WO2006083142A1 - A catalyst for the disintegration of vapor phase organic compounds and for the organic synthesis from carbon dioxide and water - Google Patents

A catalyst for the disintegration of vapor phase organic compounds and for the organic synthesis from carbon dioxide and water Download PDF

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WO2006083142A1
WO2006083142A1 PCT/KR2006/000426 KR2006000426W WO2006083142A1 WO 2006083142 A1 WO2006083142 A1 WO 2006083142A1 KR 2006000426 W KR2006000426 W KR 2006000426W WO 2006083142 A1 WO2006083142 A1 WO 2006083142A1
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catalyst
compounds
water
weight
lewis acid
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Young Sang Cho
Jae Ik Kim
Jae Chun Oh
Ju Hee Kim
So Young Kim
Yoon Hee Lee
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Korea Institute of Science and Technology KIST
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    • 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
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • 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
    • B01J23/72—Copper
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/04—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of inorganic compounds
    • C01B3/042—Decomposition of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to ceramic catalysts for decomposition of water to produce hydrogen, decomposition of vapor phase organic compounds, and organic synthesis through the reaction between carbon dioxide and water. More particularly, the present invention relates to a mixture of compounds that can be isolated by a Lewis acid, metal compounds that can offer an electron pair to a Lewis acid, transition metals or transition metal oxides, and electrolytes that can transfer electrons, decompose vapor phase organic compounds, and synthesize organic materials through the reaction between carbon dioxide and water.
  • the conventional catalysts that produce hydrogen by decomposing water or those that synthesize organic compounds such as methane by reacting carbon dioxide with water required supply of light.
  • water and carbon dioxides that are well dispersed with the catalysts were first injected into a reactor, which allows light to penetrate, then was followed by irradiation process by which concentrated light is irradiated on convex lens, a concave mirror and the like.
  • the object of the present invention is to overcome the problems of the conventional technology and is to provide catalysts that can decompose vapor organic compounds at a temperature of 100 0 C or lower and those that can synthesize organic compounds through the reaction between water and carbon dioxide at 100 0 C or higher without using a special system for light irradiation, thereby providing economically advantageous catalysts.
  • the catalysts of the present invention which have various uses, can decompose water into hydrogen and hydroxyl radical, and can decompose vapor phase organic compounds through the reaction with the decomposed species of water on their surface at a low temperature of 100 ° C or lower, particularly at a room temperature (around 25 0 C), and can synthesize organic compounds by reacting water with carbon dioxides at a medium/high temperature of 100 0 C or higher.
  • the catalysts according to the present invention are relatively inexpensive since the catalysts comprise a mixture of raw materials for catalysts such as Lewis acids and metal oxides. Therefore, particularly for water decomposition and organic synthesis through the reaction between carbon dioxide and water without light, since exhaust heat, carbon dioxides and steam produced from industrial sites can be used, the cost of production of hydrogen energy and energy from synthesized organic materials are expected to significantly decrease, and its economic efficiency is expected to be very high. Moreover, by achieving a remarkably more efficient property for the decomposition of vapor phase organic compounds, the industrial applicability of the catalysts, such as in the removal of odor-causing materials at room temperature, is expected to be significantly enhanced.
  • Figure 1 represents a schematic view of an experimental apparatus that is used for decomposition of vapor phase organic compounds and organic synthesis using the catalysts of the present invention.
  • the present invention relates to ceramic catalysts that are prepared by mixing and calcining raw materials, and they are characterized in that they can decompose water to produce active hydrogen and hydroxyl radicals, decompose vapor phase organic compounds through the reaction with active hydrogen and hydroxyl radicals at a low temperature of 100 0 C or below, and synthesize organic compounds by reacting water with carbon dioxide at temperature of 100 0 C or higher.
  • a Lewis acid uses water as a Lewis base to decompose water using the following presumptive reaction process.
  • the hydroxyl radical, active hydrogen, active oxygen and the like can decompose vapor phase organic compounds at a low temperature of 10O 0 C or below and can synthesize organic compounds at a medium/high temperature of 10O 0 C or higher.
  • the applicants of the present invention could observe that when the compounds composed of hydrophilic functional groups, that can offer electron pairs, such as oxides, hydroxides, sulfates, etc. and of alkaline metals or of alkaline earth metals are added to the Lewis acid, water decomposition or reaction between water and carbon dioxide can be induced by increasing the Lewis basicity, as shown in the following example.
  • LA e + M + -> : LA: + M + LB - M + H 2 O ⁇ MOH + 1 AH 2 T LB - + MOH ⁇ MLB + OH - OH • + OH - -> H 2 O + ⁇ ⁇ 0 2 t
  • the applicants of the present invention also discovered that when transition metal compounds were -added to the Lewis acid to be used for catalysts for reaction between water and carbon dioxide, the electrons on the metal surface of the Lewis acid migrated, thereby making organic synthesis at the surface of transition metal possible, promoting the production of a wider range of the types of organic compounds and improving the conversion rate of the carbon dioxides.
  • the ceramic catalysts according to the present invention that can decompose vapor phase organic compounds at a temperature of 10O 0 C or lower and synthesize organic compounds by reacting carbon dioxide with water at a temperature of 100 0 C or higher could only comprise compounds that can be isolated by a Lewis acid.
  • Lewis acid can be any one or a mixture of two or more from the group consisting of: natural minerals such as kaolinite, bentonite, attapulgite, zeolite, montmorillonite; oxides such as zinc oxide (ZnO) 1 aluminum oxide (AI 2 O 3 ), titanium dioxide (TiO 2 ), cerium oxide (CeO 2 ), vanadium pentoxide (V 2 O 5 ), silicon dioxide (SiO 2 ), chromium oxide (Cr 2 ⁇ 3); sulfates such as calcium sulfate (CaSO-O, manganese sulfate (MnSO 4 ), nickel sulfate (NiSO 4 ), copper sulfate (CuSO 4 ), cobalt sulfate (CoSO 4 ), cadmium sulfate (CdSO 4 ), magnesium sulfate (MgSO 4 ), iron sulfate (FeSO 4 ), aluminum sulfate (AI 2 O
  • the catalysts of the present invention can include metal compounds which can provide an electron pair to the Lewis acid in addition to being able to be isolated by the Lewis acid.
  • the Lewis acid is less than 20 weight %, the catalyst efficiency is significantly reduced.
  • the Lewis acid is more than 99.9 weight %, the efficacy of the catalysts due to combination with the metal oxides is insignificant. It is more preferable to use 60 to 95 weight % of the Lewis acid.
  • the catalyst efficiency is not improved and is even reduced when more than 80 weight % is used.
  • the metal compound that act as a Lewis base can be any one or a mixture of two or more from the group consisting of: sulfates (e.g., Li 2 SO 4 , Na 2 SO 4 ), sulfites (e.g., Li 2 SO 3 , Na 2 SO 3 ), phosphates (e.g., Li 3 PO 4 , Na 3 PO 4 ), nitrates (e.g., LiNO 3 , NaNO 3 ), nitrites (e.g., LiNO 2 , NaNO 2 ), hydroxides (e.g., LiOH, NaOH), oxides (e.g., Li 2 O, Na 2 O), peroxides (e.g., Na 2 O 2 ), superoxides (e.g., KO 2 , RbO 2 , CsO 2 ) of an alkaline metal; and sulfates (e.g., MgSO 4 , CaSO 4 ), sulfites (e.g.,
  • ceramic catalysts that are well dispersed with the metal compounds in the ceramic layers can be formed when the metal compounds are first dissolved in the water, mixed with Lewis acids and then are dried.
  • the catalysts of the present invention not only can be isolated by the Lewis acid but also can contain transition metal compounds. In this case, it is preferable to use 20 to 99.9 weight % of the compounds that can be isolated by the Lewis acid and 0.1 to 80 weight % of the transition metal compounds. When the Lewis acid is less than 20 weight %, the efficiency of the catalysts are significantly reduced. However, when the Lewis acid is more than 99.9 weight %, the catalyst efficiency according to the combination of the metal oxides is insignificant. It is more preferable to include 60 to 95 weight % of the Lewis acid. In addition, when less than 0.1 weight % of metal compounds is used, the catalyst efficiency does not show improvement and is even reduced when more than 80 weight% is used.
  • the transition metal compounds are hydrophilic compounds which can be any one or a mixture of two or more from the group consisting of: sulfate (e.g., MnSO 4 , CoSO 4 , ZnSO 4 , CuSO 4 ), sulfite (e.g., MnSO 3 , CoSO 3 , ZnSO 3 , CuSO 3 ), phosphate (e.g., Mn 3 (PO 4 J 2 , Co 3 (PO 4 ) 2 , Zn 3 (PO 4 J 2 , Cu 3 (PO 4 J 2 ), nitrate (e.g., Mn(NO 3 ) 2) CO(NO 3 J 2 , Zn(NO 3 ) 2 , Cu(NO 3 ) 2 ), nitrite (e.g., Mn(NO 2 J 2 , Co(NO 2 J 2 , Zn(NO 2 J 2 , Cu(NO 2 J 1 hydroxide (e.g., Mn(OH) 2 , Co(OH) 2 ,
  • the compounds When the compounds are calcined, they are decomposed mostly into metal oxides (e.g. MnO, Mn 2 O 3 , MnO 2 ) or metals (e.g. Pd., Pt). Therefore, ceramic catalysts that are well dispersed with metal oxides or metals in the ceramic layers can be formed when the metal compounds are first dissolved in the water, mixed with ceramic raw materials and then are calcined.
  • metal oxides e.g. MnO, Mn 2 O 3 , MnO 2
  • metals e.g. Pd., Pt
  • the ceramic catalyst of the present invention can be provided by comprising a mixture of compounds that can be isolated by a Lewis acid, the metal compounds and the transition metal compounds.
  • the Lewis acid is less than 20 weight %, the catalyst efficiency is significantly reduced; however, when the Lewis acid is more than 99.9 weight %, the catalyst efficiency with the combination with the metal oxides is insignificant. It is more preferable to comprise 60 to 95 weight % of the Lewis acid.
  • the ceramic catalysts of the present invention can be provided by using a mixture of the compounds that can be isolated by the Lewis acid and electrolytes. In this case, it is preferable to add an amount of less than 0.1 to 30 weight parts of the electrolytes compared to the compounds that can be isolated by the Lewis acid having 100 parts. When less than 0.1 weight part of the electrolyte is added, there is no improvement of the efficiency of the catalyst of the present invention. Further, when more than 30 weight parts of the electrolyte are added, the catalyst efficiency was even reduced.
  • the electrolyte should be easily ionized such that it promotes transfer of electric charges, and for which mineral (inorganic) acids and its bases are generally used, which can be any one or a mixture of two or more from the group consisting of chloride (e.g., NaCI, KCI), nitrate (e.g., NaNO 3 , KNO 3 ), sulfate (e.g., Na 2 SO 4 , K 2 SO 4 ), carbonate (e.g., Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 ), phosphate (e.g., NaH 2 PO 4 , Na 2 HPO 4 ) of an alkaline metal and chloride (e.g., CuCI 2 , NiCI 2 ), nitrate (e.g., Cu(NO 3 ) 2 , Ni(NO 3 J 2 ), sulfate (e.g.
  • chloride e.g., NaCI, KCI
  • nitrate e.g., Na
  • the ceramic catalysts of the present invention can be a mixture of compounds that can be isolated by the Lewis acid, the metal compounds and the electrolytes. In this case, it is preferable to mix 20 to 99.9 weight % of the compounds that can be isolated by the Lewis acid and 0.1 to 80 weight % of the metal compounds that can provide an electron pair to the Lewis acid, followed by adding 0.1 to 30 weight parts of the electrolytes to the mixture having 100 parts.
  • the Lewis acid is less than 20 weight %, the catalyst efficiency is significantly reduced; however, when more than 99.9 weight % of the Lewis acid is included, the catalyst efficiency in combination with the metal oxides is insignificant.
  • an amount of 0.1 weight % or less of the metal compounds is included, there is no improvement of the catalyst efficiency and the characterization of the catalysts is even reduced when more than 80 weight% is used.
  • less than 0.1 weight parts of the electrolytes were added to the mixture having 100 parts, there was no improvement in the characterization of the catalysts, and the same was also shown when more than 30 weight parts were added.
  • the ceramic catalysts of the present invention can be a mixture of the compounds that can be isolated by the Lewis acid, the transition metal compounds and the electrolytes.
  • the Lewis acid is less than 20 weight %, the efficiency of the catalysts are significantly reduced.
  • the Lewis acid is more than 99.9 weight %, the improved efficiency of the catalysts with combination with the metal oxides is insignificant. It is more preferable to mix 60 to 95 weight % of the Lewis acid.
  • the ceramic catalysts of the present invention can be a mixture of the compounds that can be isolated by the Lewis acid, the metal compounds, the transition metal compounds and the electrolytes.
  • the efficiency of the catalysts are significantly reduced; however, when the amount of the Lewis acid added is more than 99.9 weight %, the efficiency of the catalysts is insignificant. It is more preferable to add 60 to 95 weight % of the Lewis acid.
  • less than 0.1 weight % of the metal compounds is added, there is no improvement of the characterization of the catalysts and the same result is shown when more than 80 weight% is added.
  • an amount of less than 0.1 weight parts of the transition metal compounds was added to the mixture, there was no improvement of the properties of the catalysts, and no improvement of the catalyst properties was also shown when more than 50 weight parts were added.
  • less than 0.1 weight parts of the electrolytes were added there was no improvement of the efficiency of the catalysts, and the efficiency even reduced when more than 30 weight parts were added.
  • A. Decomposition of Vapor Phase Organic Compounds The Lewis acid catalysts were crushed into particles having an average size of 1 mi or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5in£/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography (10)(HP-5890) and the results thereof are shown in Table 1.
  • Example 2 Reactions to Addition of Metal Compounds 95 parts by weight of alumina Lewis acid raw material and 5 parts by weight of metal compounds were mixed to prepare a mixture of raw material of ceramic catalysts. 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped into a cylinder shape having a diameter of 3cm and a length of 10cm. The shaped mixture was dried at room temperature for 72 hours and then was calcined using electric furnace at 1 ,100 0 C for 12 hours and then was cooled at room temperature, thereby obtaining ceramic catalysts.
  • A. Decomposition of Vapor Phase Organic Compounds The Lewis acid catalysts were crushed into particles having an average size of the particles are 1mm or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5in4/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography (10)(HP-5890) and the results thereof are shown in Table 4.
  • Example 3 Reactions to the Addition of Transition Metal Compounds 1 95 parts by weight of alumina Lewis acid raw material and 5 parts by weight of metat compounds were mixed to prepare a mixture of raw material of ceramic catalysts. 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped into a cylinder shape having a diameter of 3cm and a length of 10cm. The shaped mixture was dried at room temperature for 72 hours and then was calcined using electric furnace at 1 ,100O for 12 hours and then was cooled at room temperature, thereby obtaining ceramic catalysts.
  • A. Decomposition of Vapor Phase Organic Compounds The cylinder shape ceramic catalysts were crushed into particles having an average size of the particles are 1 mm or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5in£/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography(10)(HP-5890) and the results thereof are shown in Table 7.
  • Example 4 Reactions to the Addition of Transition Metal Compounds 2 95 parts by weight of alumina Lewis acid raw material and 5 parts by weight of calcium hydroxides (Ca(OH)2) were mixed then 90 parts of the mixture and 10 parts of the transition metal compounds were added to prepare a mixture of raw material of ceramic catalysts. 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped into a cylinder shape having a diameter of 3cm and a length of 10cm. The shaped mixture was dried at room temperature for 72 hours and then was calcined using electric furnace at 1 ,10Ot: for 12 hours and then was cooled at room temperature, thereby obtaining ceramic catalysts.
  • alumina Lewis acid raw material and 5 parts by weight of calcium hydroxides (Ca(OH)2) were mixed then 90 parts of the mixture and 10 parts of the transition metal compounds were added to prepare a mixture of raw material of ceramic catalysts. 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped
  • A. Decomposition of Vapor Phase Organic Compounds The ceramic catalysts were crushed into particles having an average size of the particles are 1mm or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5in£/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography (10)(HP-5890) and the results thereof are shown in Table 10.
  • A. Decomposition of Vapor Phase Organic Compounds The ceramic catalysts were crushed into particles having an average size of the particles are 1 mm or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5m4/mi ⁇ while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography (10)(HP-5890) and the results thereof are shown in Table 13.
  • Example 6 Reactions to Addition of Electrolytes 2 95 parts by weight of alumina Lewis acid raw material and 5 parts by weight of sodium hydroxide (NaOH) were mixed, then 94 parts of the resulting mixture and 6 parts of the electrolytes were added to prepare a mixture of raw materials of ceramic catalysts. 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped into a cylinder shape having a diameter of 3cm and a length of 10cm. The shaped mixture was dried at room temperature for 72 hours and then was calcined using electric furnace at 900 0 C for 12 hours and then was cooled at room temperature, thereby obtaining ceramic catalysts.
  • NaOH sodium hydroxide
  • A. Decomposition of Vapor Phase Organic Compounds The ceramic catalysts were crushed into particles having an average size of the particles are 1 oi ⁇ i or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5in£/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography (10)(HP-5890) and the results thereof are shown in Table 16.
  • A. Decomposition of Vapor Phase Organic Compounds The ceramic catalysts were crushed into particles having an average size of the particles are Inim or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5m4/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography(10)(HP-5890) and the results thereof are shown in Table 19.
  • alumina Lewis acid raw material 90 parts by weight of alumina Lewis acid raw material and 5 parts by weight of metal compounds sodium hydroxide were mixed then 5 parts of zinc sulfates (ZnSO4) were added followed by adding 6 parts of the following electrolytes to 94 parts of the resulting mixture there from to prepare a mixture of raw materials of ceramic catalysts.
  • ZnSO4 zinc sulfates
  • 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped into a cylinder shape having a diameter of 3cm and a length of 10cm.
  • the shaped mixture was dried at room temperature for 72 hours and then was calcined using electric furnace at 900 0 C for 12 hours and then was cooled at room temperature, thereby obtaining ceramic catalysts.
  • A. Decomposition of Vapor Phase Organic Compounds The ceramic catalysts were crushed into particles having an average size of the particles are 1mm or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5m£/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propyonaldehyde was measured using Gas Chromatography(10)(HP-5890) and the results thereof are shown in Table 22.
  • the catalysts of the present invention which have various uses and can disperse soluble electrolyte salts in a raw material for the catalysts, can decompose water to produce hydrogen, can decompose vapor phase organic compounds at a low temperature of 100 "C or lower, particularly at a room temperature (around 25 "C) and can synthesize organic compounds by reacting water with carbon dioxide at a medium/high temperature of 100 1 C or higher.
  • the catalysts of the present invention comprise of a mixture of catalyst raw material such as a Lewis acid which is relatively inexpensive and metal oxides, thereby having a characteristic that the cost of the catalysts are low. Therefore, particularly for water decomposition and organic synthesis through the reaction between carbon dioxide and water without light, since exhaust heat, carbon dioxides and steam produced from industrial sites can be used, the cost of production of hydrogen energy and energy from synthesized organic materials are expected to significantly decrease, and its economic efficiency is expected to be very high. Moreover, by achieving a remarkably more efficient property for the decomposition of vapor phase organic compounds, the industrial applicability of the catalysts, such as in the removal of odor-causing materials at room temperature, is expected to be significantly enhanced.
  • catalyst raw material such as a Lewis acid which is relatively inexpensive and metal oxides

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Abstract

The present invention provides catalysts that comprise a mixture of compounds that can be isolated by a Lewis acid, metal compounds that can offer an electron pair to a Lewis acid, transition metals or transition metal oxides, and electrolytes that can decompose vapor phase organic compounds, produce hydrogen by decomposing water, and synthesize organic materials by reacting water with carbon dioxide.

Description

DESCRIPTION
[Title of Invention]
A CATALYST FOR THE DISINTEGRATION OF VAPOR PHASE ORGANIC COMPOUNDS AND FOR THE ORGANIC SYNTHESIS FROM CARBON DIOXIDE AND WATER
[Technical Field]
The present invention relates to ceramic catalysts for decomposition of water to produce hydrogen, decomposition of vapor phase organic compounds, and organic synthesis through the reaction between carbon dioxide and water. More particularly, the present invention relates to a mixture of compounds that can be isolated by a Lewis acid, metal compounds that can offer an electron pair to a Lewis acid, transition metals or transition metal oxides, and electrolytes that can transfer electrons, decompose vapor phase organic compounds, and synthesize organic materials through the reaction between carbon dioxide and water.
[Background Art]
Conventional catalysts for the decomposition of vapor phase organic compounds including odor-causing materials are generally capable of expressing their functions at 100 °C or above and, as a result, their applications were often limited. (Japan Patent Publication No. 2001 -38207, US Patent No. 6,344,987BZ). Therefore, it is not practically possible to use these catalysts to decompose odor or volatile materials at the temperature of 100°C or lower. In order to be able to use them, vapor compounds were reacted under a process condition of 100°C or higher or were artificially heated to obtain a temperature of 100°C or higher. As a result, not only the applicability of the catalysts became very limited, but decomposition of the vapor compounds also became costly.
In addition, the conventional catalysts that produce hydrogen by decomposing water or those that synthesize organic compounds such as methane by reacting carbon dioxide with water required supply of light. In order to be able to use these photo catalysts, water and carbon dioxides that are well dispersed with the catalysts were first injected into a reactor, which allows light to penetrate, then was followed by irradiation process by which concentrated light is irradiated on convex lens, a concave mirror and the like. (Science 297 (2002) p2243, Applied Catalysis. A: General 249 (2003) p11). Accordingly, when synthesizing organic compounds from carbon dioxide and water by using photo catalysts, a specially designed light penetrating reactor which can efficiently carry out light irradiation and efficient dispersion of the photo catalysts and the like are necessary. As a result, not only the existing technical difficulties of putting these photo catalysts into practical use, but also the high cost of using a special system for light irradiation need to be overcome.
[Disclosure] [Technical Problem]
The object of the present invention is to overcome the problems of the conventional technology and is to provide catalysts that can decompose vapor organic compounds at a temperature of 1000C or lower and those that can synthesize organic compounds through the reaction between water and carbon dioxide at 1000C or higher without using a special system for light irradiation, thereby providing economically advantageous catalysts.
[Technical Solution]
The catalysts of the present invention, which have various uses, can decompose water into hydrogen and hydroxyl radical, and can decompose vapor phase organic compounds through the reaction with the decomposed species of water on their surface at a low temperature of 100°C or lower, particularly at a room temperature (around 250C), and can synthesize organic compounds by reacting water with carbon dioxides at a medium/high temperature of 1000C or higher.
In other words, the catalysts according to the present invention are relatively inexpensive since the catalysts comprise a mixture of raw materials for catalysts such as Lewis acids and metal oxides. Therefore, particularly for water decomposition and organic synthesis through the reaction between carbon dioxide and water without light, since exhaust heat, carbon dioxides and steam produced from industrial sites can be used, the cost of production of hydrogen energy and energy from synthesized organic materials are expected to significantly decrease, and its economic efficiency is expected to be very high. Moreover, by achieving a remarkably more efficient property for the decomposition of vapor phase organic compounds, the industrial applicability of the catalysts, such as in the removal of odor-causing materials at room temperature, is expected to be significantly enhanced.
[Description of Drawings]
Figure 1 represents a schematic view of an experimental apparatus that is used for decomposition of vapor phase organic compounds and organic synthesis using the catalysts of the present invention.
[Mode of Invention]
The present invention relates to ceramic catalysts that are prepared by mixing and calcining raw materials, and they are characterized in that they can decompose water to produce active hydrogen and hydroxyl radicals, decompose vapor phase organic compounds through the reaction with active hydrogen and hydroxyl radicals at a low temperature of 1000C or below, and synthesize organic compounds by reacting water with carbon dioxide at temperature of 1000C or higher.
The applicants of the present invention discovered that when a suitable environment is provided (for example, enough reaction time is given or a temperature of 100°C or higher was provided), a Lewis acid uses water as a Lewis base to decompose water using the following presumptive reaction process. OH
: LA : + H2O → [ : LA : ]" + H+
OH OH
[ : LA : ]- → [ : LAΘ: j
OH [ : LAG:J + H+ → : LA : + V2H2t + OH -
OH - + OH - -> H2O + V2O2t ( LA Lewis Acid, OH • Hydroxy radical )
As mentioned above, it was observed that the hydroxyl radical, active hydrogen, active oxygen and the like can decompose vapor phase organic compounds at a low temperature of 10O0C or below and can synthesize organic compounds at a medium/high temperature of 10O0C or higher.
When water and carbon dioxide are reacted, the applicants of the present invention discovered that the electrons produced during the water decomposition migrate to the surface of metal of the Lewis acid, thereby increasing the concentration of the electrons. As a result, it is predicted that carbon dioxide and hydrogen or hydrogen ions at the metal surface of the Lewis acid undergoes, for example, the following reactions to synthesize organic compounds.
CO2 + e → COO" 2COO" + H2 → 2HC00"
HCOO" + 2H2 → CH3O" + 2H2O
In addition, the applicants of the present invention could observe that when the compounds composed of hydrophilic functional groups, that can offer electron pairs, such as oxides, hydroxides, sulfates, etc. and of alkaline metals or of alkaline earth metals are added to the Lewis acid, water decomposition or reaction between water and carbon dioxide can be induced by increasing the Lewis basicity, as shown in the following example.
:
Figure imgf000007_0001
[: LAe] + M+ -> : LA: + M + LB - M + H2O → MOH + 1AH2T LB - + MOH → MLB + OH - OH • + OH - -> H2O + ιΛ02t
( LB Lewis Base, M Alkaline Metal, OH • Hydroxy radical )
Moreover, the applicants of the present invention also discovered that when transition metal compounds were -added to the Lewis acid to be used for catalysts for reaction between water and carbon dioxide, the electrons on the metal surface of the Lewis acid migrated, thereby making organic synthesis at the surface of transition metal possible, promoting the production of a wider range of the types of organic compounds and improving the conversion rate of the carbon dioxides.
Therefore, the ceramic catalysts according to the present invention that can decompose vapor phase organic compounds at a temperature of 10O0C or lower and synthesize organic compounds by reacting carbon dioxide with water at a temperature of 100 0C or higher could only comprise compounds that can be isolated by a Lewis acid.
For compounds that can be isolated by a Lewis acid can be any one or a mixture of two or more from the group consisting of: natural minerals such as kaolinite, bentonite, attapulgite, zeolite, montmorillonite; oxides such as zinc oxide (ZnO)1 aluminum oxide (AI2O3), titanium dioxide (TiO2), cerium oxide (CeO2), vanadium pentoxide (V2O5), silicon dioxide (SiO2), chromium oxide (Cr2θ3); sulfates such as calcium sulfate (CaSO-O, manganese sulfate (MnSO4), nickel sulfate (NiSO4), copper sulfate (CuSO4), cobalt sulfate (CoSO4), cadmium sulfate (CdSO4), magnesium sulfate (MgSO4), iron sulfate (FeSO4), aluminum sulfate (Ak(SO4J3); and nitrates such as calcium nitrate (Ca(NO3)2), zinc nitrate (Zn(NO3)2), iron nitrate (Fe(NO3)3); phosphates such as aluminum phosphate (AIPO4), iron phosphate (FePO4), chromium phosphate (CrPO4), copper phosphate (Cu3(PO4J2), zinc phosphate (Zn3(PO4J4), magnesium phosphate (Mg3(PO4J2); and halides such as aluminum chloride (AICI3), titanium chloride (TiCI4), calcium chloride (CaCI2), calcium fluoride (CaF2), barium fluoride (BaF2).
Moreover, the catalysts of the present invention can include metal compounds which can provide an electron pair to the Lewis acid in addition to being able to be isolated by the Lewis acid. In this case, it is preferred that 20 to 99.9 weight % of the compounds that can be isolated by the Lewis acid and 0.1 to 80 weight % of the metal compounds are used. When the Lewis acid is less than 20 weight %, the catalyst efficiency is significantly reduced. However, when the Lewis acid is more than 99.9 weight %, the efficacy of the catalysts due to combination with the metal oxides is insignificant. It is more preferable to use 60 to 95 weight % of the Lewis acid. When less than 0.1 weight % of metal compounds is used, the catalyst efficiency is not improved and is even reduced when more than 80 weight % is used.
The metal compound that act as a Lewis base can be any one or a mixture of two or more from the group consisting of: sulfates (e.g., Li2SO4, Na2SO4), sulfites (e.g., Li2SO3, Na2SO3), phosphates (e.g., Li3PO4, Na3PO4), nitrates (e.g., LiNO3, NaNO3), nitrites (e.g., LiNO2, NaNO2), hydroxides (e.g., LiOH, NaOH), oxides (e.g., Li2O, Na2O), peroxides (e.g., Na2O2), superoxides (e.g., KO2, RbO2, CsO2) of an alkaline metal; and sulfates (e.g., MgSO4, CaSO4), sulfites (e.g., MgSO3, CaSO3), phosphates (e.g., Mg3(PO4J2, Ca3(PO4J2), nitrates (e.g., Mg(NO3)2, Ca(NO3)2), nitrites (e.g., Mg(NO2)2, Ca(NO2J2), hydroxides(e.g., Mg(OH)2, Ca(OH)2), oxides (e.g., MgO, CaO) and superoxides (e.g., BaO2) of an alkaline earth metal. When the compounds are dissolved in water, they can easily be impregnated into ceramic raw materials of the catalyst. Therefore, ceramic catalysts that are well dispersed with the metal compounds in the ceramic layers can be formed when the metal compounds are first dissolved in the water, mixed with Lewis acids and then are dried.
Additionally, the catalysts of the present invention not only can be isolated by the Lewis acid but also can contain transition metal compounds. In this case, it is preferable to use 20 to 99.9 weight % of the compounds that can be isolated by the Lewis acid and 0.1 to 80 weight % of the transition metal compounds. When the Lewis acid is less than 20 weight %, the efficiency of the catalysts are significantly reduced. However, when the Lewis acid is more than 99.9 weight %, the catalyst efficiency according to the combination of the metal oxides is insignificant. It is more preferable to include 60 to 95 weight % of the Lewis acid. In addition, when less than 0.1 weight % of metal compounds is used, the catalyst efficiency does not show improvement and is even reduced when more than 80 weight% is used.
The transition metal compounds are hydrophilic compounds which can be any one or a mixture of two or more from the group consisting of: sulfate (e.g., MnSO4, CoSO4, ZnSO4, CuSO4), sulfite (e.g., MnSO3, CoSO3, ZnSO3, CuSO3), phosphate (e.g., Mn3(PO4J2, Co3(PO4)2, Zn3(PO4J2, Cu3(PO4J2), nitrate (e.g., Mn(NO3)2) CO(NO3J2, Zn(NO3)2, Cu(NO3)2), nitrite (e.g., Mn(NO2J2, Co(NO2J2, Zn(NO2J2, Cu(NO2J2J1 hydroxide (e.g., Mn(OH)2, Co(OH)2, Zn(OH)2, Cu(OH)2) and oxides (e.g., MnO, CoO, ZnO, CuO) of a transition metal. When the compounds are calcined, they are decomposed mostly into metal oxides (e.g. MnO, Mn2O3, MnO2) or metals (e.g. Pd., Pt). Therefore, ceramic catalysts that are well dispersed with metal oxides or metals in the ceramic layers can be formed when the metal compounds are first dissolved in the water, mixed with ceramic raw materials and then are calcined.
In addition, the ceramic catalyst of the present invention can be provided by comprising a mixture of compounds that can be isolated by a Lewis acid, the metal compounds and the transition metal compounds. In this case, it is preferable to mix 20 to 99.9 weight % of the compounds that can be isolated by the Lewis acid with 0.1 to 80 weight % of the metal compound which can offer an electron pair to the Lewis acid, and then additionally adding 0.1 to 50 weight parts of a transition metal compound to the mixture having 100 weight parts. When the Lewis acid is less than 20 weight %, the catalyst efficiency is significantly reduced; however, when the Lewis acid is more than 99.9 weight %, the catalyst efficiency with the combination with the metal oxides is insignificant. It is more preferable to comprise 60 to 95 weight % of the Lewis acid. In addition, when less than 0.1 weight % of metal compounds included, there is no improvement of the efficiency of the catalysts and the catalyst efficiency is even reduced when more than 80 weight % is used. When less than 0.1 weight part of the transition metal compounds was added to the mixture having 100 parts, there was no improvement of the efficiency of the catalysts, and the same result was shown when more than 50 weight parts were added.
Further, the ceramic catalysts of the present invention can be provided by using a mixture of the compounds that can be isolated by the Lewis acid and electrolytes. In this case, it is preferable to add an amount of less than 0.1 to 30 weight parts of the electrolytes compared to the compounds that can be isolated by the Lewis acid having 100 parts. When less than 0.1 weight part of the electrolyte is added, there is no improvement of the efficiency of the catalyst of the present invention. Further, when more than 30 weight parts of the electrolyte are added, the catalyst efficiency was even reduced.
The electrolyte should be easily ionized such that it promotes transfer of electric charges, and for which mineral (inorganic) acids and its bases are generally used, which can be any one or a mixture of two or more from the group consisting of chloride (e.g., NaCI, KCI), nitrate (e.g., NaNO3, KNO3), sulfate (e.g., Na2SO4, K2SO4), carbonate (e.g., Li2CO3, Na2CO3, K2CO3), phosphate (e.g., NaH2PO4, Na2HPO4) of an alkaline metal and chloride (e.g., CuCI2, NiCI2), nitrate (e.g., Cu(NO3)2, Ni(NO3J2), sulfate (e.g. CuSO4, NisO4) of a transition metal. In addition, the ceramic catalysts of the present invention can be a mixture of compounds that can be isolated by the Lewis acid, the metal compounds and the electrolytes. In this case, it is preferable to mix 20 to 99.9 weight % of the compounds that can be isolated by the Lewis acid and 0.1 to 80 weight % of the metal compounds that can provide an electron pair to the Lewis acid, followed by adding 0.1 to 30 weight parts of the electrolytes to the mixture having 100 parts. When the Lewis acid is less than 20 weight %, the catalyst efficiency is significantly reduced; however, when more than 99.9 weight % of the Lewis acid is included, the catalyst efficiency in combination with the metal oxides is insignificant. It is more preferable to have 60 to 95 weight % of the Lewis acid. In addition, when an amount of 0.1 weight % or less of the metal compounds is included, there is no improvement of the catalyst efficiency and the characterization of the catalysts is even reduced when more than 80 weight% is used. Moreover, when less than 0.1 weight parts of the electrolytes were added to the mixture having 100 parts, there was no improvement in the characterization of the catalysts, and the same was also shown when more than 30 weight parts were added.
In addition, the ceramic catalysts of the present invention can be a mixture of the compounds that can be isolated by the Lewis acid, the transition metal compounds and the electrolytes. In this case, it is preferable to make a mixture containing 20 to 99.9 weight % of compounds that can be isolated by the Lewis acid and 0.1 to 80 weight % of the transition metal compounds, followed by adding 0.1 to 30 weight part of electrolytes to the mixture having 100 weight parts. When the Lewis acid is less than 20 weight %, the efficiency of the catalysts are significantly reduced. However, when the Lewis acid is more than 99.9 weight %, the improved efficiency of the catalysts with combination with the metal oxides is insignificant. It is more preferable to mix 60 to 95 weight % of the Lewis acid. In addition, when less than 0.1 weight % of the metal compounds is used, no improvement in the characterization of the catalysts was shown and the characterization even reduced when more than 80 weight % is used. When less than 0.1 weight parts of the transition metal compounds were added to the mixture having 100 parts, there was no improvement in the characterization of the catalysts, and the same was also shown when more than 30 weight parts were added.
In addition, the ceramic catalysts of the present invention can be a mixture of the compounds that can be isolated by the Lewis acid, the metal compounds, the transition metal compounds and the electrolytes. In this case, it is preferable to make a mixture containing 20 to 99.9 weight% of compounds that can be isolated by the Lewis acid and 0.1 to 80 weight% of the metal compounds that can provide an electron pair to the Lewis acid, followed by adding 0.1 to 50 weight parts of the transition metal compounds to the mixture having 100 weight parts and then adding 0.1 to 30 weight parts of the electrolytes to the resulting mixture having 100 weight parts. When the amount of the Lewis acid added is less than 20 weight %, the efficiency of the catalysts are significantly reduced; however, when the amount of the Lewis acid added is more than 99.9 weight %, the efficiency of the catalysts is insignificant. It is more preferable to add 60 to 95 weight % of the Lewis acid. In addition, when less than 0.1 weight % of the metal compounds is added, there is no improvement of the characterization of the catalysts and the same result is shown when more than 80 weight% is added. When an amount of less than 0.1 weight parts of the transition metal compounds was added to the mixture, there was no improvement of the properties of the catalysts, and no improvement of the catalyst properties was also shown when more than 50 weight parts were added. When less than 0.1 weight parts of the electrolytes were added, there was no improvement of the efficiency of the catalysts, and the efficiency even reduced when more than 30 weight parts were added.
The present invention is explained in detail using the following examples. The following examples of the present invention only exemplify the present invention and the scope of the present invention should not be limited by the examples.
Example 1 : Reactions to Lewis acids
Reactions to Lewis acids using the experimental device of Fig. 1 were examined.
A. Decomposition of Vapor Phase Organic Compounds: The Lewis acid catalysts were crushed into particles having an average size of 1 mi or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5in£/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography (10)(HP-5890) and the results thereof are shown in Table 1.
[Table 1 ]
Figure imgf000013_0001
B. Water Decomposition; The Lewis acid catalysts were crushed into particles having the average size of 1 nun or below. Then, 5g of the crushed particles were put into the catalyst container (8) of Fig. 1. Then, the temperature of the water bath (4) was maintained at room temperature while that of the temperature control area (6) and the catalyst container(8) was maintained at 250°C, followed by supplying argon gas at 5m£/min and distilled water from bubbler(3) is allowed to migrate to the catalyst container (8) to allow reaction to occur. After 30 minutes of reaction, the decomposed portion of water was measured using a Gas Chromatography (1O)(HP- 5890) and the results thereof are shown in Table 2.
[Table 2]
Figure imgf000014_0001
C. Reactions between carbon dioxide and water: The Lewis acid catalysts are crushed into particles having the average diameter of 1 mm or below, and then 5g of the crushed particles were placed into the catalyst container (8) as shown in Fig. 1. Then, the temperature of the water bath (4), the temperature control area (6) and the catalyst container (8) was maintained at 2501O . Carbon dioxides were injected at 5m£/min and allowed distilled water from the bubbler (3) migrate to the catalyst container (8). After 30 minutes, the carbon dioxide conversion to organic material was measured using the Gas Chromatography (1O)(HP- 5890) and the results thereof are shown in Table 3.
[Table 3]
Figure imgf000015_0001
Example 2: Reactions to Addition of Metal Compounds 95 parts by weight of alumina Lewis acid raw material and 5 parts by weight of metal compounds were mixed to prepare a mixture of raw material of ceramic catalysts. 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped into a cylinder shape having a diameter of 3cm and a length of 10cm. The shaped mixture was dried at room temperature for 72 hours and then was calcined using electric furnace at 1 ,1000C for 12 hours and then was cooled at room temperature, thereby obtaining ceramic catalysts.
A. Decomposition of Vapor Phase Organic Compounds: The Lewis acid catalysts were crushed into particles having an average size of the particles are 1mm or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5in4/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography (10)(HP-5890) and the results thereof are shown in Table 4.
[Table 4]
Figure imgf000016_0001
B. Water Decomposition: The cylinder shaped ceramic catalysts were crushed into particles having the average size of 1 mm or below. Then, 5g of the crushed particles were put into the catalyst container (8) of Fig. 1 followed by sufficient purging with an inert gas (e.g. argon). The temperature of the water bath (4) was maintained at room temperature while that of the temperature control area (6) and the catalyst container (8) was maintained at 4500C . Inert gas was supplied at 5m4/min while letting a reaction to occur by allowing distilled water from bubbler (3) to migrate into the catalyst container (8). After 30 minutes of reaction, the decomposed portion of water was measured using Gas Chromatography (10)(HP-5890) and the results are shown in Table 5.
[Table 5]
Figure imgf000017_0001
C. Reactions between carbon dioxide and water: The Lewis acid catalysts are crushed into particles having the average diameter of 1 mm or below, and then 5g of the crushed particles were placed into the catalyst container (8) as shown in Fig. 1. Then, the temperature of the waterbath (4), the temperature control area (6) and the catalyst container (8) was maintained at 45O0C . Carbon dioxides were injected at 5m£/min and allowed distilled water from the bubbler (3) migrate to the catalyst container(8). After 30 minutes, the carbon dioxide conversion to organic material was measured using the Gas Chromatography (1O)(HP- 5890)and the results thereof are shown in Table 6.
[Table 6]
Figure imgf000018_0001
Example 3: Reactions to the Addition of Transition Metal Compounds 1 95 parts by weight of alumina Lewis acid raw material and 5 parts by weight of metat compounds were mixed to prepare a mixture of raw material of ceramic catalysts. 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped into a cylinder shape having a diameter of 3cm and a length of 10cm. The shaped mixture was dried at room temperature for 72 hours and then was calcined using electric furnace at 1 ,100O for 12 hours and then was cooled at room temperature, thereby obtaining ceramic catalysts.
A. Decomposition of Vapor Phase Organic Compounds: The cylinder shape ceramic catalysts were crushed into particles having an average size of the particles are 1 mm or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5in£/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography(10)(HP-5890) and the results thereof are shown in Table 7.
[Table 7]
Figure imgf000019_0001
B. Water Decomposition: The cylinder shaped ceramic catalysts were crushed into particles having the average size of 1mm or below. Then, 5g of the crushed particles were put into the catalyst container (8) of Fig. 1 followed by sufficient purging with an inert gas (e.g. argon). The temperature of the water bath (4) was maintained at room temperature while that of the temperature control area (6) and the catalyst container (8) was maintained at 4500C. Inert gas was supplied at 5m£/min while letting a reaction to occur by allowing distilled water from bubbler (3) to migrate into the catalyst container (8). After 30 minutes of reaction, the decomposed portion of water was measured using Gas Chromatography (10)(HP-5890) and the results are shown in Table 8. [Table 8]
Figure imgf000020_0001
C. Reactions between carbon dioxide and water: The Lewis acid catalysts are crushed into particles having the average diameter of 1mm or below, and then 5g of the crushed particles were placed into the catalyst container (8) as shown in Fig. 1. Then, the temperature of the water bath (4), the temperature control area (6) and the catalyst container (8) was maintained at 450 °C. Carbon dioxides were injected at 5in£/mJn and allowed distilled water from the bubbler (3) migrate to the catalyst container(8). After 30 minutes, the carbon dioxide conversion to organic material was measured using the Gas Chromatography (1O)(HP- 5890) and the results thereof are shown in Table 9
[Table 9]
Figure imgf000020_0002
Figure imgf000021_0001
Example 4: Reactions to the Addition of Transition Metal Compounds 2 95 parts by weight of alumina Lewis acid raw material and 5 parts by weight of calcium hydroxides (Ca(OH)2) were mixed then 90 parts of the mixture and 10 parts of the transition metal compounds were added to prepare a mixture of raw material of ceramic catalysts. 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped into a cylinder shape having a diameter of 3cm and a length of 10cm. The shaped mixture was dried at room temperature for 72 hours and then was calcined using electric furnace at 1 ,10Ot: for 12 hours and then was cooled at room temperature, thereby obtaining ceramic catalysts.
A. Decomposition of Vapor Phase Organic Compounds: The ceramic catalysts were crushed into particles having an average size of the particles are 1mm or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5in£/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography (10)(HP-5890) and the results thereof are shown in Table 10.
[Table 10]
Figure imgf000021_0002
Figure imgf000022_0001
B. Water Decomposition: The cylinder shaped ceramic catalysts were crushed into particles having the average size of 1mm or below. Then, 5g of the crushed particles were put into the catalyst container (8) of Fig. 1 followed by sufficient purging with an inert gas (e.g. argon). The temperature of the water bath (4) was maintained at room temperature while that of the temperature control area (6) and the catalyst container (8) was maintained at 450°C. Inert gas was supplied at 5m£/min while letting a reaction to occur by allowing distilled water from bubbler (3) to migrate into the catalyst container (8). After 30 minutes of reaction, the decomposed portion of water was measured using Gas Chromatography (10)(HP-5890) and the results are shown in Table 11.
[Table 11 ]
Figure imgf000022_0002
Figure imgf000023_0001
C. Reactions between carbon dioxide and water: The ceramic catalysts are crushed into particles having the average diameter of 1mm or below, and then 5g of the crushed particles were placed into the catalyst container (8) as shown in Fig. 1. Then, the temperature of the water bath (4), the temperature control area (6) and the catalyst container (8) was maintained at 4500C . Carbon dioxides were injected at 5iM/min and allowed distilled water from the bubbler (3) migrate to the catalyst container^). After 30 minutes, the carbon dioxide conversion to organic material was measured using the Gas Chromatography (1O)(HP- 5890) and the results thereof are shown in Table 12.
[Table 12]
Figure imgf000023_0002
Example 5: Reactions to the Addition of Electrolytes 1
6 weight % of the following electrolytes were added to the alumina Lewis acid using the experimental device shown in Fig. 1 to prepare ceramic catalyst raw material compounds. 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped into a cylinder shape having a diameter of 3cm and a length of 10cm. The shaped mixture was dried at room temperature for 72 hours and then was calcined using electric furnace at 900 "C for 12 hours and then was cooled at room temperature, thereby obtaining ceramic catalysts.
A. Decomposition of Vapor Phase Organic Compounds: The ceramic catalysts were crushed into particles having an average size of the particles are 1 mm or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5m4/miη while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography (10)(HP-5890) and the results thereof are shown in Table 13.
[Table 13]
Figure imgf000024_0001
B. Water Decomposition: The cylinder shaped ceramic catalysts were crushed into particles having the average size of 1 mm or below. Then, 5g of the crushed particles were put into the catalyst container (8) of Fig. 1 followed by sufficient purging with an inert gas (e.g. argon). The temperature of the water bath (4) was maintained at room temperature while that of the temperature control area (6) and the catalyst container (8) was maintained at 450°C . Inert gas was supplied at 5in£/min while letting a reaction to occur by allowing distilled water from bubbler (3) to migrate into the catalyst container (8). After 30 minutes of reaction, the decomposed portion of water was measured using Gas Chromatography (10)(HP-5890) and the results are shown in Table 14.
[Table 14]
Figure imgf000025_0001
C. Reactions between carbon dioxide and water: The ceramic catalysts are crushed into particles having the average diameter of 1 nun or below, and then 5g of the crushed particles were placed into the catalyst container (8) as shown in Fig. 1. Then, the temperature of the water bath (4), the temperature control area (6) and the catalyst container (8) was maintained at 45O0C. Carbon dioxides were injected at 5m£/min and allowed distilled water from the bubbler (3) migrate to the catalyst container(8). After 30 minutes, the carbon dioxide conversion to organic material was measured using the Gas Chromatography (1O)(HP- 5890) and the results thereof are shown in Table 15.
[Table 15]
Figure imgf000026_0001
Example 6: Reactions to Addition of Electrolytes 2 95 parts by weight of alumina Lewis acid raw material and 5 parts by weight of sodium hydroxide (NaOH) were mixed, then 94 parts of the resulting mixture and 6 parts of the electrolytes were added to prepare a mixture of raw materials of ceramic catalysts. 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped into a cylinder shape having a diameter of 3cm and a length of 10cm. The shaped mixture was dried at room temperature for 72 hours and then was calcined using electric furnace at 9000C for 12 hours and then was cooled at room temperature, thereby obtaining ceramic catalysts.
A. Decomposition of Vapor Phase Organic Compounds: The ceramic catalysts were crushed into particles having an average size of the particles are 1 oiπi or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5in£/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography (10)(HP-5890) and the results thereof are shown in Table 16.
[Table 16]
Figure imgf000027_0001
B. Water Decomposition: The cylinder shaped ceramic catalysts were crushed into particles having the average size of 1mm or below. Then, 5g of the crushed particles were put into the catalyst container (8) of Fig. 1 followed by sufficient purging with an inert gas (e.g. argon). The temperature of the water bath (4) was maintained at room temperature while that of the temperature control area (6) and the catalyst container (8) was maintained at 45O0C. Inert gas was supplied at 5m£/min while letting a reaction to occur by allowing distilled water from bubbler (3) to migrate into the catalyst container (8). After 30 minutes of reaction, the decomposed portion of water was measured using Gas Chromatography (10)(HP-5890) and the results are shown in Table 17.
[Table 17]
Figure imgf000027_0002
Figure imgf000028_0001
C. Reactions between carbon dioxide and water: The ceramic catalysts are crushed into particles having the average diameter of 1mi or below, and then 5g of the crushed particles were placed into the catalyst container (8) as shown in Fig. 1. Then, the temperature of the water bath (4), the temperature control area (6) and the catalyst container (8) was maintained at 450 °C. Carbon dioxides were injected at 5in£/min and allowed distilled water from the bubbler (3) migrate to the catalyst container(8). After 30 minutes, the carbon dioxide conversion to organic material was measured using the Gas Chromatography (1O)(HP- 5890) and the results thereof are shown in Table 18.
[Table 18]
Figure imgf000028_0002
Example 7: Reactions to Addition of Electrolytes 3
95 parts by weight of alumina Lewis acid raw material and 5 parts by weight of zinc sulfate (ZnSO4) were mixed, and then 94 parts of the resulting mixture and 6 parts of the electrolytes were added to prepare ceramic catalyst raw material mixture. 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped into a cylinder shape having a diameter of 3cm and a length of 10cm. The shaped mixture was dried at room temperature for 72 hours and then was calcined using electric furnace at 900 "C for 12 hours and then was cooled at room temperature, thereby obtaining ceramic catalysts.
A. Decomposition of Vapor Phase Organic Compounds: The ceramic catalysts were crushed into particles having an average size of the particles are Inim or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5m4/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propionaldehyde was measured using Gas Chromatography(10)(HP-5890) and the results thereof are shown in Table 19.
[Table 19]
Figure imgf000029_0001
Figure imgf000030_0001
B. Water Decomposition: The cylinder shaped ceramic catalysts were crushed into particles having the average size of 1mm or below. Then, 5g of the crushed particles were put into the catalyst container (8) of Fig. 1 followed by sufficient purging with an inert gas (e.g. argon). The temperature of the water bath (4) was maintained at room temperature while that of the temperature control area (6) and the catalyst container (8) was maintained at 450 °C. Inert gas was supplied at 5m4/min while letting a reaction to occur by allowing distilled water from bubbler (3) to migrate into the catalyst container (8). After 30 minutes of reaction, the decomposed portion of water was measured using Gas Chromatography (10)(HP-5890) and the results are shown in Table 20.
[Table 20]
Figure imgf000030_0002
C. Reactions between carbon dioxide and water: The ceramic catalysts are crushed into particles having the average diameter of 1 mm or below, and then 5g of the crushed particles were placed into the catalyst container (8) as shown in Fig. 1. Then, the temperature of the water bath (4), the temperature control area (6) and the catalyst container (8) was maintained at 450 "C. Carbon dioxides were injected at 5in4/min and allowed distilled water from the bubbler (3) migrate to the catalyst container(8). After 30 minutes, the carbon dioxide conversion to organic material was measured using the Gas Chromatography (1O)(HP- 5890) and the results thereof are shown in Table 21.
[Table 21 ]
Figure imgf000031_0001
Example 8: Reactions to Addition of Electrolytes 4
90 parts by weight of alumina Lewis acid raw material and 5 parts by weight of metal compounds sodium hydroxide were mixed then 5 parts of zinc sulfates (ZnSO4) were added followed by adding 6 parts of the following electrolytes to 94 parts of the resulting mixture there from to prepare a mixture of raw materials of ceramic catalysts. 1.5 times the weight of the mixture of distilled water was mixed into the mixture and the resulting mixture was shaped into a cylinder shape having a diameter of 3cm and a length of 10cm. The shaped mixture was dried at room temperature for 72 hours and then was calcined using electric furnace at 9000C for 12 hours and then was cooled at room temperature, thereby obtaining ceramic catalysts.
A. Decomposition of Vapor Phase Organic Compounds: The ceramic catalysts were crushed into particles having an average size of the particles are 1mm or below, followed by adding 5g of the particles to catalyst container (8) of Fig. 1. The temperature of water bath (4), temperature control area (6) and catalyst container (8) was maintained at room temperature. Air was supplied at 5m£/min while propionaldehyde inside bubbler(3) was made to be injected into the catalyst container (8) at the concentration of 10,000 ppm. After 30 minutes of reaction, the decomposed portion of propyonaldehyde was measured using Gas Chromatography(10)(HP-5890) and the results thereof are shown in Table 22.
[Table 22]
Figure imgf000032_0001
B. Water Decomposition: The cylinder shaped ceramic catalysts were crushed into particles having the average size of 1mm or below. Then, 5g of the crushed particles were put into the catalyst container (8) of Fig. 1 followed by sufficient purging with an inert gas (e.g. argon). The temperature of the water bath (4) was maintained at room temperature while that of the temperature control area (6) and the catalyst container (8) was maintained at 4500C. Inert gas was supplied at 5in£/min while letting a reaction to occur by allowing distilled water from bubbler (3) to migrate into the catalyst container (8). After 30 minutes of reaction, the decomposed portion of water was measured using Gas Chromatography (10)(HP-5890) and the results are shown in Table 23. [Table 23]
Figure imgf000033_0001
C. Reactions between carbon dioxide and water: The ceramic catalysts are crushed into particles having the average diameter of 1im or below, and then 5g of the crushed particles were placed into the catalyst container (8) as shown in Fig. 1. Then, the temperature of the water bath (4), the temperature control area (6) and the catalyst container (8) was maintained at 4500C. Carbon dioxides were injected at 5in£/min and allowed distilled water from the bubbler (3) migrate to the catalyst container(8). After 30 minutes, the carbon dioxide conversion to organic material was measured using the Gas Chromatography (1O)(HP- 5890) and the results thereof are shown in Table 24.
[Table 24]
Figure imgf000033_0002
Figure imgf000034_0001
As explained above, the catalysts of the present invention, which have various uses and can disperse soluble electrolyte salts in a raw material for the catalysts, can decompose water to produce hydrogen, can decompose vapor phase organic compounds at a low temperature of 100 "C or lower, particularly at a room temperature (around 25 "C) and can synthesize organic compounds by reacting water with carbon dioxide at a medium/high temperature of 1001C or higher.
In other words, the catalysts of the present invention comprise of a mixture of catalyst raw material such as a Lewis acid which is relatively inexpensive and metal oxides, thereby having a characteristic that the cost of the catalysts are low. Therefore, particularly for water decomposition and organic synthesis through the reaction between carbon dioxide and water without light, since exhaust heat, carbon dioxides and steam produced from industrial sites can be used, the cost of production of hydrogen energy and energy from synthesized organic materials are expected to significantly decrease, and its economic efficiency is expected to be very high. Moreover, by achieving a remarkably more efficient property for the decomposition of vapor phase organic compounds, the industrial applicability of the catalysts, such as in the removal of odor-causing materials at room temperature, is expected to be significantly enhanced.

Claims

[CLAIMS]
[Claim 1]
A catalyst for decomposing water, decomposing vapor phase organic compounds and synthesizing organic materials through the reaction between carbon dioxide and water comprising compounds that can be isolated by a
Lewis acid only.
[Claim 2]
A catalyst for decomposing water, decomposing vapor phase organic compounds and synthesizing organic materials through the reaction between carbon dioxide and water comprising:
20 to 99.9 weight % of compounds that can be isolated by a Lewis acid; and
0.1 to 80 weight % of metal compounds that can offer an electron pair to the
Lewis acid.
[Claim 3]
A catalyst for decomposing water, decomposing vapor phase organic compounds and synthesizing organic materials through the reaction between carbon dioxide and water comprising:
20 to 99.9 weight % of compounds that can be isolated by a Lewis acid; and
0.1 to 80 weight % of transition metal compounds.
[Claim 4]
A catalyst for decomposing water, decomposing vapor phase organic compounds and synthesizing organic materials through the reaction between carbon dioxide and water comprising 0.1 to 30 weights parts of electrolytes added to 100 weight parts of compounds that can be isolated by a Lewis acid.
[Claim 5]
The catalyst of claim 2 further comprising additional 0.1 to 50 weight parts of transition metal compounds compared to 100 parts of the catalyst composition.
[Claim 6]
The catalyst of claim 2 further comprising additional 0.1 to 30 weight parts of electrolytes compared to 100 parts of the catalyst composition.
[Claim 7]
The catalyst of claim 3 further comprising additional 0.1 to 30 weight parts of electrolytes compared to 100 parts of the catalyst composition.
[Claim 8]
The catalyst of claim 5 further comprising additional 0.1 to 30 weight parts of electrolytes compared to 100 parts of the catalyst composition.
[Claim 9]
The catalyst of any one of claims 1 to 8, wherein the compounds that can be isolated by a Lewis acid can be any one or a mixture of two or more from the group consisting of: natural minerals such as kaolinite, bentonite, attapulgite, zeolite, montmorillonite; oxides such as zinc oxide (ZnO), aluminum oxide (AI2O3), titanium dioxide (TiO∑), cerium oxide (Ceθ2), vanadium pentoxide (V2O5), silicon dioxide (SiO2), chromium oxide (0203); sulfates such as calcium sulfate (CaSO4), manganese sulfate (MnSO4), nickel sulfate (NiSO4), copper sulfate (CuSO4), cobalt sulfate (CoSO4), cadmium sulfate (CdSO4), magnesium sulfate (MgSO4), iron sulfate (FeSO4), aluminum sulfate (Al2(SO4)3); and nitrates such as calcium nitrate (Ca(NO3^), zinc nitrate (Zn(NO3)2), iron nitrate (Fe(NO3)3); phosphates such as aluminum phosphate (AIPO4), iron phosphate (FePO4), chromium phosphate (CrPO4), copper phosphate (Cu3(PO4)2), zinc phosphate (Zn3(PO4J4), magnesium phosphate (Mg3(PO4)2); and halides such as aluminum chloride (AICI3), titanium chloride (TiCI4), calcium chloride (CaCb), calcium fluoride (CaF2), barium fluoride (BaF2).
[Claim 10] The catalyst of any one of claims 2, 5, 6 and 8, wherein the metal compounds that can provide an electron pair to the Lewis acid can be any one or a mixture of two or more from the group consisting of: sulfates (U2SO4, Na2SO4), sulfites (Li2SO3, Na2SO3), phosphates (Li3PO4, Na3PO4), nitrates (LiNO3, NaNO3), nitrites (LiNO2, NaNO2), hydroxides (LiOH, NaOH), oxides (Li2O, Na2O), peroxides (Na2O2), superoxides (KO2, RbO2, CsO2) of an alkaline metal; and sulfates (MgSO4, CaSO4), sulfites (MgSO3, CaSO3), phosphates (Mg3(PO4)2, Ca3(PO4J2), nitrates (Mg(NO3)2, Ca(NO3)2), nitrites (Mg(NO2)2) Ca(NO2)2), hydroxides(Mg(OH)2) Ca(OH)2), oxides (MgO1 CaO) and superoxides (BaO2) of an alkaline earth metal.
[Claim 11]
The catalyst of any one of claims 3, 7 and 8, wherein the transition metal compounds can be any one or a mixture of two or more from the group consisting of: sulfate (e.g., MnSO4, CoSO4, ZnSO4, CuSO4), sulfite (e.g., MnSO3, CoSO3, ZnSO3, CuSO3), phosphate (e.g., Mn3(PO4J2, Co3(PO4)2, Zn3(PO4)2, Cu3(PO4)2), nitrate (e.g., Mn(NO3)2, Co(NO3J2, Zn(NO3)2, Cu(NOa)2), nitrite (e.g., Mn(NO2J2, Co(NO2)2, Zn(NO2)2) Cu(NO2)2), hydroxide (e.g., Mn(OH)2, Co(OH)2, Zn(OH)2, Cu(OH)2) and oxides (e.g., MnO, CoO, ZnO, CuO) of a transition metal.
[Claim 12]
The catalyst of any one of claims 4, 6, 7 and 8, wherein the electrolytes can be any one or a mixture of two or more from the group consisting of chloride (NaCI, KCI), nitrate (NaNO3, KNO3), sulfate (Na2SO4, K2SO4), carbonate (Li2CO3, Na2CO3, K2CO3), phosphate (NaH2PO4, Na2HPO4) of an alkaline metal and chloride (CuCI2, NiCI2), nitrate (Cu(NO3)2, Ni(NO3)2), sulfate (CuSO4, NisO4) of a transition metal.
PCT/KR2006/000426 2005-02-07 2006-02-06 A catalyst for the disintegration of vapor phase organic compounds and for the organic synthesis from carbon dioxide and water Ceased WO2006083142A1 (en)

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CN109772427A (en) * 2019-02-22 2019-05-21 浙江大学 It is a kind of for the catalyst of sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid and its preparation and application

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