmbh Karlsruhe Procédé de traitement d'eaux usées contenant des vernis photosensibles
CN102849876A (zh) * 2012-09-25 2013-01-02 科迈化工股份有限公司 一种处理橡胶防老剂rd生产废水的方法
CN104495972A (zh) * 2014-12-08 2015-04-08 湖南科技大学 硫化亚砷的应用
CN104773888A (zh) * 2015-04-23 2015-07-15 东南大学 铁碳内电解-Fenton氧化-电解电催化氧化法联合处理废水的方法及装置
CN105776681B (zh) * 2016-04-13 2019-01-25 潘素娇 一种高效环保的医药废水处理方法
CN105776681A (zh) * 2016-04-13 2016-07-20 东莞市联洲知识产权运营管理有限公司 一种高效环保的医药废水处理方法
CN105923859A (zh) * 2016-06-28 2016-09-07 扬州大学 一种高浓度苯酸酯类工业污水循环再利用处理方法
JP2019531875A (ja) * 2016-08-10 2019-11-07 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ 塩化物含有プロセス溶液の電気化学的浄化のためのプロセス
CN107298500A (zh) * 2017-06-26 2017-10-27 招金矿业股份有限公司 一种废水处理方法
CN109399856A (zh) * 2017-08-18 2019-03-01 中国科学院大连化学物理研究所 一种基于臭氧催化氧化的兰炭废水零排放处理方法
CN107640861A (zh) * 2017-10-09 2018-01-30 北京中科康仑环境科技研究院有限公司 一种臭氧、电化学和芬顿氧化耦合联用深度处理系统及其处理工艺
CN108585304A (zh) * 2018-05-04 2018-09-28 山东默锐环境产业股份有限公司 一种bdp废水预处理方法
WO2020223366A1 (fr) * 2019-04-29 2020-11-05 Zero Discharge, LLC Appareil et procédé de traitement des eaux à rejet nul
US11390545B2 (en) 2019-04-29 2022-07-19 Zero Discharge, LLC Zero discharge water treatment apparatus and method
CN110143698A (zh) * 2019-06-14 2019-08-20 乐清市荣禹污水处理有限公司 一种电镀污水处理方法
CN111039511A (zh) * 2019-12-30 2020-04-21 何亚婷 一种化工回收废水处理的模块化集成工艺方法
CN111039511B (zh) * 2019-12-30 2022-07-22 深圳市睿维盛环保科技有限公司 一种化工回收废水处理的模块化集成工艺方法
CN112777716A (zh) * 2020-12-09 2021-05-11 北京理工大学 一种光催化降解地表水微量有机大分子方法
CN113044953A (zh) * 2021-04-21 2021-06-29 华东理工大学 经单质硼强化的芬顿体系及去除地下水中1,2-dca的方法

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