EP2276704A1 - Corps moulé en tio2 à activité photocatalytique - Google Patents

Corps moulé en tio2 à activité photocatalytique

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Publication number
EP2276704A1
EP2276704A1 EP09738209A EP09738209A EP2276704A1 EP 2276704 A1 EP2276704 A1 EP 2276704A1 EP 09738209 A EP09738209 A EP 09738209A EP 09738209 A EP09738209 A EP 09738209A EP 2276704 A1 EP2276704 A1 EP 2276704A1
Authority
EP
European Patent Office
Prior art keywords
photocatalyst
tio
strands
wastewater
strand
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.)
Withdrawn
Application number
EP09738209A
Other languages
German (de)
English (en)
Inventor
Alexandra Seeber
Goetz-Peter Schindler
Katrin Freitag
Reinhard Hess
Rudolf Piehl
Thilo Hahn
Thomas Hill
Michael Hesse
Piotr Makarczyk
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP09738209A priority Critical patent/EP2276704A1/fr
Publication of EP2276704A1 publication Critical patent/EP2276704A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/12—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of actinides
    • 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
    • B01J23/75—Cobalt
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J35/613—10-100 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
    • B01J35/61—Surface area
    • B01J35/615—100-500 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
    • B01J35/633—Pore volume less than 0.5 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
    • 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
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • 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
    • C02F2103/32—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
    • C02F2103/36—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 manufacture of organic compounds
    • C02F2103/365—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 manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • 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
    • C02F2305/10—Photocatalysts

Definitions

  • the present invention relates to a process for purifying waste water by contacting the waste water to be treated with a strand-shaped TiO 2 photocatalyst under irradiation with light, and to using a strand-shaped TiC> 2 photocatalyst for purifying waste water under irradiation with light.
  • Titanium dioxide-containing photocatalysts or the use of such catalysts for wastewater purification have already been described in the prior art.
  • CN 134 8834 discloses titanium dioxide-containing catalyst pellets having a BET surface area of 4 to 20 m 2 / g, which can be used for the purification of waste water containing organic impurities.
  • the catalyst used according to CN 134 8834 is prepared using a pore-forming reagent selected from carbon, starch and carbonate salts.
  • CN 134 8834 does not disclose a process for the purification of waste water in which a strand-shaped Ti ⁇ 2 photocatalyst with a BET surface area of 25 to 200 m 2 / g is used.
  • JP 2005/066433 discloses a photocatalytically active granules containing titanium dioxide in the anatase modification. According to JP 2005/066433, the granules used must have a minimum size of 0.5 to 1.0 millimeter in order to remain active over a long period of time. Properties such as BET surface area, pore volume or mean pore diameter of the titanium dioxide-containing granules used are not disclosed in JP 2005/066433.
  • JP 2000/354863 discloses a photocatalyst for waste water treatment containing titanium dioxide as a catalytically active compound.
  • the wastewater to be treated may contain organic contaminants.
  • JP 2000/354863 does not disclose specifications of the titanium dioxide catalyst used.
  • EP 1 175 259 B1 discloses moldings of titanium dioxide, processes for their preparation and their use.
  • the moldings contain titanium dioxide having a particle size of 0.01 to 50 mm, each consisting of primary crystallites of titanium dioxide in the anatase modification and a BET surface area of 20 to 150 m 2 / g, a pore volume of 0.1 to 0.45 cm 3 / g and have a pore diameter of 100 to 300 ⁇ .
  • the proportion of foreign ions in these catalysts is particularly low.
  • the shaped bodies show UV activity, so that they can be used as photocatalysts.
  • EP 1 175 259 B1 does not disclose a process for purifying wastewater using these titanium dioxide catalysts.
  • US 2001/0006933 A1 discloses photocatalytically active granules and a process for their preparation.
  • the photocatalytically active compound titanium dioxide is present in these moldings, and at least 10% by weight of colloidal silica are used as the binder.
  • US 2001/0006933 A1 does not disclose properties of the titanium dioxide catalyst with respect to BET surface area, pore volume or pore diameter. Furthermore, no method for wastewater treatment is disclosed.
  • EP 1 369 383 discloses a process for removing sulfur from a mixture containing hydrogen sulfide and benzene, toluene and / or xylene.
  • a catalyst comprising a support comprising at least one compound selected from the group consisting of aluminum, titanium dioxide and zirconium, the support further comprising at least one doping element selected from the group consisting of iron, is used for this purpose , Cobalt, nickel, copper and vanadium.
  • EP 1 369 383 also does not disclose a process for the purification of contaminated wastewater.
  • Object of the present invention is to provide a method for the purification of wastewater, which is characterized by a particularly high efficiency.
  • the method according to the invention should also have a consistently high cleaning effect over a longer period of time.
  • the method should effectively separate the contaminants present in the wastewater, so that a purified wastewater is obtained which has a particularly low content of pollutants.
  • Photocatalyst having a BET surface area of 25 to 200 m 2 / g, a pore volume of 0.10 to 1, 00 mL / g and an average pore diameter of 0.005 to 0.050 microns, under irradiation with light, as well as by the use of a Such strand-shaped photocatalyst for the purification of waste water under irradiation with light.
  • a special strand-shaped titanium dioxide photocatalyst is used, which is distinguished by the inventive combination of BET surface area, pore volume, average pore diameter and geometry of the individual catalyst particles.
  • This invention proper combination results in a particularly high activity, and a particularly long life of the photocatalyst used with consistently high activity.
  • titanium dioxide is used, which is present essentially in the anatase modification.
  • "Essentially” in the context of the present invention means that at least 50%, particularly preferably at least 75%, of the titanium dioxide is present in the anatase modification on the basis of the XRD measurement method known to those skilled in the art
  • the remainder of the titanium dioxide consists of amorphous metal oxide, brookite or rutile modification or a mixture thereof
  • the titanium dioxide used is completely, ie 100% determined by XRD, in the anatase modification.
  • a strand-shaped TiO 2 photocatalyst is used.
  • strand-shaped means that the photocatalyst used preferably has an oval or round base surface.
  • the diameter of this round base area or an oval base area in the largest dimension is generally 0.2 to 10 mm, preferably 0.5 to 3.0 mm.
  • the strand-shaped titanium dioxide photocatalyst generally has a length of 0.5 to 10 mm, preferably 0.8 to 8 mm, particularly preferably 1, 0 to 5.0 mm.
  • the ratio of length to diameter of the strand-shaped photocatalyst according to the invention is generally 0.05 to 50, preferably 1, 0 to 10.
  • the employed strand-form photocatalyst essentially contains titanium dioxide as the photocatalytically active material, that is to say that the photocatalyst used generally contains at least 90% by weight, preferably at least 95% by weight, particularly preferably 99%, of titanium dioxide. The remainder are inorganic or organic additives, or a mixture thereof.
  • the titanium dioxide photocatalyst contains at least one additive, more preferably selected from groups 1, 4, 8, 9, 10, 11, 13, 14, 15 of the Periodic Table of the Elements (new IU-PAC nomenclature) or the lanthanides, for example selected from the group consisting of sodium, potassium, zirconium, cobalt, zinc, iron, copper, silver, gold, palladium, platinum, gallium, nitrogen, carbon, sulfur, ytterbium, erbium, thulium, neodymium and mixtures thereof , in elemental or oxidic form.
  • groups 1, 4, 8, 9, 10, 11, 13, 14, 15 of the Periodic Table of the Elements (new IU-PAC nomenclature) or the lanthanides for example selected from the group consisting of sodium, potassium, zirconium, cobalt, zinc, iron, copper, silver, gold, palladium, platinum, gallium, nitrogen, carbon, sulfur, ytterbium, erbium, thulium, neodymium and mixtures thereof
  • Combinations of two or more of the additives mentioned may preferably also be present, particularly preferred combinations being zirconium and nitrogen, zirconium and cobalt, lanthanum and zirconium, potassium and zirconium or sodium and zirconium.
  • the at least one additive is preferably present in the strand-form titanium dioxide photocatalyst used according to the invention in an amount of 0.001 to 5% by weight, particularly preferably 0.01 to 3% by weight. If two or more of the additives mentioned are present at the same time in the photocatalyst used according to the invention, the stated quantities relate to this mixture.
  • the strand-shaped titanium dioxide photocatalyst used according to the invention generally has a BET surface area of 25 to 200 m 2 / g, preferably 50 to 180 m 2 / g, particularly preferably 80 to 150 m 2 / g.
  • the BET surface area can be determined by methods known to those skilled in the art, for example according to DIN 66 131.
  • the strand-shaped titanium dioxide photocatalyst used according to the invention generally has a pore volume of from 0.1 to 1, 00 ml / g, preferably from 0.2 to 0.7 ml / g, particularly preferably from 0.25 to 0.55 ml / g ,
  • the pore volume can be determined by methods known to those skilled in the art.
  • the strand-form titanium dioxide photocatalyst usable according to the invention generally has an average pore diameter of 0.001 to 0.050 ⁇ m, preferably 0.005 to 0.030 ⁇ m, particularly preferably 0.010 to 0.025 ⁇ m.
  • the average pore diameter can be determined by methods known to the person skilled in the art.
  • the strand-form titanium dioxide photocatalyst which can be used according to the invention can be prepared by processes known to the person skilled in the art.
  • the photocatalyst used according to the invention is characterized by the corresponding amounts of titanium dioxide and at least one organic binder, preferably selected from sugar derivatives, for example Tylose, starch solutions, for example corn starches, celluloses such as methyl cellulose and / or at least one fatty acid, for example Stearic acid, polymers such as polyethylene oxide and at least one acid, for example, mineral acid such as dilute nitric acid or hydrochloric acid or organic acid such as formic acid.
  • This mixture is mixed by conventional methods known in the art in conventional devices, for example, gekollert.
  • the resulting mixture can then be extruded to the corresponding strand-form photocatalysts.
  • the extrudate thus produced is preferably dried at a temperature of at most 120 ° C., and the strands obtained are then preferably calcined at a temperature of from 300 to 500 ° C. in an air atmosphere in order to obtain the combination of BET surface area according to the invention, To obtain pore volume and mean pore diameter.
  • tylose and stearic acid in the preparation of the titanium dioxide used in the invention causes the resulting titanium dioxide having the inventive combination of high activity and high stability with a sustained high activity over a long period of time
  • the wastewater is purified, d. H.
  • the concentration of interfering substances is lower than before the procedure.
  • the wastewater to be treated can be, for example, from industrial plants, for example oil refineries, paper mills, mines, in the food sector or in the chemical industry, the private sector, for example sports facilities, restaurants, hospitals or natural origin.
  • the interfering substances to be removed from the waste water are selected from organic or inorganic substances which, if they remained in the waste water, would have a disturbing effect, for example, by a toxic effect, odor nuisance, coloring of the waste water, etc.
  • the purification is carried out by chemical degradation of organic or inorganic compounds such as organic acids, halogenated organic substances, aromatic or aliphatic organic substances, amines, oligomeric or polymeric materials, alcohols, ethers, esters, sugars , biologically or non-biodegradable substances, surfactants, ammonia, salts, heavy metals and mixtures thereof.
  • organic or inorganic compounds such as organic acids, halogenated organic substances, aromatic or aliphatic organic substances, amines, oligomeric or polymeric materials, alcohols, ethers, esters, sugars , biologically or non-biodegradable substances, surfactants, ammonia, salts, heavy metals and mixtures thereof.
  • the substances which can be removed from the wastewater by the process according to the invention selected from organic compounds selected from the group consisting of organic acids, halogenated organic substances, aromatic or aliphatic organic substances, amines, oligomeric or polymeric materials , Alcohols, ethers, esters, sugars, biologically or non-biodegradable substances, surfactants and mixtures thereof.
  • the process according to the invention for purifying wastewater is carried out by bringing the wastewater to be treated into contact with the strand-form titanium dioxide photocatalyst. This contacting can be carried out continuously or discontinuously. Suitable devices are known in the art, for example, fixed bed reactors such as flow tubes or plate reactors.
  • the strand-shaped titanium dioxide photocatalyst is introduced into a corresponding vessel, for example a flow tube, and the wastewater to be purified flows over and / or through this catalyst.
  • the flow rate of the wastewater to be purified is to be set so that there is a sufficiently long contact time between the wastewater to be purified and the photocatalyst.
  • a suitable flow rate is for example 0.001 to 100 cm / s, preferably 0.01 to 1 cm / s.
  • the inventive method is conducted at a temperature of generally 0 to 80 0 C, preferably 10 to 60 0 C, particularly preferably from 15 to 35 ° C.
  • the process according to the invention is generally carried out at a pressure of 0.5 to 50 bar, preferably 0.8 to 5 bar, particularly preferably at atmospheric pressure.
  • the titanium dioxide photocatalyst has a particularly high long-term stability.
  • the activity of the catalyst is proportional to the degradation rate, which is measured in terms of "amount of degraded pollutant per time per amount of catalyst.”
  • the activity of the catalyst depends on the pollutant to be degraded, as well as the reaction conditions, such as temperature, concentrations, etc.
  • the stability of the catalyst can be determined by measuring the activity of the catalyst after a reaction time x with the activity of the catalyst at time 0, ie. H. at the beginning of the reaction, compares. Suitable reaction times x are, for example, 12, 24 or 36 months.
  • the photocatalyst according to the invention for example, after a reaction time of 12 months, preferably after 24 months, more preferably after 36 months, still an activity ⁇ , which is at least 80%, preferably at least 90%, particularly preferably at least 95% of the activity.
  • the catalyst according to the invention hardly loses any activity over a long period of time, which makes it particularly qualified for continuous and low-maintenance cleaning processes.
  • the inventive method comprises contacting the wastewater to be cleaned with a strand-shaped titanium dioxide photocatalyst under irradiation with light.
  • any type of light known to those skilled in the art can be used, for example light having a wavelength ⁇ of 200 to 800 nm, preferably 300 to 500 nm, very particularly preferably 360 to 420 nm.
  • ⁇ 200 to 400 nm
  • ⁇ 400 to 800 nm
  • the light intensity with which the irradiation with light takes place is generally 0.01 to 100 mW / cm 2 , preferably 0.1 to 20 mW / cm 2 .
  • the present invention also relates to the use of a strand-shaped TiO 2 photocatalyst having a BET surface area of from 25 to 200 m 2 / g, a pore volume of from 0.10 to 1, 00 ml / g and an average pore diameter of from 0.005 to 0.050 ⁇ m for purifying waste water under irradiation with light.
  • the use according to the invention is characterized in that the Ti ⁇ 2 photocatalyst at least one additive selected from the groups 1, 4, 8, 9, 10, 1 1, 13, 14, 15 of the Periodic Table of the Elements (new IUPAC nomenclature) or contains the lanthanides.
  • the at least one additive is preferably present in an amount of from 0.01 to 5% by weight, based on the TiO 2 photocatalyst.
  • the wastewater to be purified contains organic or inorganic compounds, preferably from the group consisting of organic acids, halogenated organic substances, aromatic or aliphatic organic substances, amines, oligomeric or polymeric materials, alcohols, Ethers, esters, sugars, biologically or non-biodegradable substances, surfactants, ammonia, salts, heavy metals and mixtures thereof.
  • organic or inorganic compounds preferably from the group consisting of organic acids, halogenated organic substances, aromatic or aliphatic organic substances, amines, oligomeric or polymeric materials, alcohols, Ethers, esters, sugars, biologically or non-biodegradable substances, surfactants, ammonia, salts, heavy metals and mixtures thereof.
  • Example 1 1.5 mm TiO 2 tablets (comparative example)
  • Example 3 5 mm TiO 2 tablets (comparative example)
  • Example 4 2 mm TiO 2 -coated Al 2 O 3 spheres (comparative example)
  • Al 2 O 3 balls (Fa. Sasoll, 2.0 mm diameter, annealed at 1300 0 C) are soaked in 20 ml of titanium isopropoxide and for 4 h in air dried at room temperature. The almost dried spheres are then heated in a muffle furnace in 30 minutes at 120 0 C and 2 h pre-dried at 120 0 C. The balls are then heated in 75 min to 500 0C and calcined at 500 0 C for 1 h.
  • the photoactivities are determined according to Example 35.
  • Example 5 1.5 mm strands (according to the invention)
  • An inventive TiO 2 photocatalyst is prepared as follows:
  • the strand-shaped catalyst thus obtained has the following properties.
  • the photoactivities are determined according to Example 35.
  • Example 33 (4074 ppm / h * kg ⁇ ATAi_ ⁇ sA ⁇ oR) and Example 34 (943 ppm / h * kg ⁇ ATAi_ ⁇ sA ⁇ oR).
  • the strand hardness is set by the temperature in the annealing zone of the calcination. At higher temperatures the hardness increases, but the surface gets smaller.
  • the window for operating the furnace is between 420 and 435 ° C in the hot zone. The above data is an optimized operating point.
  • Example 7 Modification of the TiO 2 Strand with Yttrium (Inventive)
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 4141 ppm / h * kg catalyst.
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 4208 ppm / h * kg catalyst.
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 4259 ppm / hr * kg of catalyst.
  • Example 11 Modification of the TiC> 2 Ranks with Neodymium (Inventive)
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 4427 ppm / h * kg catalyst.
  • Example 12 Modification of the TiO 2 Rands with Zirconium and Nitrogen (Inventive)
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 5016 ppm / hr * kg of catalyst.
  • Example 13 Modification of the TiO 2 Strands with Zirconium and Nitrogen (Inventive)
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 5218 ppm / hr * kg of catalyst.
  • Example 5 50 g of uncalcined TiO 2 extrudates from Example 5 are filled into a rotary tube and heated with 7.5 L / h NH 3 in 1 h at 550 0 C. Then the strands are held at 550 0 C for 3 h and then cooled under N 2 . The product is gray. The N content is 0.002%. The determination of the photocatalytic activity is carried out as described in Example 33. The product has a DCA degradation rate of 5538 ppm / hr * kg of catalyst.
  • Example 33 The determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 5723 ppm / hr * kg of catalyst.
  • the determination of the photocatalytic activity is carried out as described in Example 34.
  • the product has a DCA degradation rate of 1044 ppm / hr * kg of catalyst.
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 5841 ppm / hr * kg of catalyst.
  • Example 17 Modification of the TiO 2 Sands with Sodium (Inventive)
  • Example 18 Modification of the TiC> 2 Strand with Silver (Inventive)
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 5959 ppm / hr * kg of catalyst.
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 6363 ppm / hr * kg catalyst.
  • Example 20 Modification of the TiC> 2 Ranks with Zirconium and Cobalt (According to the Invention)
  • Example 21 Modification of the TiC 2 Strands with Lanthanum and Zirconium (Inventive)
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 6599 ppm / hr * kg of catalyst.
  • Example 22 Modification of the TiO 2 Strands with Potassium and Zirconium (Inventive)
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 6868 ppm / hr * kg catalyst.
  • Example 23 Modification of the TiC> 2 Ranks with Zirconium and Potassium (Inventive)
  • the almost dried strands are heated to 300 0 C in 2 h and calcined at 300 0 C for 3 h.
  • the Zr content is 0.29% and the K content is 0.26%.
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 7945 ppm / hr * kg of catalyst.
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 7996 ppm / hr * kg of catalyst.
  • Example 25 Modification of the TiO 2 Strands: Sodium and Zirconium (According to the Invention)
  • the determination of the photocatalytic activity is carried out as described in Example 33.
  • the product has a DCA degradation rate of 8484 ppm / h * kg catalyst.
  • Example 27 Preparation of Zr-doped 1.5 mm TiC 2 Strands (Inventive)
  • the photocatalytic activity of the 1.5 mm TiO 2 extrudates is determined by the method in Example 35.
  • the 1.5 mm TiO 2 rods have a DCA degradation rate of 233 ppm / h * kg of catalyst.
  • the photocatalytic activity of the 1.5 mm TiO 2 extrudates is determined by the method in Example 35.
  • the 1.5 mm TiO 2 rods have a DCA degradation rate of 250 ppm / h * kg of catalyst.
  • Example 31 Preparation of Zr-doped 1.5 mm TiC> 2 strands
  • 1, 5 mm dies are used, it is used a one-armed Whiper, so that the Whiper arm is opposite to the end of the screw spiral. It is set a torque of 50 - 150 Nm.
  • the extruder is cooled.
  • the extrudates thus obtained are dried in a three-zone dryer, 55/70/100 0 C in zone 1/2 / 3.
  • the dried extrudates are calcined in a rotary kiln oven at 435 0 C.
  • the Zr content is 0.49%.
  • the photocatalytic activity of the 1.5 mm TiO 2 extrudates is determined by the method in Example 35.
  • the 1.5 mm TiO 2 rods have a DCA degradation rate of 238 ppm / h * kg of catalyst.
  • Example 33 Determination of photocatalytic activity under UV irradiation
  • the photoactivities of the catalysts prepared are determined by the rate of photocatalytic degradation of the chlorinated hydrocarbon dichloroacetic acid (DCA) in suspension.
  • the total runtime of the experiments to check the rate of photocatalytic degradation of DCA under UV irradiation in aqueous solution is 24 hours.
  • the UV light intensity is 1 mW / cm 2 .
  • the pH of the solution is adjusted to 3 with sodium hydroxide solution.
  • the temperature in the reactor is 20 to 30 ° C.
  • the concentration of DCA is 20 mmol / L, and the concentration of the photocatalyst is 3 g / L.
  • Blank tests are carried out for the degradation of DCA under irradiation with addition of a standard photocatalyst (Degussa P25, ca. 80% anatase / 20% rutile modification via XRD (diffractometer D 4 Endeavor)). Blank tests are also carried out for the degradation of DCA under UV irradiation without the addition of photocatalyst and with rutile modification titania (Degussa P25, calcined at 900 ° C. for 18 h, 100% rutile fraction determined by XRD (Diffractometer D 4 Endeavor)).
  • TOC Total Organic Carbon
  • Example 34 Determination of photocatalytic activity under indoor irradiation
  • the photoactivities of the catalysts prepared are determined by the rate of photocatalytic degradation of the chlorinated hydrocarbon dichloroacetic acid (DCA) in suspension.
  • the total runtime of the experiments to verify the rate of photocatalytic degradation of DCA under UV irradiation in aqueous solution is included 24 hours.
  • the irradiation is carried out with an Osram Biolux (L18 / W965) lamp; the UV light intensity is ⁇ 0.1 mW / cm 2 .
  • the pH of the solution is adjusted to 3 with sodium hydroxide solution.
  • the temperature in the reactor is 20 to 30 0 C.
  • the concentration of DCA is 20 mmol / L, and the concentration of the photocatalyst is 3 g / L.
  • the photoactivities of the catalysts prepared are determined by the rate of photocatalytic degradation of the chlorinated hydrocarbon dichloroacetic acid (DCA) in suspension.
  • the total runtime of the experiments to verify the rate of photocatalytic degradation of DCA under UV irradiation in aqueous solution is 6 hours.
  • the irradiation is carried out with an Osram Biolux (L18 / W965) lamp; the UV light intensity is 1.2 mW / cm 2 .
  • the temperature in the reactor is 20 to 30 0 C.
  • the concentration of DCA is 162 ppm.
  • the pH of the DCA solution is adjusted to 3 with sodium hydroxide solution. 200 g of photocatalyst molded body are used. By titration of caustic soda, the pH is kept at 3.
  • the determination of the degradation rate (ppm / h) is determined by the added amount of sodium hydroxide solution.

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Abstract

La présente invention concerne un procédé de purification d'eaux usées par mise en contact des eaux usées à purifier avec un photocatalyseur en TiO2 sous forme de tube qui présente une surface BET de 25 à 200 m2/g, un volume des pores de 0,10 à 1,00 mL/g et un diamètre moyen des pores de 0,005 à 0,050 μm, à l'aide d'une exposition à de la lumière. L'invention concerne également l'utilisation d'un tel photocatalyseur en TiO2 sous forme de tube qui présente une surface BET de 25 à 200 m2/g, un volume des pores de 0,10 à 1,00 mL/g et un diamètre moyen des pores de 0,005 à 0,050 μm pour purifier des eaux usées à l'aide d'une exposition à de la lumière.
EP09738209A 2008-05-02 2009-04-30 Corps moulé en tio2 à activité photocatalytique Withdrawn EP2276704A1 (fr)

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US8323610B2 (en) 2010-04-12 2012-12-04 Basf Se Catalyst for the oxidation of SO2 to SO3
FR2975309A1 (fr) * 2011-05-19 2012-11-23 Centre Nat Rech Scient Monolithe macrocellulaire de dioxyde de titane, procede de preparation, utilisation a titre de photocatalyseur et procede de decontamination
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US6309758B1 (en) * 1999-05-06 2001-10-30 W. R. Grace & Co.-Conn. Promoted porous catalyst
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US20110042326A1 (en) 2011-02-24
IL209053A0 (en) 2011-01-31

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