KR100803057B1 - Solid acid catalyst for methanol decomposition and its preparation method - Google Patents

Abstract

The present invention relates to a solid acid catalyst for methanol decomposition that decomposes methanol and generates hydrogen, and a method for producing the same. According to the present invention, there is no formation of side products other than hydrogen, such as formaldehyde or methyl formate, there is no problem of lowering the amount of hydrogen due to the methanation reaction between the produced hydrogen and carbon monoxide, and the price is low, and the pretreatment and post-treatment There is no need to go through the process or constraints to maintain the reaction within the proper temperature, methanol can be decomposed continuously to generate hydrogen, and optionally an organic compound can be synthesized.

Description

Methanol decomposition catalyst based on solid acid materials and method for preparing the same

1 schematically illustrates a methanol decomposition reaction in the present invention.

2 is a schematic diagram showing an experimental apparatus for gaseous methanol decomposition reaction used in the embodiment of the present invention.

* Short description of the major reference marks *

1: air cylinder 2: methanol-mounted container

3: gas flow meter 4: electronic liquid flow meter

5: vaporization mixing mixer 6: liquid flow regulator

7: temperature control zone 8: catalyst tower

9: internal temperature meter 10: three-way valve

11: gas chromatography sample container 12: temperature control device

13: gas chromatography

The present invention relates to a solid acid catalyst for methanol decomposition that decomposes methanol and generates hydrogen, and a method for producing the same.

In the present invention, the solid acid, the metal compound, the transition metal compound, and the electrolyte each mean that one or two or more of the corresponding materials are mixed.

In the present invention, there may be materials overlapping each other in the classification of a solid acid, a metal compound, a transition metal compound, and an electrolyte, but such overlapping materials are classified and expressed differently according to the mixing order. For example, when the first (first) mixing of a substance and a metal compound belonging to a solid acid and a substance corresponding to a solid acid at the same time (the first), they are expressed as a mixture of two solid acids, not a mixture of the solid acid and the metal compound, When a mixture of two solid acids mixed is a metal compound and at the same time a second material of the solid acid is mixed again, the mixture is expressed as a mixture of two solid acids and one metal compound, not a mixture of three solid acids. do.

There is a great need to develop alternative energy due to depletion of fossil fuels or environmental issues. Among the alternative energy, methanol is preferable because it is inexpensive and decomposes to generate hydrogen (H ₂ ). In addition, the syngas obtained by methanol decomposition can be used as a chemical raw material or automobile fuel, and when used in combination with the steam reforming reaction, can be used for the production of hydrogen for fuel cells or for future hydrogen automobiles.

In addition, since methanol decomposition can be utilized as a reaction cycle for use in a chemical heat pump that converts low temperature energy into high temperature energy in addition to methanol synthesis reaction, research on this has been conducted.

In methanol cracking reactions, the main product is hydrogen and it is to be efficiently broken down without side products such as carbon monoxide (CO). For this purpose, a catalyst having high activity and selectivity should be used. Especially, in order to use the chemical heat pump, it is necessary to develop a catalyst having high activity and selectivity at low temperature.

As catalysts of conventional methanol decomposition reactions, noble metal catalysts such as platinum (Pt) and palladium (Pd), copper catalysts, copper-based mixed catalysts, nickel-based catalysts and the like are known.

In the case of using the copper and copper-based mixed catalyst, formaldehyde, methyl formate, and the like are generated in addition to hydrogen, and thus are not suitable as a synthesis gas or a catalyst for producing hydrogen.

In the case of using a catalyst such as a noble metal and a catalyst such as nickel and copper-nickel, it is reported that hydrogen and carbon monoxide are mainly produced. When these catalysts are used, a reaction between the hydrogen and carbon monoxide produced at a reaction temperature of 300 ° C. or higher is performed. There is a problem in that the amount of hydrogen is reduced while generating a considerable amount of methane. Furthermore, the noble metal catalyst has a disadvantage of being expensive.

In addition, the conventional reduction catalysts are cumbersome to undergo a pretreatment and post-treatment process at a predetermined temperature and a predetermined time or more while administering a considerable amount of hydrogen, etc. before and after the reaction, and also has a disadvantage of maintaining the reaction within an appropriate temperature. .

Accordingly, the present invention has been made to solve the above problems, and an object of the present invention is to produce no side products such as formaldehyde and methyl formate other than hydrogen, and to produce a methanation reaction between hydrogen and carbon monoxide. There is no problem of lowering the amount of hydrogen, it is inexpensive, there is no need to go through pre-treatment and post-treatment, and there is no restriction to keep the reaction within the proper temperature, methanol is decomposed continuously to generate hydrogen. It is to provide a solid acid catalyst composition for methanol decomposition and a method for producing the compound which can synthesize a compound.

The object of the present invention as described above, kaolinite (benolinite), bentonite (bentonite), attapulgite (attapulgite), zeolites (zeolites), montmorillonite (montmorillonite), zinc oxide (ZnO), aluminum oxide (Al ₂ O ₃ ) , Titanium oxide (TiO ₂ ), cesium oxide (CeO ₂ ), vanadium oxide (V ₂ O ₅ ), silicon oxide (SiO ₂ ), chromium oxide (Cr ₂ O ₃ ), calcium sulfate (CaSO ₄ ), 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 II (FeSO ₄ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ), zinc sulfate (ZnSO ₄ ), calcium nitrate (Ca (NO ₃ ) ₂ ), zinc nitrate (Zn (NO ₃ ) ₂ ), iron nitrate III (Fe (NO ₃ ) ₃ ), phosphoric acid Aluminum (AlPO ₄ ), iron phosphate III (FePO ₄ ), chromium phosphate (CrPO ₄ ), copper phosphate (Cu ₃ (PO ₄ ) ₂ ), zinc phosphate (Zn ₃ (PO ₄ ) ₄ ), magnesium phosphate (Mg ₃ (PO ₄ ) ₂ ), aluminum chloride (AlCl ₃ ), titanium chloride (TiCl ₄ ), calcium chloride (CaCl ₂ ), silver chloride (AgCl), calcium fluoride (CaF ₂ ) Or a mixture of two or more solid acids of barium fluoride (BaF ₂ ) is obtained by firing a solid acid catalyst and a method for producing the same.

The solid acid is preferably mixed with sulfuric acid or phosphoric acid and calcined.

At this time, when the sulfuric acid is used 1.5 times by weight based on the solid acid, it is preferable to use diluted to more than 0% 30% or less.

Preferably, the solid acid is mixed with a second metal compound different from the solid acid, a transition metal compound different from the solid acid, or an electrolyte different from the solid acid, and in the final mixture, 20 to 99.9 wt% of the solid acid ; And 0.1 to 80% by weight of the metal compound or the transition metal compound; or, in the final mixture, 20 to 99.9% by weight of the solid acid; And 0.1 to 30% by weight of the electrolyte; It is preferable to contain.

The solid acid is mixed with the second metal compound different from the solid acid or the solid oxidation second transition metal compound, and then, in the second mixed mixture, the transition metal compound different from the solid acid or the metal compound different from the solid acid is third It is preferably mixed with, in the final mixture, 20 to 99.9% by weight of the solid acid; 0.1 to 80% by weight of the metal compound; And 0.1 to 50% by weight of the transition metal compound.

The solid acid is mixed with the metal compound different from the solid acid or the transition metal compound different from the solid oxidation second, and then, in the second mixed mixture, different from the solid acid and different from the metal compound or the transition metal compound. Preferably, the electrolyte is mixed third, and in the final mixture, 20 to 99.9 weight percent of the solid acid; 1 to 80% by weight of the metal compound or the transition metal compound; And 0.1 to 30% by weight of the electrolyte; It is preferable to contain.

After the solid acid is mixed with the metal compound different from the solid acid or the transition metal compound different from the solid acid for the second time, the solid acid and the transition metal compound different from the solid acid or the metal compound different from the solid acid are mixed thirdly, and thirdly In the mixed mixture, an electrolyte different from the solid acid and different from the metal compound or the transition metal compound is preferably mixed fourth, and in the final mixture, 20 to 99.9 wt% of the solid acid; 0.1 to 80% by weight of the metal compound; 0.1-50% by weight of the transition metal compound; And 0.1 to 30% by weight of the electrolyte; It is preferable to contain.

The above metal compounds are sulfates of alkali metals, sulfites of alkali metals, phosphates of alkali metals, nitrates of alkali metals, nitrites of alkali metals, hydroxides of alkali metals, oxides of alkali metals, peroxides of alkali metals, and excess of alkali metals. Metals of any one or a mixture of oxides, sulfates of alkaline earth metals, sulfites of alkaline earth metals, phosphates of alkaline earth metals, nitrates of alkaline earth metals, nitrites of alkaline earth metals, hydroxides of alkaline earth metals, oxides of alkaline earth metals or peroxides of alkaline earth metals It is preferable that it is a compound.

The transition metal compound is a transition metal which is any one or a mixture of sulfates of transition metals, sulfites of transition metals, phosphates of transition metals, nitrates of transition metals, nitrites of transition metals, hydroxides of transition metals, or oxides of transition metals. It is preferable that it is a compound.

The electrolyte may be any one or two or more of chlorides of alkali metals, nitrates of alkali metals, sulfates of alkali metals, carbonates of alkali metals, phosphates of alkali metals, chlorides of transition metals, nitrates of transition metals or sulfates of transition metals. It is preferable that it is an electrolyte which is a mixture.

Hereinafter, a solid acid catalyst for methanol decomposition and a method for producing the same according to the present invention will be described in detail.

1 schematically shows a methanol decomposition reaction, in which a catalyst comprising a solid acid that can function as an acid, in particular, is used in pure or hydrous methanol cracking reactions, as shown in FIG. And the like. In addition, organic substances such as dimethyl ether can be selectively synthesized, and there is no generation of side products such as formaldehyde and methyl formate. Furthermore, hydrogen is continuously generated at the beginning of the catalytic reaction as well as after 24 hours, and there is no decrease in the amount of hydrogen due to the methanation reaction between the generated hydrogen and carbon monoxide. In addition, there is no problem of having to go through the pre-treatment and post-treatment process or maintain the reaction within the appropriate temperature.

First, the solid acid is a solid exhibiting surface acidity, and in the present invention, natural inorganic substances such as kaolinite, bentonite, benpulite, attapulgite, zeolites, montmorillonite, and zinc oxide (ZnO) are preferred. ), Aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), cesium oxide (CeO ₂ ), vanadium oxide (V ₂ O ₅ ), silicon oxide (SiO ₂ ), chromium oxide (Cr ₂ O ₃ ), etc. Oxide, calcium sulfate (CaSO ₄ ), manganese sulfate (MnSO ₄ ), nickel sulfate (NiSO ₄ ), copper sulfate (CuSO ₄ ), cobalt sulfate (CoSO ₄ ), cadmium sulfate (CdSO ₄ ), magnesium sulfate (MgSO ₄ ) , Sulfur oxides such as iron sulfate II (FeSO ₄ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ), zinc sulfate (ZnSO ₄ ), calcium nitrate (Ca (NO ₃ ) ₂ ), zinc nitrate (Zn (NO ₃₎ ) ₂ ), nitrates such as iron nitrate III (Fe (NO ₃ ) ₃ ), aluminum phosphate (AlPO ₄ ), iron phosphate III (FePO ₄ ), chromium phosphate (CrPO ₄ ), copper phosphate (Cu ₃ (PO ₄₎ ) _2), zinc phosphate _{(Zn 3 (PO 4) 4} ), phosphoric town Magnesium _{(Mg 3 (PO 4) 2} ) phosphate, aluminum chloride, such as (AlCl _3), titanium chloride (TiCl _4), calcium chloride (CaCl _2), silver chloride (AgCl), calcium fluoride (CaF _2), barium fluoride ( A halide such as BaF ₂ ) is used, and when the solid acid is mixed alone or in combination of two or more kinds, the material obtained by first mixing two or more kinds at the same time is calcined, that is, heated (for example, 100 ° C.) and dried (for example, for 24 hours) to form a catalyst. (S1). In addition, it is preferable to calcinate by mixing sulfuric acid or phosphoric acid in the material, especially sulfuric acid is preferably used by diluting by 30% when used 1.5 times by weight relative to the solid acid, since it increases the methanol decomposition efficiency, In the case of using more than this, there is no increase in decomposition efficiency, which is not preferable because it is unnecessary. On the other hand, in the present invention, especially when using a mixture of two or more kinds of solid acids greatly increase the decomposition rate, each solid acid to be mixed in the mixture of the solid acid may be contained in more than 0% by weight and less than 100% by weight, respectively.

In the present invention, a second complex is mixed with the solid acid, a metal compound different from the solid acid, a transition metal compound different from the solid acid, or an electrolyte different from the solid acid, to form a second complex, or a third mixture is mixed again with a third complex. Four kinds of complexes are made by mixing them or the fourth mixture, and methanol decomposition efficiency increases with two, three and four complexes. In this mixing, since the catalytic activity reproducibility of the materials to be mixed differs according to the order of the mixing, the solid acid, the metal compound, the transition metal compound or the electrolyte must be mixed in the order of the mixing. In the present invention, the same materials are not mixed several times in different mixing orders, and in this case, there is no increase in methanol decomposition efficiency.

At least 20% by weight of the solid acid should be used to maintain reproducibility of the catalytic activity. On the other hand, in the 2, 3 and 4 composites, each metal compound or transition metal compound is up to 80% by weight in view of reproducibility of catalytic activity (when both the metal compound and the transition metal compound are contained, the metal compound is It can be prepared by adding up to 80% by weight, but the transition metal compound (up to 50% by weight), but in the case of an electrolyte in excess of 30% by weight, it is not preferable to exceed 30% by weight since there is little reproducibility of the catalytic activity.

Specifically, when the blending ratio is described based on the final mixture, it is preferable to contain 20 to 99.9 wt% of the solid acid and 0.1 to 80 wt% of the metal compound or the transition metal compound in the case of the two composites, Or 20 to 99.9% by weight of solid acid and 0.1 to 30% by weight of electrolyte is preferred in view of catalytic activity reproducibility.

In the case of the three composites, it is preferable to contain 20 to 99.9% by weight of the solid acid, 0.1 to 80% by weight of the metal compound and 0.1 to 50% by weight of the transition metal compound from the viewpoint of catalytic activity reproducibility, or 20 to 99.9% by weight of the solid acid. %, 1 to 80% by weight of the metal compound or transition metal compound, and 0.1 to 30% by weight of the electrolyte are preferable in view of catalyst activity reproducibility.

In the case of the four composites, it is preferable to contain 20 to 99.9% by weight of the solid acid, 0.1 to 80% by weight of the metal compound, 0.1 to 50% by weight of the transition metal compound and 0.1 to 30% by weight of the electrolyte from the viewpoint of catalytic activity reproducibility.

The metal compound capable of providing an electron pair to the solid acid is a substance serving as a base, preferably a sulfate of an alkali metal group (eg, Li ₂ SO ₄ , Na ₂ SO ₄ ), sulfite (eg, Li ₂ SO ₃ , Na ₂ SO ₃ ), phosphates (eg Li ₃ PO ₄ , Na ₃ PO ₄ ), nitrates (eg LiNO ₃ , NaNO ₃ ), nitrites (eg LiNO ₂ , NaNO ₂ ), hydroxides (eg, LiOH, NaOH), oxides (eg Li ₂ O, Na ₂ O), peroxides (eg Na ₂ O ₂ ), superoxides (eg KO ₂ , RbO ₂ , CsO ₂ ), sulfates of alkaline earth metal groups (eg , MgSO ₄ , CaSO ₄ ), sulfite (eg MgSO ₃ , CaSO ₃ ), phosphate (eg Mg ₃ (PO ₄ ) ₂ , Ca ₃ (PO ₄ ) ₂ ), nitrate (eg Mg (NO ₃ ) ₂ , Ca (NO ₃ ) ₂ ), nitrite (eg Mg (NO ₂ ) ₂ , Ca (NO ₂ ) ₂ ), hydroxides (eg Mg (OH) ₂ , Ca (OH) ₂ ), oxides (eg MgO , CaO) and peroxides (eg, BaO ₂ ) alone or in combination.

The metal compound has a property of decomposing into a metal oxide or metal when fired. Therefore, when the metal compound is dissolved in water and mixed with the solid acid catalyst to be fired, a metal oxide or a metal well dispersed catalyst composition is formed.

The transition metal compound is a water-soluble transition metal compound, preferably a sulfate of a transition metal group (eg, MnSO ₄ , CoSO ₄ , ZnSO ₄ , CuSO ₄ ), sulfite (eg, MnSO ₃ , CoSO ₃ , ZnSO ₃ , CuSO ₃ ) , Phosphates (eg Mn ₃ (PO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , Cu ₃ (PO ₄ ) ₂ ), nitrates (eg Mn (NO ₃ ) ₂ , Co (NO ₃ ) ₂ , Zn (NO ₃ ) ₂ , Cu (NO ₃ ) ₂ ), nitrite (eg Mn (NO ₂ ) ₂ , Co (NO ₂ ) ₂ , Zn (NO ₂ ) ₂ , Cu (NO ₂₎ ) ₂ ), hydroxides (eg Mn (OH) ₂ , Co (OH) ₂ , Zn (OH) ₂ , Cu (OH) ₂ ), oxides (eg MnO, CoO, ZnO, CuO) alone or in combination It is a substance.

The materials have a property of decomposing into a multivalent metal oxide (eg, MnO, Mn ₂ O ₃ , MnO ₂ ) or a metal (eg, Mn) when fired. Therefore, when the water-soluble transition metal compound is dissolved in water and mixed with the solid acid to be calcined, various metal oxides or metal-dispersed ceramic catalyst compositions are formed.

As the electrolyte is easily ionized to assist charge transfer, a compound mainly composed of an inorganic acid and a paired salt thereof is used. Preferably, a chloride salt of an alkali metal group (eg, NaCl, KCl), a nitrate (eg, NaNO ₃ , KNO) is used. ₃ ), sulfates (eg Na ₂ SO ₄ , K ₂ SO ₄ ), carbonates (eg Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ ), phosphates (eg NaH ₂ PO ₄ , Na ₂ HPO ₄ ), chlorides (eg CuCl ₂ , NiCl ₂ ), nitrates (eg Cu (NO ₃ ) ₂ , Ni (NO ₃ ) ₂ ), sulfates (eg CuSO ₄ , NiSO ₄ ) Or mixed materials.

The raw materials are calcined after kneading or impregnation to produce a catalyst. The ceramic catalyst of the desired composition prepared by mixing and calcining has various pores that disperse the water-soluble metal, metal salt, electrolyte, etc., and continuously decomposes methanol to continuously produce hydrogen, carbon dioxide, methane, and the like. It has the property to synthesize | combine. In addition, since the catalyst itself is composed of a combination of solid acids and the like, it is not only inexpensive, but the cost of hydrogen energy and renewable organic energy is very low since catalyst regeneration is performed by drying and heating in air.

Hereinafter, the present invention will be described in more detail by explaining preferred embodiments of the present invention. However, the present invention is not limited to the following examples, and various forms of embodiments can be implemented within the scope of the appended claims, and the following examples are only common in the art while making the disclosure of the present invention complete. It is intended to facilitate the implementation of the invention to those with knowledge.

[Experimental device]

FIG. 2 is a schematic view showing an experimental apparatus for gaseous methanol decomposition reaction used in the experiment of the present invention. Referring to FIG. 2, air is introduced into the methanol mounting vessel 2 from the air cylinder 1. A gas flow meter 3 is connected to the methanol mounting vessel 2. Methanol flows into the vaporization control mixer 5 from the methanol mounting vessel 2 via an electronic liquid flow meter 4. On the other hand, a liquid flow regulator 6 is connected to the electronic liquid flow meter (4). Methanol enters the temperature control zone (7) from the vaporization control mixer (5) and directly into the gas chromatography sampling vessel (11) through the three-way valve (10) or after entering the temperature control zone (7). It enters into the catalyst tower 8 and then into the gas chromatography sampling vessel 11. After charging a predetermined amount of the porous catalyst prepared in the catalyst tower (8), the temperature control section (7) and the catalyst tower (8) are fixed at a desired temperature. The catalyst tower 8 is provided with an internal temperature measuring device 9 and a temperature control device 12 is connected. Methanol is introduced into the gas chromatography (13; HP-5890) from the gas chromatography sampling container (11) via the three-way valve (10). The thermostat 12 is also connected between 10 and 11 and between 10 and 13. In FIG. 2, an area indicated by diagonal lines means a heating band.

Experimental Example 1-Methanol Decomposition of Solid Acid Catalyst

Each solid acid catalyst or a composite catalyst shown in Table 1 (94 parts by weight of zinc oxide solid acid, the first mixture of 6 parts by weight of a solid acid of cobalt sulfate, zinc sulfate, copper sulfate or vanadium oxide, respectively, respectively in Table 1 40 g was taken into the catalyst tower 8 of FIG. 2 and the temperature of the temperature control zone 7 and the catalyst tower 8 was maintained at 250 ° C.

The gas flow meter (3) and the liquid flow meter (4) were adjusted so that nitrogen was 1.0 ml / min and 100% methanol was 0.2 g / hr. The decomposition rate of the hydrogen bath of methanol after 24 hours of reaction was measured using the gas chromatography (13), and the result is shown in Table 1.

Example Solid acid / mixed solid acid Methanol decomposition rate (% by volume) One Aluminum oxide 8.2 2 Titanium oxide 7.8 3 Cesium oxide 8.2 4 Zinc oxide 8.6 5 Kaolinite 8.7 6 Zeolite 8.0 7 Cadmium sulfate 6.5 8 Cobalt sulfate 6.9 9 Calcium nitrate 7.1 10 Zinc nitrate 7.6 11 Iron phosphate III 6.8 12 Zirconium Phosphate 7.2 13 Silver chloride 7.3 14 Cobalt sulfate 30.3 15 Zinc sulfate 29.0 16 Copper sulfate 19.9 17 Vanadium oxide 29.8

Experimental Example 2-Reaction Characteristics by Addition of Sulfuric Acid

A mixed catalyst raw material mixture was prepared by simultaneously mixing 60 parts by weight of zinc oxide solid acid and 40 parts by weight of each solid acid of Table 2 by weight.

Sulfuric acid diluted to 10%, 20%, and 30% concentrations in the mixture was kneaded by 1.5 times in weight ratio, and then molded into a cylindrical shape having a diameter of 3 mm and a length of 10 mm, and dried at room temperature for 72 hours. The dried mixture was calcined at 1,100 ° C. for 12 hours in an electric furnace and cooled to room temperature to obtain a ceramic catalyst.

40 g of the solid acid composite catalyst prepared above was taken and placed in the catalyst tower 8 of FIG.

The gas flow meter 3 and the liquid flow meter 4 were adjusted so that nitrogen was 1.0 ml / min and 100% methanol was 0.2 g / hr in the catalyst tower 8.

The decomposition rate of the hydrogen bath of methanol after 3 hours of reaction was measured using gas chromatography (13), and the result is shown in Table 2.

Example Mixed solid acid Methanol decomposition rate (vol%) according to sulfuric acid concentration 10% 20% 30% One Aluminum oxide 23.5 27.3 28.5 2 Titanium oxide 22.8 26.5 28.3 3 Silicon oxide 22.3 26.4 27.9 4 Magnesium oxide 21.9 25.8 26.8 5 Kaolinite 23.4 26.7 27.5 6 Montmorillonite 22.0 22.5 22.5 7 Cobalt sulfate 23.5 23.8 23.9 8 Iron phosphate III 22.6 22.9 23.0

Experimental Example 3-Reaction Characteristics of Metal Compounds Added

50 parts by weight of zinc oxide solid acid and 45 parts by weight of aluminum oxide solid acid were first mixed by weight, and then 5 parts by weight of each metal compound of Table 3 was mixed again to prepare a composite catalyst raw material mixture. On the other hand, a mixture of a metal compound of sodium nitrate and sodium sulfate (which is initially mixed but does not act as the solid acid, which is a metal compound) was added to 94 parts by weight of a zinc oxide solid acid in 6 parts by weight, respectively. 3 is shown.

The mixture was kneaded with 1.5 times the weight ratio of distilled water, and then molded into a cylindrical shape having a diameter of 3 mm and a length of 10 mm, and dried at room temperature for 72 hours.

The dried mixture was calcined at 1,100 ° C. for 12 hours in an electric furnace and cooled to room temperature to obtain a ceramic catalyst.

40 g of the combined catalyst of the solid acid and the metal compound was taken into the catalyst tower 8 of FIG. 2, and the temperature of the temperature control section 7 and the catalyst tower 8 was maintained at 250 ° C.

The gas flow meter 3 and the liquid flow meter 4 were adjusted so that nitrogen was 1.0 ml / min and 100% methanol was 0.2 g / hr in the catalyst tower 8.

The decomposition rate of the hydrogen bath of methanol after reaction 3 hours was measured using the gas chromatography (13), and the result is shown in Table 3.

Example Mixed metal compound Methanol decomposition rate (%) One Sodium sulfate 32.8 2 Lithium phosphate 26.5 3 Magnesium nitrate 25.6 4 Calcium phosphate 30.7 5 Potassium oxide 27.5 6 Barium peroxide 31.4 7 Calcium hydroxide 33.1 8 Sodium hydroxide 32.1 9 Magnesium oxide 31.3 10 Sodium nitrate 19.7 11 Sodium sulfate 19.3

Experimental Example 4-Reaction Characteristics of Transition Metal Compound Added 1

A composite catalyst mixture was prepared by mixing 6 parts by weight of each of the water soluble transition metal compounds of Table 4 (which are initially mixed but do not act as the solid acid) by 94 parts by weight of zinc oxide solid acid by weight.

The mixture was kneaded with 1.5 times the weight ratio of distilled water, and then molded into a cylindrical shape having a diameter of 3 mm and a length of 10 mm, and dried at room temperature for 72 hours.

The dried molded product was calcined at 1,100 ° C. for 12 hours in an electric furnace, and cooled to room temperature to obtain a ceramic catalyst.

40 g of the solid acid complex catalyst was taken into the catalyst tower 8 of FIG. 2 and the temperature of the temperature control section 7 and the catalyst tower 8 was maintained at 250 ° C.

The gas flow meter 3 and the liquid flow meter 4 were adjusted so that nitrogen was 1.0 ml / min and 100% methanol was 0.2 g / hr in the catalyst tower 8.

The decomposition rate of the hydrogen bath of methanol 3 hours after the reaction was measured using gas chromatography (13), and the results are shown in Table 4.

Example Mixed transition metal compound Methanol decomposition rate (%) One Manganese Phosphate 28.9 2 Zinc hydroxide 28.1 3 Cadmium hydroxide 29.7 4 Chromium hydroxide 29.3 5 Cobalt nitrate 28.3 6 Copper Nitrate 28.5

Experimental Example 5-Reaction Characteristics by Addition of Metal Compound and Transition Metal Compound

50 parts by weight of zinc oxide solid acid and 45 parts by weight of aluminum oxide solid acid were first mixed by weight, and then 5 parts by weight of the metal compound calcium hydroxide (Ca (OH) ₂ ) was mixed again, followed by 85 parts by weight of the mixture. Finally, 15 parts by weight of the transition metal compound was mixed to prepare a composite catalyst raw material mixture (in terms of% by weight, 80.75% by weight of total solid acid, 4.25% by weight of calcium hydroxide and 15% by weight of transition metal compound).

The mixture was kneaded with 1.5 times the weight ratio of distilled water, and then molded into a cylindrical shape having a diameter of 3 mm and a length of 10 mm, and dried at room temperature for 72 hours.

The dried molded product was calcined at 1,000 ° C. for 12 hours in an electric furnace, and cooled to room temperature to obtain a ceramic catalyst.

40 g of the solid acid complex catalyst was taken into the catalyst tower 8 of FIG. 2 and the temperature of the temperature control section 7 and the catalyst tower 8 was maintained at 250 ° C.

The gas flow meter 3 and the liquid flow meter 4 were adjusted so that nitrogen was 1.0 ml / min and 100% methanol was 0.2 g / hr in the catalyst tower 8.

The decomposition rate of the hydrogen bath of methanol 3 hours after the reaction was measured using gas chromatography (13), and the results are shown in Table 5.

Example Mixed transition metal compound Methanol decomposition rate (%) One Cobalt sulfate 75.3 2 Zinc sulfate 73.4 3 Manganese Phosphate 77.1 4 Zinc hydroxide 68.3 5 Cadmium hydroxide 67.9 6 Vanadium oxide 76.9 7 Cobalt nitrate 74.8 8 Copper Nitrate 65.5

Experimental Example 6-Reaction Characteristics by Addition of Electrolyte

By weight of 94 parts by weight of zinc oxide solid acid by adding each of the electrolytes of Table 6 (which is the first mixed but does not act as the solid acid and is not the metal compound or transition metal compound, it is an electrolyte) The composite catalyst raw material mixture was prepared.

The mixture was kneaded with 1.5 times the weight ratio of distilled water, and then molded into a cylindrical shape having a diameter of 3 mm and a length of 10 mm, and dried at room temperature for 72 hours.

The dried molded product was calcined at 900 ° C. for 12 hours in an electric furnace, and cooled to room temperature to obtain a ceramic catalyst.

40 g of the solid acid complex catalyst was taken into the catalyst tower 8 of FIG. 2 and the temperature of the temperature control section 7 and the catalyst tower 8 was maintained at 250 ° C.

The gas flow meter 3 and the liquid flow meter 4 were adjusted so that nitrogen was 1.0 ml / min and 100% methanol was 0.2 g / hr in the catalyst tower 8.

The decomposition rate of the hydrogen bath of methanol after 3 hours of reaction was measured using gas chromatography (13), and the result is shown in Table 6.

Example Mixed electrolyte Methanol decomposition rate (%) One Sodium chloride 19.5 2 Potassium chloride 19.2 3 Lithium carbonate 20.0 4 Sodium carbonate 20.4 5 Potassium carbonate 19.6

Experimental Example 7 Reaction Characteristics According to Methanol Concentration

50 parts by weight of a zinc oxide solid acid raw material and 45 parts by weight of an aluminum oxide solid acid raw material were mixed on a weight basis, and then 8 parts by weight of sodium sulfate as an electrolyte based on 92 parts by weight of a mixture obtained by mixing 5 parts by weight of sodium hydroxide (NaOH), a metal compound. In addition, a composite catalyst raw material mixture was prepared (in terms of weight%, respectively, 87.4 weight% of solid acid, 4.6 weight% of calcium hydroxide, and 8 weight% of sodium sulfate).

The mixture was kneaded with 1.5 times the weight ratio of distilled water, and then molded into a cylindrical shape having a diameter of 3 mm and a length of 10 mm, and dried at room temperature for 72 hours.

The dried molded product was calcined at 900 ° C. for 12 hours in an electric furnace, and cooled to room temperature to obtain a ceramic catalyst.

40 g of the solid acid complex catalyst is taken into the catalyst tower 8 of FIG. 2 and the temperature of the temperature control section 7 and the catalyst tower 8 is maintained at 250 ° C.

By adjusting the gas flow meter 3 and the liquid flow meter 4, nitrogen is introduced into the catalyst tower 8 at 100 g of methanol, 70% methanol and 40% methanol at 0.2 g / hr at 1.0 ml / min, respectively.

According to the reaction time, the decomposition rate of the hydrogen bath of methanol was measured using gas chromatography (13), and the results are shown in Table 7.

Example Methanol concentration (%) Methanol decomposition rate (vol%) according to reaction time 1 hours 15 hours 24 hours 36 hours 48 hours 60 hours One 100 9.7 83.6 89.3 91.7 92.7 95.9 2 70 9.5 61.0 85.1 89.1 94.2 97.6 3 40 9.6 52.3 60.8 67.1 72.5 92.2

According to the present invention, there is no formation of by-products such as formaldehyde and methyl formate other than hydrogen, there is no problem of lowering the amount of hydrogen by methanation reaction between the produced hydrogen and carbon monoxide, and the price is low, and the pretreatment and post-treatment There is no need to go through the process or constraints to maintain the reaction within the proper temperature, methanol can be decomposed continuously to generate hydrogen, and optionally an organic compound can be synthesized.

Although the present invention has been described in connection with the above-mentioned preferred embodiments, it is possible to make various modifications or variations without departing from the spirit and scope of the invention. Accordingly, the appended claims will cover such modifications and variations as fall within the spirit of the invention.

Claims (17)

Kaolinite, bentonite, attapulgite, zeolite, montmorillonite, zinc oxide (ZnO), aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), oxide Cesium (CeO ₂ ), vanadium oxide (V ₂ O ₅ ), silicon oxide (SiO ₂ ), chromium oxide (Cr ₂ O ₃ ), calcium sulfate (CaSO ₄ ), 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 II (FeSO ₄ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ), sulfuric acid Zinc (ZnSO ₄ ), calcium nitrate (Ca (NO ₃ ) ₂ ), zinc nitrate (Zn (NO ₃ ) ₂ ), iron nitrate III (Fe (NO ₃ ) ₃ ), aluminum phosphate (AlPO ₄ ), iron phosphate III (FePO ₄ ), chromium phosphate (CrPO ₄ ), copper phosphate (Cu ₃ (PO ₄ ) ₂ ), zinc phosphate (Zn ₃ (PO ₄ ) ₄ ), magnesium phosphate (Mg ₃ (PO ₄ ) ₂ ), aluminum chloride (AlCl ₃ ), titanium chloride (TiCl ₄ ), calcium chloride (CaCl ₂ ), silver chloride (AgCl), calcium fluoride (CaF ₂ ) or barium fluoride (BaF ₂ ) Or a solid acid catalyst obtained by firing a mixture of two or more solid acids simultaneously. The method of claim 1, Wherein said solid acid is mixed with sulfuric acid or phosphoric acid and calcined. The method of claim 2, The sulfuric acid is a solid acid catalyst, characterized in that the sulfuric acid diluted to more than 0% 30% or less when used 1.5 times by weight relative to the solid acid. The method of claim 1, In the solid acid, Sulfates of alkali metals different from the above solid acids, sulfites of alkali metals, phosphates of alkali metals, nitrates of alkali metals, nitrites of alkali metals, hydroxides of alkali metals, oxides of alkali metals, peroxides of alkali metals, superoxides of alkali metals, Metal compounds which are any one or a mixture of sulfates of alkaline earth metals, sulfites of alkaline earth metals, phosphates of alkaline earth metals, nitrates of alkaline earth metals, nitrites of alkaline earth metals, hydroxides of alkaline earth metals, oxides of alkaline earth metals or peroxides of alkaline earth metals; Transition metal compounds which are any one or a mixture of sulfates of transition metals different from the solid acid, sulfites of transition metals, phosphates of transition metals, nitrates of transition metals, nitrites of transition metals, hydroxides of transition metals or oxides of transition metals; or Any one or two of chlorides of alkali metals different from the solid acid, nitrates of alkali metals, sulfates of alkali metals, carbonates of alkali metals, phosphates of alkali metals, chlorides of transition metals, nitrates of transition metals or sulfates of transition metals An electrolyte which is a mixture of the above; Solid acid catalyst, characterized in that any one of the second mixture and calcined. The method of claim 4, wherein 20 to 99.9 weight percent of the solid acid; And 0.1 to 80% by weight of the metal compound or the transition metal compound. The method of claim 4, wherein 20 to 99.9 weight percent of the solid acid; And 0.1 to 30% by weight of the electrolyte; solid acid catalyst comprising the. The method of claim 4, wherein In the solid acid, the metal compound different from the solid acid or the transition metal compound different from the solid acid is secondly mixed, and then, in the second mixed mixture, the transition metal compound different from the solid acid or the different from the solid acid Solid acid catalyst, characterized in that the metal compound is mixed and calcined for the third time. The method of claim 7, wherein 20 to 99.9 weight percent of the solid acid; 0.1 to 80% by weight of the metal compound; And 0.1 to 50% by weight of the transition metal compound; Solid acid catalyst comprising a. The method of claim 4, wherein In the solid acid, the metal compound different from the solid acid or the transition metal compound different from the solid acid is secondly mixed, and then, in the second mixed mixture, the metal acid or the transition metal compound is different from the solid acid. And wherein said different electrolytes are mixed and calcined for the third time. The method of claim 9, 20 to 99.9 weight percent of the solid acid; 1 to 80% by weight of the metal compound or the transition metal compound; And 0.1 to 30% by weight of the electrolyte; solid acid catalyst comprising the. The method of claim 4, wherein In the solid acid, the metal compound different from the solid acid or the transition metal compound different from the solid acid is secondly mixed, and then, in the second mixed mixture, the transition metal compound different from the solid acid or the different from the solid acid And a third metal mixture is mixed with the third, and the third mixed mixture is calcined by the fourth mixture of the electrolyte different from the solid acid and different from the metal compound or the transition metal compound. The method of claim 11, 20 to 99.9 weight percent of the solid acid; 0.1-80% by weight of the metal compound; 0.1-50% by weight of the transition metal compound; And 0.1 to 30% by weight of the electrolyte; solid acid catalyst comprising the. Kaolinite, bentonite, attapulgite, zeolites, zeolites, montmorillonite, zinc oxide (ZnO), aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), oxide Cesium (CeO ₂ ), vanadium oxide (V ₂ O ₅ ), silicon oxide (SiO ₂ ), chromium oxide (Cr ₂ O ₃ ), calcium sulfate (CaSO ₄ ), 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 II (FeSO ₄ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ), sulfuric acid Zinc (ZnSO ₄ ), calcium nitrate (Ca (NO ₃ ) ₂ ), zinc nitrate (Zn (NO ₃ ) ₂ ), iron nitrate III (Fe (NO ₃ ) ₃ ), aluminum phosphate (AlPO ₄ ), iron phosphate III (FePO ₄ ), chromium phosphate (CrPO ₄ ), copper phosphate (Cu ₃ (PO ₄ ) ₂ ), zinc phosphate (Zn ₃ (PO ₄ ) ₄ ), magnesium phosphate (Mg ₃ (PO ₄ ) ₂ ), aluminum chloride (AlCl _3), in which titanium tetrachloride (TiCl _4), calcium chloride (CaCl _2), silver chloride (AgCl), calcium fluoride (CaF ₂₎ or barium fluoride (BaF ₂₎ Method for producing a solid acid or or 2 characterized in that at the same time mixing the at least one solid acid and a step (S1) of calcining the catalyst. The method of claim 13, In the step S1, to the solid acid, Sulfates of alkali metals different from the above solid acids, sulfites of alkali metals, phosphates of alkali metals, nitrates of alkali metals, nitrites of alkali metals, hydroxides of alkali metals, oxides of alkali metals, peroxides of alkali metals, superoxides of alkali metals, Metal compounds which are any one or a mixture of sulfates of alkaline earth metals, sulfites of alkaline earth metals, phosphates of alkaline earth metals, nitrates of alkaline earth metals, nitrites of alkaline earth metals, hydroxides of alkaline earth metals, oxides of alkaline earth metals or peroxides of alkaline earth metals; Transition metal compounds which are any one or a mixture of sulfates of transition metals different from the solid acid, sulfites of transition metals, phosphates of transition metals, nitrates of transition metals, nitrites of transition metals, hydroxides of transition metals or oxides of transition metals; or Any one or two of chlorides of alkali metals different from the solid acid, nitrates of alkali metals, sulfates of alkali metals, carbonates of alkali metals, phosphates of alkali metals, chlorides of transition metals, nitrates of transition metals or sulfates of transition metals An electrolyte which is a mixture of the above; Method for producing a solid acid catalyst, characterized in that any one of the second mixture and calcining. The method of claim 14, In the step S1, after the second mixture of the metal compound different from the solid acid or the transition metal compound different from the solid acid to the solid acid, the transition metal compound different from the solid acid to the second mixed mixture or And a third mixture of the metal compound different from the solid acid is fired. The method of claim 14, In the step S1, after mixing the solid acid with the metal compound different from the solid acid or the transition metal compound different from the solid acid for the second time, the second mixed mixture is different from the solid acid and the metal compound or And a third mixture of the electrolyte different from the transition metal compound is fired. The method of claim 14, In the step S1, after the second mixture of the metal compound different from the solid acid or the transition metal compound different from the solid acid to the solid acid, the transition metal compound different from the solid acid to the second mixed mixture or And mixing the third metal compound different from the solid acid into a third mixture, and mixing the third mixed mixture with the electrolyte different from the solid acid and different from the metal compound or the transition metal compound into a fourth mixture. Method for preparing a solid acid catalyst.

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