KR20120133751A

KR20120133751A - Three-dimensional bimodal mesoporous carbon-supported metallic catalyst and method for aqueous-phase reforming of oxygenated compounds using the same

Info

Publication number: KR20120133751A
Application number: KR1020110052570A
Authority: KR
Inventors: 정영민; 김태진; 오승훈; 정순용; 김철웅; 정광은; 채호정; 김태완; 박현주
Original assignee: 에스케이이노베이션 주식회사; 한국화학연구원
Priority date: 2011-06-01
Filing date: 2011-06-01
Publication date: 2012-12-11
Also published as: KR101843974B1

Abstract

PURPOSE: A carbon supported metal catalyst with a three dimensional bimodal mesoporous structure and an aqueous phase reforming method of oxygenated compounds using the same are provided to directly form carbon with a bimodal porous structure without a separate template material. CONSTITUTION: An aqueous phase reforming method of oxygenated compounds using a carbon supported metal catalyst with a three dimensional bimodal mesoporous structure includes the following steps: a carbon precursor is impregnated into silica; the impregnated product is dried and carbonated to prepare a silica/carbon complex; and the silica is removed from the silica/carbon complex. The silica is one or more selected from silica gel with mesopores, silica nanoparticles, silica beads, aluminum anodic oxide, and alumino silicagel. [Reference numerals] (AA) Adsorption; (BB) Desorption; (CC) Adsorption amount; (DD) Relative pressure

Description

Three-dimensional bimodal mesoporous carbon-supported metallic catalyst and method for aqueous-phase reforming of oxygenated compounds using the same}

The present invention discloses a carbon-supported metal catalyst having a three-dimensional binary mesoporous structure and an aqueous phase reforming method of an oxygen compound using the same. More specifically, the present invention discloses a metal catalyst supported on a carbon material having three-dimensional binary mesopores and a method for selectively producing hydrogen by an aqueous phase reforming reaction using an oxygen compound as a raw material in the presence of the catalyst.

The rapid increase in the consumption of fossil-based energy sources such as coal, oil and natural gas has led to the emergence of energy security and environmental pollution, which has become an important issue in creating a sustainable society. Renewable energy is the only alternative to solve these problems at the same time, and various countries are developing various related technologies. In particular, recently, as interest in hydrogen as a feedstock and a major clean energy source for the synthesis of various chemicals has increased, various studies for producing hydrogen from biomass, which is a representative renewable energy source, have been conducted. Conversion techniques that can produce hydrogen from biomass include gasification, pyrolysis and enzymatic degradation, but the process itself is complex or the conversion rate to hydrogen is low (Huber et al., Chem. Rev. 106 (2006) p.4044; Navarro et al. , Chem. Rev. 107 (2007) p.3952).

In addition, steam reforming, which is known as one of the most effective methods for producing hydrogen, has the disadvantage of high energy consumption because it is generally composed of gasification and linkage system and operates above 700 ° C.

Recently, an aqueous phase reforming process (APR) was developed by the University of Wisconsin, USA, to effectively produce hydrogen in a liquid state from biomass-derived oxygen carbohydrates compounds. It has been spotlighted as an alternative to overcome the disadvantages. In other words, the water reforming process can be operated at a lower temperature of less than 300 ℃ because the toxic by-products are generated little during operation. In addition, since the reaction takes place in the liquid phase, the reforming reaction and the water-gas shift (WGS) reaction occur simultaneously in one system, so that the concentration of carbon monoxide in the product is very low (100 ppm or less) and separate as in steam reforming. It is known to have high hydrogen production rate and selectivity because no methanization reaction step is required. Therefore, APR studies based on various oxygen compounds such as glucose, glycerol, ethylene glycol, and sugar alcohols are being actively conducted (Cortright et al., Nature. 418 (2002) p.964; Huber et al., Science. 300 (2003) p. 2075; Davda et al., Appl. Catal., B: Environ., 56 (2005) p.171).

The known water phase reforming process is a process for producing hydrogen using an oxygen compound as a raw material, but from the reaction mechanism, carbon-carbon bond cleavage, water gas conversion, dehydrogenation / hydrogenation reaction, methanation reaction, It is accompanied by complex chemical reactions such as the Fischer-Tropsch reaction, and finally light hydrocarbons, carbon dioxide and low concentrations of carbon monoxide as well as the desired hydrogen are side reactions. Therefore, to obtain high hydrogen selectively, the carbon-carbon bond splitting rate and the methanation / Fischer-Tropsch reaction must be very large (Davda et al., Appl. Catal., B: Environ., 56 (2005) p.171). The complex chemical reactions in the water reforming process are greatly influenced by the reaction conditions such as catalyst, feedstock, temperature and pressure, and the most essential element technology is known as a catalyst.

Reported to date, it is known that noble metal catalysts such as platinum (Pt), rhodium (Rh) and ruthenium (Ru) are excellent in water phase reforming reactions. The composite metal catalyst prepared by the addition of Re) shows excellent activity even with a low metal content. In order to improve the conversion rate and hydrogen selectivity of the oxygen compound, researches on various metal types as well as carriers of these metals have been extensively performed. In particular, the importance of metal carriers is well illustrated by studies by Shabaker et al. (Catal. Lett. 88 (2003) p. 1) and Wen et al. (Int. J. Hydrogen Energy. 33 (2008) p. 6657). According to the results of these studies comparing metal-supported catalysts, the activity and hydrogen selectivity of the catalysts are reported to be significantly influenced by the catalyst carrier rather than the dispersity of the metals. Alumina oxide (Al ₂ O ₃ ), zirconia oxide Various studies have been conducted using metal oxides such as (ZrO ₂ ), silica oxide (SiO ₂ ), cerium oxide (CeO ₂ ), zinc oxide (ZnO), titanium dioxide (TiO ₂ ), and the like as a catalyst support. However, these metal oxides are susceptible to sintering due to low hydrothermal stability, collapse of pores, and phase transitions in small surface areas in meta-stable phases with large surface areas, depending on the carrier. It is known that it is not possible to maintain stable activity in the reforming reaction (Johnson et al., J. Catal. 123 (1990) p.245; Shabaker et al., Catal. Lett. 88 (2003) 1; Ketchie et al., Chem. Mater. 19 ( 2007) p. 3406; Wen et al., Int. J. Hydrogen Energy. 33 (2008) p.6657). Therefore, studies on carbon materials have been made as a support for overcoming the disadvantages of such metal oxides.

Korean Patent Publication No. 10-2008-0078911 (International Patent WO 2007/075476) discloses a water phase modification method for various oxygen-containing compounds using a catalyst in which Group VIIIB transition metals and Group VIII transition metals are supported on activated carbon in the form of single or complex metals. This is described. See also, Shabaker et al. (Catal. Lett. 88 (2003) p.1), Wen et al. (Int. J. Hydrogen Energy. 33 (2008) p.6657; Catal. Commun. 11 (2010) p.522), King (Appl. Catal. B: Environ. 99 (2010) p.206) also used activated carbon as catalyst support, and Wang et al. (Catal. Today. 146 (2009) p.160) described single-walled carbon nanotubes (single). wall carbon nanotube (SWCNT) was used as a catalyst carrier. However, despite the high surface area and excellent hydrothermal stability, these activated carbons have irregular pore arrays and wide pore distributions ranging from micro (less than 2 nm) to macro (more than 50 nm). In particular, the intrinsic nature of activated carbon, which is mostly composed of micropores, can prevent the reactants from contacting catalytically active sites in liquid phase reactions. It does not escape, but fills the micro pores to prevent the catalytic active point in the micro pores from contacting the reactants, so that in order to improve the selectivity and formation rate of hydrogen in the water reforming reaction using activated carbon having such a structure There is a limit.

In Korean Patent Application Nos. 10-2010-0029422 and 10-2010-0029421, in order to solve the above-mentioned problems, alumina or carbon having mesopores of regular and uniform size is synthesized to support a catalyst for such a reaction. Sieve was used. As a result, the conversion rate and the hydrogen production rate of the oxygen compound is improved compared to the case of using the known alumina and activated carbon. However, the two-dimensional structure of the CMK-3 and CMK-5 synthetic carbon carriers may cause low mass transfer and diffusion rates of reactants and products in the aqueous phase reforming reaction where gas-liquid reactions occur simultaneously in one system. In the step, since the mesoporous silica compound must be prepared by hydrothermal synthesis in advance, the synthesis process is complicated, and the material cost of the silica precursor required for the synthesis is very high, and various kinds of oxygen compounds applicable to the water phase reforming reaction are considered. The pore size is difficult to control. The pore size control and structural limitations of CMK-3 and CMK-5 are somewhat resolved when applying the dual templating method reported by Lee et al. (Adv. Mater. 20 (2008) p.757). However, since the carbon of the binary pore structure manufactured by this method also needs to separately prepare a mold material having a certain pore size, there is a complicated synthesis process and a high material cost problem, and it is not easy to control the size of the mesopores, Further particle shaping processes are needed to produce large scale catalysts.

In one embodiment of the present invention, by using a low-cost commercial mold material having mesopores of various sizes, the carbon of the binary pore structure is directly manufactured in the form of molded particles, and thus, unlike the conventional carbon carrier, it is necessary to separately prepare the mold material. It is intended to provide a catalytic synthesis process.

In addition, an embodiment of the present invention provides a carbon carrier having various pore sizes and three-dimensional binary structures by using a commercial template material and controlling the drying time of the carrier and the degree of polymerization of the carbon precursor accordingly. By supporting metal catalysts, various oxygen-containing compounds are effectively converted into hydrogen, and material transfer and diffusion rates are increased.

In addition, another embodiment of the present invention, to provide a method for producing hydrogen by the water phase modification of the oxygen compound using a carbon-supported metal catalyst having a three-dimensional binary mesoporous structure.

According to one aspect of the present invention, a carbon precursor is impregnated into commercial silica, which is a template, and then dried and carbonized to obtain a silica / carbon composite, and silica is removed from the silica / carbon composite to prepare carbon having three-dimensional binary mesopores. Provide a way to.

According to another aspect of the present invention, a silica precursor is impregnated with commercially available silica, followed by drying and carbonization to obtain a silica / carbon composite, and having a three-dimensional binary mesoporous prepared by removing silica from the silica / carbon composite. Provide carbon.

According to another aspect of the present invention, using a commercial silica having a variety of particle sizes and three-dimensional mesopores as a template material to prepare a carbon carrier having a three-dimensional binary mesopores, platinum alone or platinum on the carbon carrier Provided is a carbon-supported metal catalyst supported on a transition metal complex such as rhenium, iron, or manganese.

According to another aspect of the present invention, in order to maximize the conversion rate and hydrogen production through the water phase reforming of the biomass-derived oxygen compound prepared by supporting a metal on carbon having a three-dimensional binary mesopores prepared according to the present invention It provides a method for selectively producing hydrogen by the water phase reaction of the oxygen compound in the presence of the catalyst.

Since the carbon carrier having the three-dimensional binary mesopores according to one embodiment of the present invention does not need to prepare a separate mold material by using inexpensive commercial silica as a template material, a complicated process of manufacturing a conventional carbon supported catalyst, High material cost and the problem of further molding process can be solved. In addition, the carbon carrier according to the embodiment of the present invention has excellent hydrothermal stability and excellent physical properties such as large surface area and large pore volume.

In addition, the carbon-supported metal catalyst according to one embodiment of the present invention uses a carbon carrier having regularly arranged pores, so that the disadvantages of the existing carrier, that is, gas products do not easily escape micropores, fill the pores. The problem of preventing the contact between the catalyst active point in the micropores and the reactants can be reduced.

In addition, when the carbon-supported catalyst according to an embodiment of the present invention is applied to the water phase reforming of the biomass-derived oxygen compound, the conversion to gas and the hydrogen yield may be increased.

1 is a flow chart schematically illustrating a process for producing a three-dimensional binary mesoporous carbon carrier according to one embodiment of the present invention.
Figure 2 is a carbon support having a three-dimensional binary mesopores according to one embodiment of the present invention prepared by the mesoporous template material ((a) silica gel; (c) silica beads) and replica thereof ((b) carbon Particles; (d) carbon beads; (a) and (c) are FE-SEM images using JSM 6700F (JEOL KOREA Co.), and (b) and (d) are images taken with a normal camera. to be.
3 is a nitrogen adsorption and desorption curve and pore size distribution according to the drying time of the carbon carrier according to the embodiment of the present invention.
4 is SEM (a, c) and TEM (b, d) images of the carbon carrier according to an embodiment of the present invention, (a) and (b) is for Example 1 (3D-MC-1 ), (c) and (d) are for Example 4 (3D-MC-12).
FIG. 5 is a flow chart schematically showing a process for producing a composite metal catalyst according to one embodiment of the present invention based on platinum.

Hereinafter, the present invention will be described more specifically.

The present invention comprises impregnating a carbon precursor into a commercial silica that is a template followed by drying and carbonizing to obtain a silica / carbon composite; And it provides a method for producing carbon having a three-dimensional binary mesopores comprising the step of removing the silica from the silica / carbon composite and the carbon having a three-dimensional binary mesopores obtained therefrom.

In one embodiment, a series of processes of impregnating, drying, and carbonizing a carbon precursor in commercial silica may be repeated two or more times, one or more of which may each independently be repeated two or more times.

The method of impregnating the carbon precursor with silica may use conventional impregnation methods known in the art, such as, but not limited to, incipient wetness impregnation or excess water impregnation.

In one embodiment, drying may be carried out at a temperature of 80 to 150 ° C. for 1 to 24 hours, and carbonization may be performed at 300 to 400 ° C. for 2 to 4 hours, or more. If carbonization is carried out two or more times, the initial carbonization is carried out at 300 to 400 ° C. for 2 to 4 hours, and the subsequent carbonization may be carried out at a higher temperature, for example, at 800 to 950 ° C. for 2 to 4 hours. .

In one embodiment of the present invention, binary mesopores can be prepared by controlling the size of the mesopore according to the structure of the commercial silica and impregnating the carbon precursor into the commercial silica and controlling the mesopore size in accordance with the drying time. have. Conventionally, in order to manufacture binary mesoporous carbon, it is not only necessary to synthesize a template material having binary mesopores primarily, but also to control the size of the external mesopore. However, in the present invention, by forming the primary mesopores having a size corresponding to the wall thickness of the mold material, by controlling the drying temperature and time of the carbon precursor impregnated in the mold material by controlling the size of the mesopore formed second Mesopores can be dualized. The longer the drying time, the greater the degree of polymerization of the carbon precursor or the greater the amount of secondary mesopores (FIG. 3). For example, the primary silica concentrated at about 4 nm, corresponding to the wall thickness of the commercial silica, by impregnating the carbon precursor into the commercial silica and then varying from 2 to 12 hours at 100 ° C., as described in the Examples below. Together with the mesopores, open secondary mesopores of 10 nm or more can be formed at the pore inlet.

In one embodiment, the silica may be removed by etching the silica material from the silica / carbon composite under a solution such as, for example, aqueous HF or NaOH solution.

In the present invention, the commercial silica has three-dimensional mesopores and includes all commercially available commercially available silicas without requiring a separate manufacturing process. Representative examples thereof include silica gel, silica nanoparticles, silica beads, aluminum anodization, Or alumino silica gel. As used herein, the term "silica" is to be interpreted to include all types of silica that are naturally present or artificially produced, such as crystalline, amorphous, crystalline, and hydrated compounds.

Examples of carbon precursors impregnated with silica include carbohydrates, acetylene, furfuryl alcohol, divinylbenzene, and phenyl acetyl nitrile, and include carbon that can form a complex with silica as a template to replicate the mesopores of the template. The material is not particularly limited.

As used herein, "silica / carbon composite" refers to a composite of silica as a template and a carbon material impregnated thereon.

1 is a flow chart schematically illustrating a method of manufacturing a three-dimensional binary mesoporous carbon carrier according to an embodiment of the present invention. As shown in FIG. 1, in one embodiment of the present invention, three-dimensional dual mesoporous carbon carriers may be prepared using silica gel as a template material. An example of a representative carbon support prepared according to an embodiment of the invention is shown in FIG. 2. In the examples described below, examples of preparing a three-dimensional binary mesoporous carbon carrier prepared using silica gel as a template and furfuryl alcohol as a carbon precursor are described.

The carbon carrier prepared according to the present invention having three-dimensional binary mesopores can be confirmed through nitrogen adsorption and desorption isotherms, SEM and TEM images of the prepared carbon carrier. As an embodiment, nitrogen adsorption and desorption isotherms, SEM, and TEM images of the carbon carrier prepared according to the embodiment of the present invention are shown in FIGS. 3 and 4, respectively. 3 and 4, it can be seen that the carbon carrier according to the embodiment of the present invention forms mesopores concentrated at about 4 nm corresponding to the wall thickness of the silica gel as a template. In addition, since the drying process plays a role of promoting polymerization of the carbon precursor (for example, polymerization of furfuryl alcohol to polyfurfuryl alcohol), polymerization of the carbon precursor proceeds gradually in proportion to the drying time. Large mesopores between 10 and 17 nm may be additionally formed outside the pore inlet, thereby producing a three-dimensional mesoporous carbon carrier having a wormhole shape.

Another aspect of the present invention provides a metal catalyst supported on carbon having three-dimensional binary mesopores. In one embodiment of the present invention, the metal supported on carbon may be platinum alone or a composite metal of platinum and a transition metal.

In one embodiment of the invention, examples of transition metals in the composite metal of platinum and transition metal include rhenium (Re), iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), or mixtures thereof. Although it is not limited thereto, each composite metal may be composed of various compositions.

Non-limiting examples of platinum precursors for impregnation of platinum include hexachloroplatinic acid (H ₂ PtCl ₆ ), platinum ammonium chloride (Pt (NH ₃ ) ₄ Cl ₂ ), platinum ammonium nitrate (Pt (NH ₃ ) ₄ (NO ₃ ) ₂ ), and the like.

Precursors for impregnation of rhenium, iron, manganese, nickel or cobalt include perrhenic acid (HReO ₄ ), iron (III) nitrate nonahydrate, Fe (NO ₃ ) ₃ 9H ₂ O), manganese (II) nitrate hydrate (manganese (II) nitrate hydrate, Mn (NO ₃ ) ₂ ? XH ₂ O), nickel (II) nitrate hexahydrate, Ni (NO ₃ ) ₂ ˜6H ₂ O), cobalt (II) nitrate hexahydrate (Cobalt (II) nitrate hexahydrate, Co (NO ₃ ) ₂ ˜6H ₂ O), and the like. Various precursors can be used.

The method of supporting the metal on the carrier is not particularly limited, and conventional impregnation methods known in the art may be used. Specifically, an incipient wetness method that allows for uniform dispersion when the catalyst is dispersed in the carrier is exemplified.

In one embodiment of the present invention, the content of the metal in the catalyst is 1 to 7% by weight (wt%) based on the total weight of the catalyst when the platinum alone, and when supporting the composite metal of platinum and transition metal, The platinum content is 1 to 5 wt% based on the total weight of the catalyst, and the remaining metal content may be impregnated with each metal in the range of 0.1 to 10 moles based on 1 mole of platinum.

In another embodiment, the amount of platinum supported is 1 to 5 wt% based on the total weight of the catalyst and the amount of other transition metals supported may range from 0.1 to 10 moles based on 1 mole of platinum.

A method of preparing a catalyst by impregnating a metal using a carbon carrier having mesopores according to one embodiment of the invention is shown in FIG. 5.

Another aspect of the present invention provides a method for producing hydrogen by reforming a raw material solution containing an oxygen compound using a carbon supported metal catalyst according to the present invention.

In the present specification, the oxygen-containing compound may or may not be biomass-derived, and is interpreted broadly to include an oxygen-containing compound that generates hydrogen through an aqueous reforming reaction such as ethylene glycol, propylene glycol, glycerol, glycerin, sorbitol, mannitol, and the like. do.

In one embodiment, the raw material solution comprising an oxygenated compound is at least 10% by weight of one or more compounds selected from ethylene glycol, propylene glycol, glycerol, glycerin, sorbitol, mannitol, and the like.

In the present invention, in order to maximize the conversion rate and hydrogen production through the water phase reforming of the oxygen compound, the carbon having the three-dimensional binary mesopores prepared according to the present invention is used as a carrier and platinum alone or platinum, rhenium, iron Hydrogen may be selectively produced by an aqueous phase reforming reaction using an oxygen-containing compound as a raw material in the presence of a catalyst prepared by supporting transition metals such as manganese, nickel, and cobalt.

Since the water phase reforming of oxygenated compounds occurs simultaneously in a system, gas-liquid reactions are determined by physical properties such as pore size, volume, and surface area of the catalyst, as well as mass transfer and diffusion rates of reactants and products. Therefore, it is advantageous to use a catalyst having three-dimensional mesopores in order to convert oxygen-containing compounds into gas and increase hydrogen yield. In particular, when a metal-supported catalyst is used in three-dimensional mesopores having a binary pore system, the oxygen-containing compound as a reactant is introduced into the large pores outside, and the decomposition reaction takes place primarily at the catalytic active point supported therein, and the remaining reactants. The rapid migration back to the interior of the pores results in the decomposition at the catalytically active sites finally impregnated therein, leading to a complete conversion to gas depending on the external pore size and very high hydrogen yields.

In one embodiment, a certain amount of the catalyst according to the present invention is charged to a reactor, for example a tubular fixed bed catalytic reactor, and reduction of the catalyst is carried out at 200 to 550 ° C. for 8 to 15 hours by flowing a certain amount of hydrogen gas. do. Subsequently, after maintaining a desired reaction temperature, a certain amount of ethylene glycol in aqueous solution as a reaction raw material is continuously supplied into the reactor by using a high performance liquid chromatography pump (HPLC pump). At this time, the weight hour space velocity (WHSV) is kept constant, and by using a back pressure regulator, the reactor pressure is kept slightly high so that the liquid phase can be maintained based on the reaction temperature and the vapor pressure of water. Let's do it. As described in detail in Examples below, at this time, a certain amount of nitrogen gas not participating in the reaction was flowed into an internal standard material, and each component of the product was subjected to quantitative analysis using gas chromatography based on this material. Formation rate, conversion rate and hydrogen yield can be checked.

Hereinafter, the present invention will be described in detail based on representative examples, but these examples are only for illustrating the embodiments of the present invention, and the scope of the present invention is not limited by the following examples.

Example

Manufacturing example 1: carbon Carrier Produce

10 g of silica gel was impregnated with 8.5 g of furfuryl alcohol and diffused at 35 ° C. for 1 hour, the temperature was raised to 100 ° C., dried for 1 hour, and maintained at 350 ° C. for 3 hours for initial carbonization. Subsequently, the silica gel / carbon composite was further impregnated with 5.5 g of furfuryl alcohol, followed by diffusion at 35 ° C. for 1 hour, and drying at 100 ° C. for 1 hour. The carbonization is then initially carbonized at 350 ° C. for 3 hours and finally carbonized at 900 ° C. for 2 hours. The silica gel / carbon composite thus prepared is etched silica material twice using 10% HF solution to dissolve the silica gel, washed and filtered twice with ethanol and distilled water, and then subjected to 100 ° C. The carrier was prepared by drying at least 12 hours.

The prepared carrier was “3D-MC-X (where 3D means three-dimensional, MC means mesoporous carbon, and X means drying time of the carbon precursor) according to the drying time of the carbon precursor.” Named.

Example One

A platinum supported catalyst was prepared as follows. Platinum precursor was dissolved in 3.2 mL of acetone corresponding to 7 wt% of the total weight of the catalyst using H ₂ PtCl ₆ as a platinum precursor, and the carbon carrier prepared according to Preparation Example 1 was initially wetted, dried and calcined. A platinum supported catalyst was prepared through the steps.

The activity evaluation of the platinum-supported carbon catalyst in the water phase reforming of ethylene glycol using this catalyst was carried out using a 1/2 inch tubular fixed bed catalysis system. The amount of catalyst used was 0.3 g, and after the reduction for 6 hours at 260 ° C. under hydrogen flow, a 10 wt% aqueous solution of ethylene glycol was fed to the reactor at a rate of 0.1 mL / min using an HPLC pump. The water phase reforming was performed at 250 ° C and 45 atmospheres, and the gaseous product after the reaction was carboxen 1000 packed column and gS-GASPRO capillary column using nitrogen as an internal standard. ) Were quantitatively analyzed using GC-TCD and FID.

The conversion of ethylene glycol into the gas phase and the hydrogen yield were calculated using the following formulas (1) and (2).

The production rate of hydrogen was expressed as the production rate of hydrogen per minute per gram of catalyst after quantifying the amount of hydrogen detected in TCD of GC based on the internal standard of nitrogen.

Catalytic activity confirmed results The conversion rate (%) Hydrogen yield (%), and the hydrogen production rate (cc / g _cat .min) data of the gas phase as shown in Table 1.

Example 2-4

Example 2-4 was impregnated with a silica precursor of furfuryl alcohol in silica gel and the drying process was performed for 2 hours (Example 2), 8 hours (Example 3), 12 hours (Example 4) at 100 ° C, respectively. Except that except that the carbon carrier and the platinum-carrying catalyst was prepared in the same manner as in Preparation Example 1 and Example 1 and the catalytic activity was confirmed. Table 1 shows the results of the catalytic activity check.

Comparative example 1-3

Instead of the carbon carrier as a catalyst carrier, Comparative Example 1 is gamma-alumina (manufactured by sterm), Comparative Example 2 is Cadapal B (Catapal B, manufactured by Sasol), and Comparative Example 3 is activated carbon (AC). A platinum supported catalyst was prepared in the same manner as in Example 1 except for using the same, and the catalytic activity was confirmed. Table 1 shows the results of confirming the catalytic activity.

Used catalyst At 100 ° C
Drying time (hr) In gas phase
Conversion Rate (%) Hydrogen yield
(%) Hydrogen production rate
(cc / g _cat .min) Example 1 7 wt% Pt / 3D-MC-1 One 82.6 76.1 50.7 Example 2 7 wt% Pt / 3D-MC-2 2 84.8 77.1 50.6 Example 3 7 wt% Pt / 3D-MC-8 8 91.2 93.8 62.5 Example 4 7 wt% Pt / 3D-MC-12 12 99.6 98.5 66.7 Comparative Example 1 7 wt% Pt / γ-alumina - 38.6 14.3 14.3 Comparative Example 2 7 wt% Pt / Catapal B - 25.4 15.1 10.1 Comparative Example 3 7 wt% Pt / AC - 40.5 38.5 18.0

Example 5-7

Examples 5 to 7 were prepared in the same manner as in Example 4, except that the platinum metal content was changed to 5 wt%, 2 wt%, and 1 wt% of the total weight of the catalyst, and the catalyst activity It was confirmed. Table 2 shows the results of confirming catalytic activity.

Used catalyst Catalyst loading
(wt%) In gas phase
Conversion Rate (%) Hydrogen yield
(%) Hydrogen production rate
(cc / g _cat .min) Example 5 5 wt% Pt / 3D-MC-12 5 89.1 86.4 57.6 Example 6 2 wt% Pt / 3D-MC-12 2 56.4 55.0 35.4 Example 7 1 wt% Pt / 3D-MC-12 One 41.5 42.4 28.1

Example 8-13

Examples 8 to 13 prepared the composite metal supported catalyst in substantially the same manner as in Example 4, except that the composite metal of the platinum-transition metal was supported as shown in Table 3, and the catalytic activity was confirmed. The results of confirming the catalytic activity are shown in Table 3.

Composite metal In gas phase
Conversion Rate (%) Hydrogen yield
(%) Hydrogen production rate
(cc / g _cat .min) Example 8 3 wt% Pt-Re (molar ratio 1: 1) / 3D-MC-12 91.8 55.3 36.8 Example 9 3 wt% Pt-Fe (molar ratio 1: 2) / 3D-MC-12 78.2 80.6 53.4 Example 10 3 wt% Pt-Fe (molar ratio 1: 3) / 3D-MC-12 85.4 86.1 57.3 Example 11 3 wt% Pt-Fe (molar ratio 1: 5) / 3D-MC-12 96.7 95.3 64.2 Example 12 3 wt% Pt-Mn (molar ratio 1: 1) / 3D-MC-12 69.8 66.2 46.9 Example 13 3 wt% Pt-Mn (molar ratio 1: 2) / 3D-MC-12 75.6 70.1 49.8

Claims

Impregnating a carbon precursor into a commercial silica that is a template followed by drying and carbonizing to obtain a silica / carbon composite; And removing the silica from the silica / carbon composite. A method for producing carbon having one or more three-dimensional binary mesopores selected from the group consisting of no silica gel.

The method for producing carbon having three-dimensional binary mesopores according to claim 1, wherein impregnation, drying, carbonization, or two or more of these processes are performed two or more times.

The method of claim 1, wherein the drying is carried out for 1 to 24 hours at a temperature of 80 to 150 ℃, the mesopore dualized by controlling the mesopore size in accordance with the mesopore size of the commercial silica and the drying time of the carbon precursor Method for producing a carbon having a three-dimensional binary mesopores to prepare.

The method of claim 1, wherein the carbon precursor is at least one selected from the group consisting of carbohydrates, acetylene, ethyl alcohol, furfuryl alcohol, divinylbenzene, and phenyl acetyl nitrile.

Carbon with three-dimensional binary mesopores prepared according to the method according to any one of claims 1 to 4.

A carbon supported metal catalyst having three-dimensional binary mesopores prepared according to any one of claims 1 to 4, wherein the metal is carbon alone or a carbon-supported complex metal of platinum-transition metal. Metal catalyst.

The carbon supported metal catalyst of claim 6, wherein the transition metal is at least one metal selected from the group consisting of rhenium, iron, manganese, nickel, and cobalt.

7. The method of claim 6, wherein when platinum is supported alone, the amount of platinum supported is 1 to 7 wt% based on the total weight of the catalyst; When the platinum-transfer metal is supported, the amount of platinum supported is 1 to 5 wt% based on the total weight of the catalyst, and the content of the transition metal is 0.1 to 10 moles based on 1 mol of platinum. catalyst.

The carbon supported metal catalyst according to claim 6, wherein the carbon supported metal catalyst is used for the aqueous phase reforming reaction of the oxygen compound.

A method for reforming a raw material solution containing an oxygen compound using the carbon supported metal catalyst according to claim 6.

A method for producing hydrogen by modifying a raw material solution containing an oxygen compound using the carbon supported metal catalyst according to claim 6.

The method of claim 10 or 11, wherein the raw material solution containing the oxygen compound is 10% by weight of at least one compound selected from ethylene glycol, propylene glycol, glycerol, glycerin, sorbitol, mannitol, or a mixture of two or more thereof. It will contain more than.