WO2006075840A1 - Manganese oxide-titania aerogel catalysts, preparing method of the same, and oxidative destruction of chlorinated aromatic compounds using the same - Google Patents

Manganese oxide-titania aerogel catalysts, preparing method of the same, and oxidative destruction of chlorinated aromatic compounds using the same Download PDF

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WO2006075840A1
WO2006075840A1 PCT/KR2005/003623 KR2005003623W WO2006075840A1 WO 2006075840 A1 WO2006075840 A1 WO 2006075840A1 KR 2005003623 W KR2005003623 W KR 2005003623W WO 2006075840 A1 WO2006075840 A1 WO 2006075840A1
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manganese oxide
catalyst
manganese
aerogel
oxide
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PCT/KR2005/003623
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French (fr)
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Dong Jin Suh
Tae Jin Park
Young Hyun Yoon
Jin Soon Choi
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Korea Institute Of Science And Technology
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    • G06Q—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
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    • B01D2255/00—Catalysts
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    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
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    • B01D2255/2073—Manganese
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    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons
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    • 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
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the present invention relates to a manganese oxide-titania aerogel catalyst having high speci fic surface area and porosity, a method of preparing the same and a method of completely oxidatively-decomposing a chlorinated aromatic compound under air condit ions using the catalyst .
  • a chlorinated aromatic compound exhibits toxicity itself and can serve as a chemical generation precursor of polychlorinated biphenyl , polychlorinated dibenzo furan, polychlorinated dibenzo dioxin or the l ike, it has been taken many interests.
  • a catalytic control method of a chlorinated organic material is divided into a hydrodechlorination reaction and an oxidat ion react ion.
  • metal oxide catalysts of noble metals such as platinum, rhodium and pal ladium and the l ike, zero valence metals such as nickel , iron and the l ike, and a variety of transition metals.
  • a Korean Patent Appl ication No. 10-2001-0001198 discloses a hydrodechlorination reaction using a noble metal-supported catalyst .
  • the catalyst costs too much and an activity of the noble metal is decreased due to chlorine poisoning.
  • Many catalysts of the metal oxides have the poisoning problem.
  • chromium which is much used for a decomposition reaction of a chlorinated material , forms Cr ⁇ 2Cl2 (boi l ing point : 117 ° C ) to constraint a l ife span or use of the catalyst .
  • the manganese oxide may serve as a main catalyst or cocatalyst .
  • An aerogle type catalyst has al l the above properties and high thermal stabi l ity, uniformity and degree of dispersion, so that it is used as a catalyst in a variety of reactions [Dong Jin Suh, Tae-Jin Park, Seo-Ho Lee and Kyung-Lim Kim, J . Non-crystal . Sol . 285 (2001) 309 and U.S. Patent No. 6,271, 170] .
  • a non-uniform catalyt ic oxidat ion is a very useful industrial process and has been mainly used for a partial oxidation process for obtaining a chemical product .
  • it has been concerned about a complete oxidation of a low concentration-toxic halogen compound as wel l as a volat i le organic compound.
  • the manganese oxide has an advantage of a complete oxidative decomposit ion because it suppresses production of carbon monoxide and converts al l the carbon sources into the carbon dioxides.
  • An object of the invention is to provide a manganese oxide-titania aerogel catalyst of low cost and high efficiency having high specific surface area and porosity propert ies and high resistance to chlorine poisoning and physical stabi l ity, obtained by performing a supercrit ical drying of manganese oxide-t itania wet gel , which is prepared by a sol-gel method, using carbon dioxide and then firing the dried manganese oxide-t itania, and to provide a method of preparing the catalyst .
  • Another object of the invent ion is to provide an environment-friendly oxidat ive decomposit ion method of a chlorinated aromat ic compound performing an oxidat ion react ion of the chlorinated aromat ic compound under air atmosphere using the manganese oxide-t itania aerogel catalyst to remove a byproduct of the chlorinated material having a high toxicity, thereby improving select ivity to a carbon dioxide of carbon oxides which are products of the oxidat ive decomposit ion.
  • a manganese oxide-t itania aerogel catalyst having an aerogel form dried by a supercrit ical drying method with a micro porosity structure being maintained and having many porosit ies and a wide speci fic surface area and consist ing of a manganese oxide and t itania, a manganese content of the manganese oxide being 1-15 wt% of an overal l catalyst weight .
  • a structure of the t itania is changed into a rut i le structure, so that an act ivity of the catalyst is decreased.
  • a method of preparing a manganese oxide- t itania aerogel catalyst comprising a first step of adding an acid catalyst to a solut ion of alkoxide or non-alkoxide inorganic gel raw material which is a precursor of a manganese oxide and a t itanium oxide and maintaining a temperature to be constant , thereby synthesizing gel ; a second step of maturing the gel prepared in the first step at constant temperature; a third step of solvent-exchanging the gel matured in the second step using carbon dioxides and then drying it via a supercritical process; and a fourth step of removing an organic of the aerogel dried in the third step under inert atmosphere and then heat-treating the aerogel under air or oxygen atmosphere.
  • one or more epoxides selected from a group consisting of ethylene oxide, propylene oxide and butylene oxide may be together used.
  • the acid catalyst in the first step may be at least one selected from a group consisting of hydrochloric acid, nitric acid, acetic acid and oxal ic acid.
  • the precursor of the manganese oxide may be manganese nitrate, manganese acetate or manganese hydrochloride.
  • an oxidative decomposit ion method of a chlorinated aromatic compound wherein the chlorinated aromatic compound is subject to an oxidat ion reaction using the manganese oxide-titania aerogel catalyst .
  • the manganese oxide-titania aerogle catalyst of the invention causes an oxidation react ion of the chlorinated aromat ic compound under air atmosphere to remove the by-product of the chlorinated material having a high toxicity, it is environment-friendly and has the very high conversion rate for the complete oxidation reaction of the chlorinated aromatic compound and high selectivity to the carbon dioxide of the products of the oxidative decomposition and is very thermal ly stable, so that it can be useful ly used in the oxidat ion reaction having a high heating value capable of generating local heat spots .
  • the manganese oxide-titania aerogel catalyst of the invention is provided to a rear end of an incinerator, it is possible to maintain a proper temperature at which the catalyst can exhibit an activity thereof , so that it is efficient in cost reduction.
  • the manganese oxide-titania aerogel catalyst of the invention is not l imi ted to the oxidation reaction of the chlorinated aromatic compound and can be also useful ly used for an oxidation reaction of a volati le organic compound.
  • FIG. 1 is an electron microscope (TEM) photograph of manganese oxide (4 wt% manganese)-t itania aerogel catalyst according to an embodiment of the invent ion;
  • FIGS. 2 and 3 show results of temperature programmed reductions measured so as to compare reduction characteristics of manganese oxide- t itania aerogel catalyst of the invention and manganese dioxide, wherein FIG.
  • FIG. 2 is a graph of temperature programmed reductions of manganese oxide (5 wt% manganese)-titania aerogel catalyst and manganese oxide (10 wt% manganese)- t itania aerogel catalyst according to embodiments of the invention, and FIG.
  • FIG. 4 is a graph comparing a conversion rate of a chlorinated material and a yield of a carbon oxide obtained by oxidation-reacting a chlorinated aromatic compound using a manganese oxide-titania aerogel catalyst according to an embodiment of the invent ion.
  • a method of preparing a manganese oxide-titania aerogel catalyst according to the invent ion is as fol lows.
  • wet gel is formed using a sol-gel method.
  • Alkoxide or non-alkoxide is used as a precursor of a manganese oxide and a titanium oxide.
  • Ethanol or methanol is used as a solvent and a temperature is maintained to be constant .
  • An acid catalyst such as hydrochloric acid, nitric acid, acet ic acid, oxal ic acid and the l ike is added for a structural characteristic of the gel and water of a stoichioraetrical ratio is added for the gel l ing.
  • epoxide such as ethylene oxide, propylene oxide and butylene oxide is used for the gel l ing.
  • the gel is matured.
  • the gel is stabi l ized for a maturat ion period of l ⁇ 30 days at a room temperature under sealed conditions.
  • a refrigeration maturation (4°C ) or high temperature maturation (40 ⁇ 60°C ) may be performed.
  • an aerogel by supercritical-drying the gel using carbon dioxides.
  • an exchange process of l iquid carbon dioxide and the solvent a pressure-increasing process, a temperature-increasing process, a pressure-reducing process and a temperature-reducing process are carried out .
  • the carbon dioxide between the temperature-increasing process and the pressure-reducing process is maintained under supercritical condit ions with a temperature of 40 ⁇ 90°C and a pressure of 100-300 atm. Any supercritical conditions are possible if the conditions are above a crit ical temperature of 31.1°C and a critical pressure of 72.8 atm of the carbon dioxide. Preferably, it is maintained conditions of 50-70 ° C and 150-200 atm.
  • the dried aerogel is heat-treated.
  • a 300 ⁇ 400°C heat treatment is carried out under hel ium or argon atmosphere so to remove an organic and a 500 ⁇ 600°C heat treatment is performed under air or oxygen atmosphere.
  • the speci fic surface area of the aerogel after the heat treatment is 50-200 m /g.
  • a chlorinated aromatic compound such as 1,2-dichlorobenzene is subject to an oxidation reaction using the manganese oxide-titania aerogel catalyst prepared as described above.
  • the catalyst is fi l led in a fixed-bed reactor and then oxygen 20%, nitrogen 80% and 1,2-dichlorobenzen 1,000 ppm are passed to.
  • a spatial speed of the gas in the reaction is 5,000-60,000 h and a reaction temperature is 150 ⁇ 600°C . At this time, a preferred temperature is 450 1 C .
  • a solution was prepared so that a mole rat io of titanium (IV) butoxide (Ti [O(CH 2 )SCHs] 4 ) , water , nitric acid and ethanol was 1:4:0.1:30.
  • To the solution was added manganese nitrate (Mn(NOs) 2 ) so that a content of manganese was 2 wt%, 3 wt%, 4, wt%, 5 wt% and 10 wt%.
  • the gel after the three days of maturat ion was put in a high-pressure reactor and l iquid carbon dioxide was introduced to be exchanged with the ethanol solvent . It was al lowed an exchange time of four hours for sufficient solvent exchange and then it was maintained supercritical condit ions of 60 ° C and 200 atm through processes of increasing pressure and temperature. The carbon dioxide was al lowed to flow so as to remove even a very smal l amount of the solvent with the supercritical condit ions being maintained. After about 6 hours, it was obtained aerogel dried through the processes of reducing pressure and temperature. The aerogel obtained through the supercritical drying process was subject to heat treatment so as to have a metal oxide structure.
  • the aerogel was subject to hel ium treatment (300 ° C , 2 hours) so as to remove an organic and treated under oxygen atmosphere (500 ° C , 2 hours) so as to obtain an oxide. As a result , it was final ly obtained a manganese oxide-titania aerogel catalyst .
  • Fig. 1 is an electron microscope (TEM) photograph of a manganese oxide (4 wt% manganes)-titania aerogel catalyst according to an embodiment of the invention. From the TEM photograph of Fig. 1, it can be seen that the catalyst exhibit a uni form particle dispersion of about 10 nm.
  • TEM electron microscope
  • Figs. 2 and 3 show results of temperature programmed reductions measured so as to compare reduction characteristics of manganese oxide- titania aerogel catalyst of the invention and manganese dioxide, wherein Fig.
  • FIG. 2 is a graph of temperature programmed reductions of manganese oxide (5 wt% manganese) ⁇ titania aerogel catalyst and manganese oxide (10 wt% manganese)- t itania aerogel catalyst according to embodiments of the invention, and FIG.
  • 3 is a graph of a temperature programmed reduction of bulk manganese dioxide.
  • the 0.5g catalyst prepared in the example 1 was fi l led in the fixed-bed reactor and then subject to a reaction so as to examine react ivity thereof for a reaction time of 2 hours at an interval of 50 ° C from 150°C to 600°C , respectively.
  • 1,2-dichlorobenzene was used as a reactant and maintained to be 1,000 ppm.
  • a gas stream having an air composition of oxygen 20% and nitrogen 80% was maintained to be 50 m ⁇ /min. and a heater box was provided to prevent the reactant from being condensed in a tube connected to the reactor .
  • a gas chromatography was used so as to establish a stoichiometry of carbons in the reactant and product .
  • the carbon dioxide and carbon monoxide were measured in a ppm unit using a methanation apparatus.
  • a Table 1 shows conversion rates of 1,2-dichlorobenzene obtained from oxidat ion reaction experiments of the manganese oxide (5 wt% manganese)- titania aerogel catalyst and the manganese oxide (10 wt% manganese)-titania aerogel catalyst .
  • the conversion rate is a value obtained by dividing an amount of 1,2-dichlorobenzene exhausted in the catalytic reaction by an amount of 1,2-dichlorobenzene before the reaction and then multiplying it by 100 for conversion into a percent unit .
  • Fig. 4 is a graph comparing a conversion rate of a chlorinated material and a yield of carbon oxide obtained by oxidation-reacting a chlorinated aromatic compound using manganese oxide-t itania aerogel catalysts prepared in the example 1.
  • O indicates manganese oxide (5 wt% manganese)-titania aerogel catalyst and ⁇ indicates manganese oxide (10 wt% manganese)-titania aerogel catalyst .
  • a solution was prepared so that a mole ratio of titanium (IV) tetrachloride (TiCl 4 ) , water , propylene oxide, nitric acid and ethanol was
  • non-alkoxide was used as the precursor of manganese oxide and t itanium oxide, rather than the alkoxide.
  • the composition and form of manganese oxide-titania aerogel catalyst final ly obtained were almost same or simi lar to the example 1.
  • a Table 2 shows a difference of production amounts, i .e. , selectivity of carbon oxides (carbon monoxide and carbon dioxide) produced when 1 ,2-dichlorobenzene was decomposed in accordance with the weight percent of the manganese in the manganese oxide.
  • a react ion experiment was performed using commercial vanadia-t itania catalyst purchased under same condit ions as the example 1 and it was compared the select ivity of carbon dioxide .
  • the production rat io of the carbon monoxide was below 35% at 350°C or more and below 15% at the reaction condit ion of 450°C or more.
  • the react ion temperature was required so as to decrease the production of the carbon monoxide to 10% or less.
  • the manganese oxide-titania catalyst had better selectivity to the carbon dioxide of the carbon oxides than the vanadia-titania catalyst .
  • the manganese oxide-titania aerogel catalyst of the invention is more efficient as the catalyst for the complete oxidat ive-decomposit ion reaction
  • the manganese oxide-t itania aerogle catalyst of the invention causes an oxidation reaction of the chlorinated aromatic compound under air atmosphere to remove the by-product of the chlorinated material having a high toxicity, it is environment-friendly and has the very high conversion rate for the complete oxidation react ion of the chlorinated aromat ic compound and high select ivity to the carbon dioxide of the products of the oxidative decomposition and is very thermal ly stable, so that it can be useful ly used in the oxidation reaction having a high heating value capable of generating local heat spots.
  • the manganese oxide- titania aerogel catalyst of the invention is provided to a rear end of an incinerator , it is possible to maintain a proper temperature at which the catalyst can exhibit an act ivity thereof , so that it is efficient in cost reduct ion.
  • the manganese oxide-t itania aerogel catalyst of the invention is not l imited to the oxidat ion reaction of the chlorinated aromatic compound and can be also useful ly used for an oxidat ion react ion of a volat i le organic compound.

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Abstract

Disclosed are a manganese oxide-t itania aerogel catalyst having high specific surface area and porosity, a method of preparing the same and a method of completely ox i datively-decomposing a chlorinated aromatic compound using the catalyst under air condition. The manganese oxide-titania aerogel catalyst of the invention is an aerogel form having many porosities and a high specific surface area obtained by performing a supercritical drying of manganese oxide-titania wet gel, which is prepared by a sol-gel method, using carbon dioxide and then firing the dried manganese oxide-titania, with a micro porosity structure being maintained, and consists of manganese oxide and titania wherein a content of the manganese oxide is 1-15 wt% of an overall catalyst weight. Since the manganese oxide-titania aerogle catalyst of the invention has the very high conversion rate for the complete oxidation reaction of the chlorinated aromatic compound and high selectivity to the carbon dioxide of the products of the oxidative decomposition and is very thermally stable, so that it can be usefully used in the oxidation reaction having a high heating value capable of generating local heat spots.

Description

[DESCRIPTION] [ Invent ion Ti t le]
MANGANESE OXIDE-TITANIA AEROGEL CATALYSTS, PREPARING METHOD OF THE SAME, AND OXIDATIVE DESTRUCTION OF CHLORINATED AROMATIC COMPOUNDS USING THE
SAME
[Technical Field]
The present invention relates to a manganese oxide-titania aerogel catalyst having high speci fic surface area and porosity, a method of preparing the same and a method of completely oxidatively-decomposing a chlorinated aromatic compound under air condit ions using the catalyst .
[Background Art]
Since a chlorinated aromatic compound exhibits toxicity itself and can serve as a chemical generation precursor of polychlorinated biphenyl , polychlorinated dibenzo furan, polychlorinated dibenzo dioxin or the l ike, it has been taken many interests. A catalytic control method of a chlorinated organic material is divided into a hydrodechlorination reaction and an oxidat ion react ion. There have been performed researches on metal oxide catalysts of noble metals such as platinum, rhodium and pal ladium and the l ike, zero valence metals such as nickel , iron and the l ike, and a variety of transition metals.
For example, a Korean Patent Appl ication No. 10-2001-0001198 discloses a hydrodechlorination reaction using a noble metal-supported catalyst . However , in this case, it has limitations such that the catalyst costs too much and an activity of the noble metal is decreased due to chlorine poisoning. Many catalysts of the metal oxides have the poisoning problem. For example, it may be possible that chromium, which is much used for a decomposition reaction of a chlorinated material , forms Crθ2Cl2 (boi l ing point : 117°C ) to constraint a l ife span or use of the catalyst .
To the contrary, in case of a manganese oxide, an activity thereof is not decreased even during the reaction for 50 hours or more and a volati le chlorinated material is not formed, so that the manganese oxide has a high possibi l ity of an industrial appl icabi l ity [Yan Liu, Zhaobin Wei , Zhaochi Feng, Mengfei Luo, Pinl iang Ying and Can Li , J . Catal . 202 (2001) 200-204] . As in cases of a halogenated material decomposition using a copper oxide (II) and a manganese oxide (IV) [Korean Patent Appl ication No. 1997-0061340] and a halogenated material decomposition of a catalyst having a manganese oxide and a noble metal supported in a zirconium oxide [U.S. Patent Nos. 5,653,949 and 5,283,041] , the manganese oxide may serve as a main catalyst or cocatalyst .
In the mean time, a catalytic reaction general ly occurs on a surface of the catalyst . Accordingly, the larger a speci fic surface area and the less a resistance to di ffusion between porosities of the catalyst , the higher a reactivity. An aerogle type catalyst has al l the above properties and high thermal stabi l ity, uniformity and degree of dispersion, so that it is used as a catalyst in a variety of reactions [Dong Jin Suh, Tae-Jin Park, Seo-Ho Lee and Kyung-Lim Kim, J . Non-crystal . Sol . 285 (2001) 309 and U.S. Patent No. 6,271, 170] .
A non-uniform catalyt ic oxidat ion is a very useful industrial process and has been mainly used for a partial oxidation process for obtaining a chemical product . However , as it has been increased environment-friendly needs, it has been concerned about a complete oxidation of a low concentration-toxic halogen compound as wel l as a volat i le organic compound. In part icular , the manganese oxide has an advantage of a complete oxidative decomposit ion because it suppresses production of carbon monoxide and converts al l the carbon sources into the carbon dioxides.
[Disclosure]
[Technical Problem]
Accordingly, the present invention has been made to solve the above problems. An object of the invention is to provide a manganese oxide-titania aerogel catalyst of low cost and high efficiency having high specific surface area and porosity propert ies and high resistance to chlorine poisoning and physical stabi l ity, obtained by performing a supercrit ical drying of manganese oxide-t itania wet gel , which is prepared by a sol-gel method, using carbon dioxide and then firing the dried manganese oxide-t itania, and to provide a method of preparing the catalyst .
Another object of the invent ion is to provide an environment-friendly oxidat ive decomposit ion method of a chlorinated aromat ic compound performing an oxidat ion react ion of the chlorinated aromat ic compound under air atmosphere using the manganese oxide-t itania aerogel catalyst to remove a byproduct of the chlorinated material having a high toxicity, thereby improving select ivity to a carbon dioxide of carbon oxides which are products of the oxidat ive decomposit ion.
[Technical Solut ion]
In order to achieve the above objects , there is provided a manganese oxide-t itania aerogel catalyst having an aerogel form dried by a supercrit ical drying method with a micro porosity structure being maintained and having many porosit ies and a wide speci fic surface area and consist ing of a manganese oxide and t itania, a manganese content of the manganese oxide being 1-15 wt% of an overal l catalyst weight . When the content of the manganese is more than 15 wt%, a structure of the t itania is changed into a rut i le structure, so that an act ivity of the catalyst is decreased.
In order to achieve the above objects , according to another aspect of the invent ion, there is provided a method of preparing a manganese oxide- t itania aerogel catalyst , the method comprising a first step of adding an acid catalyst to a solut ion of alkoxide or non-alkoxide inorganic gel raw material which is a precursor of a manganese oxide and a t itanium oxide and maintaining a temperature to be constant , thereby synthesizing gel ; a second step of maturing the gel prepared in the first step at constant temperature; a third step of solvent-exchanging the gel matured in the second step using carbon dioxides and then drying it via a supercritical process; and a fourth step of removing an organic of the aerogel dried in the third step under inert atmosphere and then heat-treating the aerogel under air or oxygen atmosphere.
According to an embodiment of the invention, when the inorganic gel raw material in the first step is non-alkoxide, one or more epoxides selected from a group consisting of ethylene oxide, propylene oxide and butylene oxide may be together used.
According to an embodiment of the invention, the acid catalyst in the first step may be at least one selected from a group consisting of hydrochloric acid, nitric acid, acetic acid and oxal ic acid.
According to an embodiment of the invention, the precursor of the manganese oxide may be manganese nitrate, manganese acetate or manganese hydrochloride.
According to another aspect of the invention, there is provided an oxidative decomposit ion method of a chlorinated aromatic compound wherein the chlorinated aromatic compound is subject to an oxidat ion reaction using the manganese oxide-titania aerogel catalyst .
[Advantageous Effects]
Since the manganese oxide-titania aerogle catalyst of the invention causes an oxidation react ion of the chlorinated aromat ic compound under air atmosphere to remove the by-product of the chlorinated material having a high toxicity, it is environment-friendly and has the very high conversion rate for the complete oxidation reaction of the chlorinated aromatic compound and high selectivity to the carbon dioxide of the products of the oxidative decomposition and is very thermal ly stable, so that it can be useful ly used in the oxidat ion reaction having a high heating value capable of generating local heat spots . In particular , since most of the chlorinated materials are general ly incinerated, when the manganese oxide-titania aerogel catalyst of the invention is provided to a rear end of an incinerator, it is possible to maintain a proper temperature at which the catalyst can exhibit an activity thereof , so that it is efficient in cost reduction.
The manganese oxide-titania aerogel catalyst of the invention is not l imi ted to the oxidation reaction of the chlorinated aromatic compound and can be also useful ly used for an oxidation reaction of a volati le organic compound.
[Description of Drawings]
FIG. 1 is an electron microscope (TEM) photograph of manganese oxide (4 wt% manganese)-t itania aerogel catalyst according to an embodiment of the invent ion;
FIGS. 2 and 3 show results of temperature programmed reductions measured so as to compare reduction characteristics of manganese oxide- t itania aerogel catalyst of the invention and manganese dioxide, wherein FIG.
2 is a graph of temperature programmed reductions of manganese oxide (5 wt% manganese)-titania aerogel catalyst and manganese oxide (10 wt% manganese)- t itania aerogel catalyst according to embodiments of the invention, and FIG.
3 is a graph of a temperature programmed reduction of the manganese dioxide; and
FIG. 4 is a graph comparing a conversion rate of a chlorinated material and a yield of a carbon oxide obtained by oxidation-reacting a chlorinated aromatic compound using a manganese oxide-titania aerogel catalyst according to an embodiment of the invent ion.
[Best Mode]
A method of preparing a manganese oxide-titania aerogel catalyst according to the invent ion is as fol lows.
In a first step, wet gel is formed using a sol-gel method. Alkoxide or non-alkoxide is used as a precursor of a manganese oxide and a titanium oxide. Ethanol or methanol is used as a solvent and a temperature is maintained to be constant . An acid catalyst such as hydrochloric acid, nitric acid, acet ic acid, oxal ic acid and the l ike is added for a structural characteristic of the gel and water of a stoichioraetrical ratio is added for the gel l ing. In case of the non-alkoxide, epoxide such as ethylene oxide, propylene oxide and butylene oxide is used for the gel l ing.
In a second step, the gel is matured. The gel is stabi l ized for a maturat ion period of l~30 days at a room temperature under sealed conditions. In some cases, a refrigeration maturation (4°C ) or high temperature maturation (40~60°C ) may be performed.
In a third step, it is obtained an aerogel by supercritical-drying the gel using carbon dioxides. In the drying process, an exchange process of l iquid carbon dioxide and the solvent , a pressure-increasing process, a temperature-increasing process, a pressure-reducing process and a temperature-reducing process are carried out . The carbon dioxide between the temperature-increasing process and the pressure-reducing process is maintained under supercritical condit ions with a temperature of 40~90°C and a pressure of 100-300 atm. Any supercritical conditions are possible if the conditions are above a crit ical temperature of 31.1°C and a critical pressure of 72.8 atm of the carbon dioxide. Preferably, it is maintained conditions of 50-70°C and 150-200 atm. A specific surface area of the aerogel after the
2 drying is about 600-700 m /g.
In a fourth step, the dried aerogel is heat-treated. A 300~400°C heat treatment is carried out under hel ium or argon atmosphere so to remove an organic and a 500~600°C heat treatment is performed under air or oxygen atmosphere. The speci fic surface area of the aerogel after the heat treatment is 50-200 m /g.
A chlorinated aromatic compound such as 1,2-dichlorobenzene is subject to an oxidation reaction using the manganese oxide-titania aerogel catalyst prepared as described above. The catalyst is fi l led in a fixed-bed reactor and then oxygen 20%, nitrogen 80% and 1,2-dichlorobenzen 1,000 ppm are passed to. A spatial speed of the gas in the reaction is 5,000-60,000 h and a reaction temperature is 150~600°C . At this time, a preferred temperature is 4501C .
[Mode for Invent ion]
Hereinafter , the invention wi l l be more speci fical ly described with reference to preferred embodiments. However , it should be noted that the embodiments are provided only to i l lustrate the invention and the invention is not l imited thereto.
<Example 1: Preparation of manganese oxide-titania aerogel catalyst (alkoxide was used)>
A solution was prepared so that a mole rat io of titanium (IV) butoxide (Ti [O(CH2)SCHs]4) , water , nitric acid and ethanol was 1:4:0.1:30. To the solution was added manganese nitrate (Mn(NOs)2) so that a content of manganese was 2 wt%, 3 wt%, 4, wt%, 5 wt% and 10 wt%. When gel was formed through a st irring for a predetermined t ime, the stirring was stopped and then the gel was matured at a room temperature. The gel after the three days of maturat ion was put in a high-pressure reactor and l iquid carbon dioxide was introduced to be exchanged with the ethanol solvent . It was al lowed an exchange time of four hours for sufficient solvent exchange and then it was maintained supercritical condit ions of 60°C and 200 atm through processes of increasing pressure and temperature. The carbon dioxide was al lowed to flow so as to remove even a very smal l amount of the solvent with the supercritical condit ions being maintained. After about 6 hours, it was obtained aerogel dried through the processes of reducing pressure and temperature. The aerogel obtained through the supercritical drying process was subject to heat treatment so as to have a metal oxide structure. The aerogel was subject to hel ium treatment (300°C , 2 hours) so as to remove an organic and treated under oxygen atmosphere (500°C , 2 hours) so as to obtain an oxide. As a result , it was final ly obtained a manganese oxide-titania aerogel catalyst . O
Fig. 1 is an electron microscope (TEM) photograph of a manganese oxide (4 wt% manganes)-titania aerogel catalyst according to an embodiment of the invention. From the TEM photograph of Fig. 1, it can be seen that the catalyst exhibit a uni form particle dispersion of about 10 nm.
Figs. 2 and 3 show results of temperature programmed reductions measured so as to compare reduction characteristics of manganese oxide- titania aerogel catalyst of the invention and manganese dioxide, wherein Fig.
2 is a graph of temperature programmed reductions of manganese oxide (5 wt% manganese)~titania aerogel catalyst and manganese oxide (10 wt% manganese)- t itania aerogel catalyst according to embodiments of the invention, and FIG.
3 is a graph of a temperature programmed reduction of bulk manganese dioxide.
As shown in Fig. 2, it could be seen that the reduction characteristic of the manganese oxide-t itania aerogel catalyst was different from that of the bulk manganese dioxide of Fig. 3 due to the interaction of the manganese oxide formed on the surface of the titania and the titania. In addition, with regard to the oxidat ion states of the manganese oxide in the manganese oxide-t itania aerogel catalyst , it could be seen through a X-ray photoelectron spectrum (XPS) that there was a four-valence state 60% or more.
<Experimental example 1: Oxidation reaction of chlorinated aromatic compound>
It was measured a conversion rate and a selectivity of the catalysts prepared in the example 1 for a chlorinated aromatic compound in an oxidation reaction.
Specifical ly, the 0.5g catalyst prepared in the example 1 was fi l led in the fixed-bed reactor and then subject to a reaction so as to examine react ivity thereof for a reaction time of 2 hours at an interval of 50°C from 150°C to 600°C , respectively. 1,2-dichlorobenzene was used as a reactant and maintained to be 1,000 ppm. A gas stream having an air composition of oxygen 20% and nitrogen 80% was maintained to be 50 m^/min. and a heater box was provided to prevent the reactant from being condensed in a tube connected to the reactor . A gas chromatography was used so as to establish a stoichiometry of carbons in the reactant and product . In particular, the carbon dioxide and carbon monoxide were measured in a ppm unit using a methanation apparatus.
A Table 1 shows conversion rates of 1,2-dichlorobenzene obtained from oxidat ion reaction experiments of the manganese oxide (5 wt% manganese)- titania aerogel catalyst and the manganese oxide (10 wt% manganese)-titania aerogel catalyst . The conversion rate is a value obtained by dividing an amount of 1,2-dichlorobenzene exhausted in the catalytic reaction by an amount of 1,2-dichlorobenzene before the reaction and then multiplying it by 100 for conversion into a percent unit .
[Table 1]
Figure imgf000010_0001
As can be seen from the Table 1, as the reaction temperature was increased, an oxidat ive reactivity of 1,2-dichlorobenzene was increased, so that the manganese oxide (5 wt% manganese)-titania aerogel catalyst exhibited 85% of conversion rate and the manganese oxide (10 wt% manganese)-titania aerogel catalyst exhibited 99.5% or more of conversion rate at 500°C . Fig. 4 is a graph comparing a conversion rate of a chlorinated material and a yield of carbon oxide obtained by oxidation-reacting a chlorinated aromatic compound using manganese oxide-t itania aerogel catalysts prepared in the example 1. In Fig. 4, O indicates manganese oxide (5 wt% manganese)-titania aerogel catalyst and Δ indicates manganese oxide (10 wt% manganese)-titania aerogel catalyst .
In Fig. 4, the conversion rate of 1,2-dichlorobenzene and the yield of the carbon oxide show a l inear relationship of about 1: 1. Accordingly, it can be seen that the chlorinated material was wel l decomposed into the carbon oxide without a by product .
<Example 2: Preparation of manganese oxide-titania aerogel catalyst (non-alkoxide was used)>
A solution was prepared so that a mole ratio of titanium (IV) tetrachloride (TiCl4) , water , propylene oxide, nitric acid and ethanol was
1:4:4:0.1:30. To the solut ion was added manganese nitrate (Mn(NOa)2) so that a content of manganese was 2 wt%, 3 wt%, 4, wt%, 5 wt% and 10 wt%. When gel was formed through a stirring for a predetermined time, the stirring was stopped and then the gel was matured at a room temperature. The subsequent supercrit ical drying and heat treatment processes were same as in the example 1.
In the example 2, non-alkoxide was used as the precursor of manganese oxide and t itanium oxide, rather than the alkoxide. However , the composition and form of manganese oxide-titania aerogel catalyst final ly obtained were almost same or simi lar to the example 1.
As a result , the conversion rate of the manganese oxide-titania aerogel catalyst prepared in the example 2 for the chlorinated aromatic compound in the oxidation reaction was almost simi lar to the example 1.
In addition, a Table 2 shows a difference of production amounts, i .e. , selectivity of carbon oxides (carbon monoxide and carbon dioxide) produced when 1 ,2-dichlorobenzene was decomposed in accordance with the weight percent of the manganese in the manganese oxide.
[Table 2]
Figure imgf000012_0001
As can be seen from the Table 2, in case of manganese oxide (10 wt% manganese)-t itania catalyst , i t was possible to increase the select ivity of the carbon dioxide up to 95% or more at 500°C .
"Comparison example 1>
A react ion experiment was performed using commercial vanadia-t itania catalyst purchased under same condit ions as the example 1 and it was compared the select ivity of carbon dioxide .
As a resul t , in the react ion of the commercial vanadia-t itania catalyst having a high decomposit ion react ivity for the chlorinated aromat ic compound, 35% or more of carbon dioxide was produced in the react ions from ±0
150O to 600°C . To the contrary, in case of the manganese oxide (10 wt% manganese, refer to the Table 2)-titania aerogel catalyst , the production rat io of the carbon monoxide was below 35% at 350°C or more and below 15% at the reaction condit ion of 450°C or more. However , it was required the react ion temperature of 500°C or more so as to decrease the production of the carbon monoxide to 10% or less.
Through the result , it was val idated that the manganese oxide-titania catalyst had better selectivity to the carbon dioxide of the carbon oxides than the vanadia-titania catalyst .
Accordingly, it can be seen that the manganese oxide-titania aerogel catalyst of the invention is more efficient as the catalyst for the complete oxidat ive-decomposit ion reaction,
Whi le the invention has been shown and described with reference to certain preferred embodiments thereof , it wi l l be understood by those ski l led in the art that various changes in form and detai ls may be made thereto without departing from the spirit and scope of the invention as defined by the appended claims.
[Industrial Appl icabi l ity]
As described above, since the manganese oxide-t itania aerogle catalyst of the invention causes an oxidation reaction of the chlorinated aromatic compound under air atmosphere to remove the by-product of the chlorinated material having a high toxicity, it is environment-friendly and has the very high conversion rate for the complete oxidation react ion of the chlorinated aromat ic compound and high select ivity to the carbon dioxide of the products of the oxidative decomposition and is very thermal ly stable, so that it can be useful ly used in the oxidation reaction having a high heating value capable of generating local heat spots. In particular , since most of the chlorinated materials are general ly incinerated, when the manganese oxide- titania aerogel catalyst of the invention is provided to a rear end of an incinerator , it is possible to maintain a proper temperature at which the catalyst can exhibit an act ivity thereof , so that it is efficient in cost reduct ion.
The manganese oxide-t itania aerogel catalyst of the invention is not l imited to the oxidat ion reaction of the chlorinated aromatic compound and can be also useful ly used for an oxidat ion react ion of a volat i le organic compound.

Claims

[CLAIMS]
[Claim 1]
A manganese oxide-t itania aerogel catalyst having an aerogel form dried by a supercrit ical drying method with a micro porosity structure being maintained and having many porosit ies and a wide speci fic surface area, and consist ing of a manganese oxide and t itania, a manganese content of the manganese oxide being 1-15 wt% of an overal l catalyst weight .
[Claim 2]
A method of preparing a manganese oxide-t itania aerogel catalyst , the method comprising: a first step of adding an acid catalyst to a solut ion of alkoxide or non-alkoxide inorganic gel raw material which is a precursor of a manganese oxide and a t itanium oxide and maintaining a temperature to be constant , thereby synthesizing gel ; a second step of maturing the gel prepared in the first step at constant temperature; a third step of solvent-exchanging the gel matured in the second step using carbon dioxides and then drying it via a supercrit ical process; and a fourth step of removing an organic of the aerogel dried in the third step under inert atmosphere and then heat-treat ing the aerogel under air or oxygen atmosphere.
[Claim 3]
The method according to claim 2, wherein when the inorganic gel raw material in the first step is non-alkoxide, one or more epoxides selected from a group consist ing of ethylene oxide, propylene oxide and butylene oxide are together used.
[Claim 4]
The method according to claim 2, wherein the acid catalyst in the first step is at least one selected from a group consisting of hydrochloric acid, nitric acid, acetic acid and oxal ic acid.
[Claim 5]
The method according to claim 2, wherein the precursor of the manganese oxide is manganese nitrate, manganese acetate or manganese hydrochloride.
[Claim 6]
An oxidative decomposition method of a chlorinated aromatic compound wherein the chlorinated aromatic compound is subject to an oxidation reaction using the manganese oxide-titania aerogel catalyst according to claim 1.
[Claim 7]
The method according to claim 6, wherein the manganese-titania aerogel catalyst is used to improve select ivity to carbon dioxide of products of the oxidat ive decomposition.
PCT/KR2005/003623 2005-01-11 2005-11-29 Manganese oxide-titania aerogel catalysts, preparing method of the same, and oxidative destruction of chlorinated aromatic compounds using the same WO2006075840A1 (en)

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