KR20130092711A - A noble catalyst of aqueous phase reforming reaction and manufacturing method of the same - Google Patents
A noble catalyst of aqueous phase reforming reaction and manufacturing method of the same Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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Abstract
Description
The present invention relates to a novel catalyst for water phase reforming and a preparation method thereof. More specifically, the present invention is a metal component selected from the group consisting of Group VIIB and Group VIII metal is SBA-1, SBA-6, SBA-16, FDU-5, KIT-6, and MCM-48 The present invention relates to a catalyst for water reforming reaction supported on a mesoporous carbon carrier prepared using one of the medium 3D porous silica molecular sieves selected from the group consisting of, and a method for producing the same and a method for producing hydrogen using the same.
Aqueous phase reforming reactions refer to techniques for selectively producing hydrogen from various types of oxygenated hydrocarbons derived from biomass such as glycerol, ethylene glycol, sugars and sugar alcohols. As can be seen from the reaction scheme shown below, the reforming reaction and the water-gas shift (WGS) reaction in a single reactor using an oxygen-containing hydrocarbon as a reaction material are performed at a low temperature below 300 ° C. Occurring simultaneously, the carbon monoxide (CO) concentration obtained from the product has the advantage of being very low, below 100 ppm. Therefore, this water reforming reaction does not require a reforming reaction at high temperature, a two-stage water gas shift reaction, and a separate methanation step to reduce carbon monoxide to less than 100 ppm, which is a problem of steam reforming reaction, which is a conventionally known representative method of producing hydrogen. There is an advantage. Therefore, toxic by-products are rarely generated and have high hydrogen production rate and selectivity compared to steam reforming.
C n H 2n +2 + nH 2 O ↔ nCO + (2n + 1) H 2 reforming
CO + H 2 O ↔ CO 2 + H 2 Water gas conversion
These studies on the water-reforming reaction have been carried out for the purpose of producing hydrogen in the liquid phase from oxygenated carbohydrate compounds induced by hydrolysis of biomass, a renewable energy source (RD Cortright, RR Davda, JA Dumesic). 418 (2002) 964-967; GW Huber, JW Shabaker, JA Dumesic, Science. 300 (2003) 2075-2077; RR Davda, JW Shabaker, GW Huber, RD Cortright, JA Dumesic, Appl. Catal., B. 56 (2005) 171-186).
Looking at the reactors of the water reforming reaction, the carbon cleavage (CC cleavage), carbon-oxygen cleavage (CO cleavage), water gas conversion, dehydrogenation / hydrogenation reaction, methanation reaction, Fischer-Tropsch reaction And the like are converted to carbon dioxide and hydrocarbons, including hydrogen. These various chemical reactions are intimately related to the active metal components, feed, reaction conditions, and catalyst carriers. Therefore, in order to increase the selectivity of hydrogen from oxygen-containing hydrocarbons by the water phase reforming reaction, the carbon-carbon splitting reaction should be maximized on the surface of the catalytic metal as the active material, while the carbon-oxygen splitting rate and the methanation / Fischer-Tropsch The reaction requires the selection of an appropriate catalyst to control and the adjustment of the reaction parameters.
Therefore, much research is being conducted to control the hydrogen production rate and selectivity in such water reforming reactions (MFL Johnson, J. Catal. 123 (1990) 245-259; JW Shabaker, GW Huber, RR Davda, RD Cortright). , JA Dumesic, Catal. Lett. 88 (2003) 1-8; WC Ketchie, EP Maris, RJ Davis, Chem. Mater. 19 (2007) 3406-3411; G. Wen, Y. Xu, H. Ma, Z Xu, Z. Tian, Int. J. Hydrogen Energy. 33 (2008) 6657-6666), and in particular, the catalyst carrier is attracting attention as the most important factor for increasing the activity of this water reforming reaction. That is, studies on catalysts impregnated with active materials based on platinum as the active ingredient mainly on various carriers have a major influence on the activity of the reaction depending on the characteristics of the carriers. For example, most metal oxide catalysts, such as Al 2 O 3 , ZrO 2 , SiO 2 , CeO 2 , ZnO, and TiO 2 , can collapse pores by sintering under the reaction conditions of high temperature, high pressure aqueous solution. Because of the phase transition in the form of reducing the specific surface area of the carrier in a wide range of meta stable phases, it is known to exhibit very unstable carrier properties during the water phase reaction.
Therefore, in order to solve this problem, a porous support having excellent hydrothermal stability is required. A porous carbon-based material having a large surface area, an appropriate pore volume, and mechanical / chemical stability that can disperse the metal to be impregnated and promote the reaction in a liquid phase. Carriers are receiving attention and much research has been done on them. Representative examples include oxygenated hydrocarbons using a catalyst impregnated with a VIIB group metal and a group VIII transition metal using vulcan carbon carriers in Korean Patent Publication No. 10-2008-0078911 and WO 2007/075476. Examples applied to the water phase reforming reaction of are known. There have also been various attempts to use activated carbon and single wall carbon nanotubes (SWCNT) as catalyst carriers (JW Shabaker, GW Huber, RR Davda, RD Cortright, JA Dumesic, Catal. Lett) 88 (2003) 1-8 and G. Wen, Y. Xu, H. Ma, Z. Xu, Z. Tian, Int. J. Hydrogen Energy.33 (2008) 6657-6666, X. Wang, N. Li, LD Pfefferle, GL Haller, Catal. Today.146 (2009) 160-165). However, when activated carbon is used as a carrier, it shows high surface area and hydrothermal stability, but due to irregular pore arrangement and wide pore distribution, especially due to the nature of activated carbon itself such as micro pores with small pore size In addition to preventing the transport of reactants to the catalytic active site in the liquid phase reaction, the gaseous reaction products generated in the aqueous phase reforming reaction do not easily escape and fill the micro pores with the catalytic active site and reactants. There is a limit to increase the selectivity and production rate of hydrogen in general because it interferes with the contact.
In Korean Patent Application No. 2010-0029421, in order to solve the above-mentioned problem, the structure of CMK-3 and CMK-5 having a two-dimensional structure in which the structure is a carbon carrier having mesopores of regular and uniform size Carbon was used as the catalyst carrier for this reaction. As a result, it was confirmed that the conversion rate and the hydrogen production rate of the oxygen compound is significantly improved compared to the case of using the known activated carbon. However, the synthetic carbon carriers of CMK-3 and CMK-5 are also reactants and products in this reaction, in which gas-liquid reactions occur simultaneously in one reaction system, which is characteristic of aqueous phase reforming due to its two-dimensional structure. There may be some limitations to expect high mass transfer and diffusion rates for C, which still requires further development of catalyst carriers.
The present invention is to solve the above-mentioned problems of the prior art, the present inventors carried out a study to develop a carbon-based support that exhibits excellent properties suitable for increasing the selectivity of hydrogen and the amount of hydrogen produced in the water phase reforming reaction As a result, Group VIIB and Group VIII metals as active ingredients in the mesoporous carbon support prepared by using a medium-sized porous silica molecular sieve having the characteristics of three-dimensional structure that can be applied to an aqueous phase reforming reaction can exhibit high activity catalytic properties. Supporting any one of the metal components selected from the group consisting of a novel catalyst exhibiting excellent properties compared to the carbon support known in the water phase reforming reaction.
Due to the characteristics of the three-dimensional structure, the carrier according to the present invention can accelerate the material transfer and diffusion speed, have a uniform skeleton structure, and in some cases, the carbon skeleton structure may have a rod or tube shape. Accordingly, the present invention is to provide a novel aqueous phase reforming catalyst and a method for preparing the same, which not only structurally stabilize the catalyst in the phase reforming catalytic reaction step but also greatly increase the conversion rate and generation rate of hydrogen.
In one embodiment of the present invention, the catalyst for the water reforming reaction is any one metal component selected from the group consisting of Group VIIB and Group VIII metal SBA-1, SBA-6, SBA-16, FDU-5, KIT-6 It may be a catalyst supported on the mesoporous carbon carrier prepared by using any one of the medium three-dimensional porous silica molecular sieve selected from the group consisting of, and MCM-48. The metal component may be any one selected from the group consisting of platinum, rhodium, rhenium, palladium, ruthenium, and iridium. The loading amount of the metal component may be 1 to 30% by weight based on the support.
In one embodiment of the present invention, the specific surface area of the mesoporous carbon carrier may be 1000 to 2000 m 2 / g, preferably 1100 to 1800 m 2 / g. The pore size of the mesoporous carbon carrier may have a uniform mesopore size of 3.0 to 6.0 nm, preferably 3.8 to 5.8 nm. The pore volume of the mesoporous carbon carrier may be 1.0 to 2.0 cm 3 / g. The mesoporous carbon carrier may be CMK-8 or CMK-9.
In still another embodiment of the present invention, a method for preparing a water phase reforming catalyst includes adsorbing a mixture of an aqueous carbohydrate solution and an acid or a carbon polymer precursor into pores of a medium-sized three-dimensional porous silica molecular sieve as a template, and performing drying and polymerization reactions. Pyrolyzing the polymerized carbon compound in the pores of the molecular sieve, preparing a mesoporous carbon carrier by removing the medium three-dimensional porous silica molecular sieve provided as a template, and the mesoporous carbon And impregnating the carrier with a precursor of any one metal component selected from the group consisting of Group VIIB and Group VIII metals. Here, the medium three-dimensional porous silica molecular sieve may be any one selected from the group consisting of SBA-1, SBA-6, SBA-16, FDU-5, KIT-6, and MCM-48. The precursors include hexachloro platinum extract (H 2 PtCl 6 ), platinum ammonium chloride (Pt (NH 3 ) 4 Cl 2 ), platinum ammonium nitrate (Pt (NH 3 ) 4 (NO 3 ) 2 ), perenic acid (HReO 4 ), rhenium chloride (ReCl 2 ), rhenium sulfide (ReS), rhodium nitrate (Rh (NO 3 ) 3 ), rhodium chloride (RhCl 3 ), or rhodium acetate dimer (Rh (CH 3 COO) 2 ] 2. The impregnating the precursor may use an initial wetting method or an impregnation method.
In one embodiment of the present invention, hydrogen may be produced through an aqueous phase reforming reaction from an oxygen compound using a catalyst according to one embodiment of the present invention. The oxygen compound may be any one selected from the group consisting of propylene glycol, ethylene glycol, glycerol, sorbitol, xylitol, mannitol, and erythritol. Hydrogen production method through the water phase reforming reaction may be carried out at a reaction temperature of 210 ~ 290 ℃, weight space velocity (WHSV) of the oxygen compound per hour catalyst weight of 1 ~ 10h -1 .
The catalyst of the water phase reforming reaction according to one embodiment of the present invention is not only structurally stable, but also greatly increases the conversion rate and generation rate of hydrogen compared to the existing catalyst. In addition, it is possible to provide hydrogen economically and environmentally using the catalyst according to the present invention.
The catalyst for the water reforming reaction according to an embodiment of the present invention has an advantage of greatly increasing the conversion rate of hydrogen gas in the gaseous form and the generation rate of hydrogen based on the carbon component of the reaction raw material, compared to the known catalyst.
FIG. 1 is a diagram showing a structural diagram of mesoporous carbon having a three-dimensional pore structure prepared from KIT-6, a three-dimensional porous silica molecular sieve.
FIG. 2 is a graph showing X-ray diffraction analysis (XRD) (a) and nitrogen physisorption isotherm (b) of a mesoporous carbon carrier of CMK-8 type. The Brunauer-Emmett-Teller (BET) surface area and total pore volume and pore size of the material are the results from nitrogen physisorption.
3 is a graph showing X-ray diffraction analysis (XRD) (a) and nitrogen physisorption isotherm (b) of a mesoporous carbon carrier of CMK-9 type. The Brunauer-Emmett-Teller (BET) surface area and total pore volume and pore size of the material are the results from nitrogen physisorption.
Figure 4 is a graph showing the results of wide-angle X-ray diffraction analysis (wide-angle XRD) before and after the reaction of the platinum-supported CMK-8 type mesoporous carbon carrier and the CMK-9 type mesoporous carbon carrier.
The objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description and preferred embodiments associated with the accompanying drawings. Hereinafter, preferred embodiments of the present invention will be described in detail.
One embodiment of the present invention uses mesoporous carbon having not only high surface area and hydrothermal stability but also mesopores of regular and uniform size of mesopores, comprising a VIIB group and a Group VIII metal. A catalyst supporting any one metal component selected from the group may be a catalyst suitable for water phase reforming. According to the present invention, the three-dimensional structural regular carriers impart a fast material transfer and diffusion rate.
In addition, the catalyst according to an embodiment of the present invention is a stable carrier during the water phase reforming reaction, which is generated during the reaction compared to the conventional carrier by using mesoporous carbon material having a three-dimensional structure having uniform pores. Gases and reactants move more freely into and out of the pores to increase the reaction activity, and also reactants and catalyst active sites during the water reforming reaction when using a metal-supported catalyst on a three-dimensional mesoporous carbon carrier. The more frequent the reactions in between, the greater the conversion to gas and the higher the hydrogen yield.
In addition, according to one embodiment of the present invention, the shape of the carbon skeleton having a three-dimensional arrangement, as well as the rod-shaped carbon skeleton to provide additional mesopores and a wider surface area by providing a reactant compared to the rod shape It is possible to improve the water phase reforming reaction because the free diffusion of the product and the higher degree of dispersion of the supported metal components. Referring to Figure 4, the award for the rod-shaped three-dimensional mesoporous carbon carrier (hereinafter 'CMK-8') and the tube-shaped three-dimensional mesoporous carbon carrier (hereinafter 'CMK-9') In the wide-angle XRD before and after the reforming reaction, the diffraction peaks of the platinum supported after the reaction do not appear clearly compared to before and after the reaction, indicating that both carriers have very high dispersion of platinum. Can be. In addition, it can be seen that the CMK-9 carrier having a tubular carbon skeleton has a higher platinum dispersion because the diffraction peak of platinum is lower than that of the CMK-8 carrier having a rod-shaped carbon skeleton. The -9 carrier is more preferred for the water phase reforming reaction.
In one embodiment of the present invention, the loading amount of the metal component may be 1 to 30% by weight based on the support. Preferably 1 to 15% by weight. When the supporting amount of any one metal component selected from the group consisting of Group VIIB and Group VIII metals, which are active metals compared to mesoporous carbon, is less than 1.0 wt%, the content of the active metals is low, and thus the utilization rate is low as a catalyst for water reforming reaction. If the supported amount of the metal component exceeds 30% by weight, there is a problem in that the catalytic activity is not high compared to the amount of expensive precious metal catalyst because the aggregation of the supported active metal occurs a lot.
In one embodiment of the present invention, the catalyst can be used to produce hydrogen through an aqueous phase reforming reaction with oxygen-containing compounds such as propylene glycol, ethylene glycol, glycerol, sorbitol, xylitol, mannitol and erythol as raw materials. The catalyst according to one embodiment of the present invention can be used to greatly increase the conversion and production rate of hydrogen.
In one embodiment of the present invention, all of the mesoporous carbon may be used as long as the mesoporous carbon is generally used, and may be prepared by the following manufacturing method.
Adsorbing a mixture of an aqueous solution of carbohydrate and an acid or a carbon polymer precursor in the pores of the medium-sized porous 3D silica molecular sieve as a template, carrying out drying and polymerization reactions, pyrolyzing the polymerized carbon compound in the pores of the molecular sieve, And removing the medium porous silica molecular sieve provided as a template.
The three-dimensional mesoporous silica that can be used as a template in the above synthesis method can be used as long as it is generally used in the art. For example, SBA-1, SBA-6, SBA-16, FDU-5, KIT-6, or MCM-48 with three-dimensional structure can be used. However, the present invention is not limited thereto. Specifically, KIT-6 contains a larger amount of mesopores than other silica castings such as MCM-48, and because the pores are not only large in size but also excellent in hydrothermal and thermal stability, the molds collapse during heat treatment. It has the advantage of not being able to be a mold with a representative three-dimensional structure that is most suitable for producing mesoporous carbon. More specifically, the rod-shaped carbon molecular sieve CMK-8 prepared by using the mesoporous silica molecular sieve having a similar cubic structure as KIT-6 and sucrose, acetylene, furfuryl alcohol, divinylbenzene, etc. Or carbon molecular sieve CMK-9 in the form of a tube can be used (F. Kleitz, SH Choi, R. Ryoo, Chem. Comm. (2003), 2136-2137). Since the CMK-8 and CMK-9 carbons have uniform mesopores of a certain size compared to other mesoporous carbons, and the arrangement of mesopores has structural regularity, the movement of the reactants is more smooth. . 1 is a diagram showing the structure of mesoporous carbon having a three-dimensional pore structure made from KIT-6, a typical mesoporous silica.
Referring to the XRD diffraction analysis and nitrogen adsorption / desorption isotherm of FIGS. 2 and 3 for the three-dimensional mesoporous carbon carriers CMK-8 and CMK-9 prepared above, it can be seen that they have mesopores. It can be seen that -9 has a larger surface area than additional mesopores and CMK-8.
In another embodiment of the present invention, a novel method for preparing a water reforming catalyst is adsorbing a mixture of an aqueous solution of carbohydrate and an acid or a carbon polymer precursor in pores of a medium-sized three-dimensional porous silica molecular sieve as a template, and drying and polymerizing. Preparing a mesoporous carbon carrier by performing thermal decomposition of the polymerized carbon compound in the pores of the molecular sieve, removing the medium three-dimensional porous silica molecular sieve provided as a template, and Impregnating the mesoporous carbon support with a precursor of any one metal component selected from the group consisting of Group VIIB and Group VIII metals. Here, the medium three-dimensional porous silica molecular sieve may be any one selected from the group consisting of SBA-1, SBA-6, SBA-16, FDU-5, KIT-6, and MCM-48.
The precursor of the metal component may use any one of the precursor of the metal component selected from the group consisting of Group VIIB and Group VIII metals known in the art, for example, hexacholoroplatinic acid as a platinum precursor , H 2 PtCl 6 ), platinum ammonium chloride (Pt (NH 3 ) 4 Cl 2 ), platinum ammonium nitrate (Pt (NH 3 ) 4 (NO 3 ) 2 ), etc. can be used. Rhenium acid (HReO 4 ), Rhenium chloride (ReCl 2 ), Rhenium sulfide (ReS), etc. may be used, and as a precursor of rhodium, rhodium nitrate (Rh (NO 3 ) 3 ), rhodium chloride (RhCl 3 ), or Rhodium acetate dimer (Rh (CH 3 COO) 2 ] 2, etc. may be used as the impregnating method for the carrier, but all known methods known in the art can be used, but incipient wetness method or Acupuncture disperses catalyst on carrier When it is preferred because it can be uniformly dispersed.
In one embodiment of the present invention, hydrogen may be produced through an aqueous phase reforming reaction from an oxygen compound using a catalyst according to one embodiment of the present invention. The oxygen compound may be any one selected from the group consisting of propylene glycol, ethylene glycol, glycerol, sorbitol, xylitol, mannitol, and erythritol. Hydrogen production method through the water phase reforming reaction may be carried out at a reaction temperature of 210 ~ 290 ℃, weight space velocity (WHSV) of the oxygen compound per weight of the catalyst per hour 1 ~ 10 h -1 . The reactor for generating hydrogen by the water phase reforming reaction is not particularly limited, but a fixed-bed catalytic reactor in which the catalyst is filled in the reaction may be used. In this water phase reforming reaction, it is important to carry out the reaction in a state in which the reaction temperature and pressure and the weight hourly space velocity are maintained in an appropriate range. The process of generating hydrogen by the aqueous phase reforming reaction of the present invention may be a reaction temperature of 210 ~ 290 ℃, for example, 220 ~ 280 ℃, 240 ~ 250 ℃. If the reaction temperature is less than 210 ℃ reaction rate is very low, and if the reaction temperature is more than 290 ℃ reaction pressure is also increased in proportion to this there is a problem in that the difficulty of the operation and the reactor price increases. In addition, the weight hourly space velocity (WHSV) based on the catalyst weight may be 1 to 10 h −1 , and preferably 2 to 5 h −1 .
Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are only intended to illustrate the present invention, but are not intended to limit the present invention.
Evaluation of the activity of the catalyst in the following examples was carried out in the water phase reforming reaction using a fixed bed catalytic reaction system. That is, the catalyst was filled with 0.3 g in a tubular reactor, the hydrogen gas was constantly flowed at 50 cc / min, and the catalyst was reduced at 260 ° C. for 6 hours. Subsequently, the temperature of the reactor was kept constant at 250 ° C., the reaction temperature, and then a liquid chromatography pump (HPLC pump) was continuously supplied to the reactor at a constant 0.1 cc / min. The weight hour space velocity (WHSV) was fixed at 0.1 cc / gcat.min. The reaction pressure was maintained at a constant pressure of 45 bar using a back pressure regulator, slightly higher than 0.5 bar based on the 45 bar of the liquid phase based on the water vapor pressure based on the reaction temperature. At this time, a certain amount of nitrogen gas not participating in the reaction was flowed into the internal standard at 5 cc / min, and each component of the product was subjected to quantitative analysis using gas chromatography.
The gas conversion rate based on the production rate of hydrogen and the carbon component of the reaction material was calculated according to the following criteria. First, the rate of hydrogen production was expressed as the rate of hydrogen per minute per gram of catalyst after quantifying the amount of hydrogen detected in the TCD of GC based on the internal standard of nitrogen. Gas conversion was calculated by the following equation. The higher the gas conversion rate based on the carbon component of the reaction raw material, the higher the production of hydrogen.
[Equation 1]
Gas conversion = [moles of carbon in product in gas phase] / [moles of carbon in reactants] × 100%
Example 1 APR Reaction with 7 wt% Pt / CMK-8 Catalyst
10 g of mesoporous silica KIT-6 was impregnated with 8.5 g of furfuryl alcohol in five steps and diffused at 35 ° C. for 1 hour, heated to 100 ° C. for 1 hour, and then maintained at 350 ° C. for 3 hours. Early carbonization. Subsequently, 5.5 g of furfuryl alcohol was again impregnated into the mesoporous silica / carbon composite, 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 / carbon composites thus prepared are etched silica twice using 10% HF solution to dissolve silica, washed and filtered twice using ethanol and distilled water, and then heated to 100 ° C. After drying for at least 12 hours to prepare a CMK-8 carrier.
The method of impregnating platinum with the carbon carrier thus prepared is as follows.
First, impregnation using a platinum precursor was prepared by using an initial wetting method after mixing 0.1859 g of hexachloroplatinic acid (H 2 PtCl 6 ) and 3 ml of acetone as a precursor of platinum. In other words, the platinum mixture solution was injected into 1.0 gram of CMK-8 in three portions, and then mixed well using a vortex unit, and then allowed to stand at room temperature for about 1 hour, and the lid of the glass bottle was slightly opened. After drying at 60 ° C. for 2 hours, the glass bottle was further dried at 60 ° C. for 6 hours with the lid completely open. The final catalyst was completed by drying at 120 ° C. for 12 hours. The prepared catalyst was named 7 wt% Pt / CMK-8.
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 before the reaction, after reduction for 6 hours to 260 ° C. under hydrogen flow, an aqueous 10 wt% ethylene glycol solution 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. Columns were quantitatively analyzed using GC-TCD and FID. The conversion of ethylene glycol into the gas phase and the rate of hydrogen production were calculated using Equation 1. The experimental results of the catalyst prepared according to Example 1 are shown in Table 1 using the conversion rate into the gas phase based on the production rate of hydrogen and the carbon component of the reaction raw material.
Example 2 APR Reaction with 7 wt% Pt / CMK-9 Catalyst
10g of mesoporous silica KIT-6 was impregnated with 10g of furfuryl alcohol in five steps, and the pores were removed by partially removing the carbon precursors filling the inside of the mesoporous silica pores by lyophilizing the impregnated silica / carbon composite under vacuum. It was prepared so that the carbon precursor is attached only to the wall. Thereafter, the mixture was diffused at 35 ° C. for 1 hour, and the drying was performed at 100 ° C. for 1 hour. Subsequently, the temperature was raised to initial carbonization at 350 ° C. for 3 hours and finally carbonized at 900 ° C. for 2 hours. The silica / carbon composites thus prepared are etched silica twice using 10% HF solution to dissolve silica, washed and filtered twice using ethanol and distilled water, and then heated to 100 ° C. After drying for at least 12 hours to prepare a CMK-9 carrier. When carrying 7 wt% Pt, the support was carried out by the same method as Example 1 except for using the prepared CMK-9, and the results of the performance evaluation of the catalyst are shown in Table 1.
Comparative Example 1: APR Reaction Using 7 wt% Pt / CMK-3 Catalyst
When carrying 7 wt% Pt was carried out in the same manner as in Example 1 except that the support was changed to a mesoporous material (CMK-3) having a carbon skeleton in the form of a two-dimensional rod, the performance evaluation of the catalyst The results are shown in Table 1.
Comparative Example 2: APR Reaction with 7 wt% Pt / CMK-5 Catalyst
When carrying 7 wt% Pt was carried out in the same manner as in Example 1 except that the support was changed to a mesoporous material (CMK-5) having a carbon skeleton in the form of a two-dimensional tube, the performance evaluation of the catalyst The results are shown in Table 1.
Comparative Example 3 APR Reaction Using 7 wt% Pt / Activated Carbon Catalyst
When carrying 7 wt% Pt was carried out in the same manner as in Example 1 except that the carrier was changed to activated carbon, the results of the performance evaluation of the catalyst are shown in Table 1.
Comparative Example 4: APR Reaction Using 7 wt% Pt / Activated Alumina Catalyst
When carrying 7 wt% Pt was carried out in the same manner as in Example 1 except that the carrier was changed to activated alumina (catapal B), the results of the performance evaluation of the catalyst are shown in Table 1.
(cc / gcat.min)
(Catapal B)
As can be seen in Table 1, Examples 1 and 2 and the above Examples and experiments were carried out to prepare a catalyst carrying a platinum carrying a mesoporous carbon having a carbon skeleton in the form of a rod or tube in a three-dimensional structure regular Compared to Comparative Examples 1 to 4 using different carriers, it was confirmed that the conversion rate of the hydrogen gas of Examples 1 and 2 according to one embodiment of the present invention is excellent, the generation rate of hydrogen is relatively fast. .
Example 3 APR Reaction with 10 wt% Pt / CMK-8 Catalyst
Example 3 was carried out by the experiment to prepare a metal-supported catalyst in the same manner as in Example 1, except that the amount of platinum supported by the active material was changed to 10 wt%, and the results are shown in Table 2.
Example 4 APR Reaction with 5 wt% Pt / CMK-8 Catalyst
Example 4 was carried out by the experiment to prepare a metal-supported catalyst in the same manner as in Example 1 except that the amount of platinum supported by the active material was changed to 5 wt%, and the results are shown in Table 2.
Example 5 APR Reaction with 3 wt% Pt / CMK-8 Catalyst
Example 5 was carried out by the experiment to prepare a metal-supported catalyst in the same manner as in Example 1 except that the amount of platinum supported by the active material was changed to 3 wt%, and the results are shown in Table 2.
Example 6 APR Reaction with 1 wt% Pt / CMK-8 Catalyst
Example 6 was carried out by the experiment to prepare a metal-supported catalyst in the same manner as in Example 1 except that the amount of platinum supported by the active material was changed to 1 wt%, and the results are shown in Table 2.
Example 7 APR Reaction with 15 wt% Pt / CMK-9 Catalyst
Example 7 was carried out by the experiment to prepare a metal-supported catalyst in the same manner as in Example 2 except that the amount of platinum supported by the active material was changed to 15 wt%, and the results are shown in Table 2.
Example 8 APR Reaction with 10 wt% Pt / CMK-9 Catalyst
Example 8 was carried out by the experiment to prepare a metal-supported catalyst in the same manner as in Example 2, except that the amount of platinum supported by the active material was changed to 10 wt%, and the results are shown in Table 2.
Example 9 APR Reaction with 5 wt% Pt / CMK-9 Catalyst
Example 9 was carried out by the experiment to prepare a metal supported catalyst in the same manner as in Example 2 except for changing the amount of platinum to 5 wt% as an active material and the results are shown in Table 2.
Example 10 APR Reaction with 3 wt% Pt / CMK-9 Catalyst
Example 10 was carried out to prepare a metal-supported catalyst in the same manner as in Example 2 except that the amount of platinum supported by the active material was changed to 3 wt%, and the results are shown in Table 2.
Example 11 APR Reaction with 1 wt% Pt / CMK-9 Catalyst
Example 11 was carried out by the experiment to prepare a metal-supported catalyst in the same manner as in Example 2, except that the amount of platinum supported by the active material was changed to 1 wt%, and the results are shown in Table 2.
(cc / gcat.min)
As can be seen in Table 2, the lower the platinum content, the lower the conversion rate of hydrogen gas and the generation rate of hydrogen, and the higher the platinum content, the higher the conversion rate of hydrogen gas and the rate of hydrogen production. I could confirm it. When the amount of platinum metal, which is an active metal, is less than 1.0% by weight, the amount of platinum metal decreases, so that the utilization of the metal as a catalyst for water phase reforming becomes low. When the amount of platinum metal exceeds 30% by weight, As a result, the dispersibility of the supported platinum metal is lowered so that the catalytic activity is not higher than that of the expensive precious metal platinum catalyst.
Example 12
Example 12 was carried out in the same manner as in Example 2 except that the polyol type was changed to 10 wt% 1,2-propylene glycol, and the amount of platinum was changed to 10 wt%. The results are shown in Table 3.
Example 13
Example 13 was carried out in the same manner as in Example 2 except that the polyol type was changed to 10 wt% 1,3-propylene glycol, and the amount of platinum was changed to 10 wt%. The results are shown in Table 3.
Example 14
Example 14 was carried out in the same manner as in Example 2 except that the polyol type was changed to 10 wt% glycerol, and the amount of platinum was changed to 10 wt%. Table 3 shows.
Example 15
Example 15 was carried out in the same manner as in Example 2 except that the polyol type was changed to 10 wt% sorbitol, and the amount of platinum was changed to 10 wt%. Table 3 shows.
Example 16
Example 16 was carried out in the same manner as in Example 2 except that the polyol type was changed to 10 wt% xylitol, and the amount of platinum was changed to 10 wt%. Table 3 shows.
Comparative Example 9
Comparative Example 9 was carried out in the same manner as in Comparative Example 1 except that the polyol type was changed to 10 wt% sorbitol, and the amount of platinum was changed to 10 wt%. 3 is shown.
Comparative Example 10
Comparative Example 10 was carried out in the same manner as in Comparative Example 2 except that the polyol type was changed to 10 wt% sorbitol, and the amount of platinum was changed to 10 wt%, and the experiment was performed. 3 is shown.
Conversion Rate (%)
(cc / gcat.min)
1,3-propylene glycol
Table 3 shows the results of the APR reaction with various polyols using 7 wt% Pt / CMK-9 catalyst. As can be seen in Table 3, in any of the oxygen compounds used in Examples 12 to 15 showed a conversion rate of 50% or more stable hydrogen gas, it was confirmed that the generation rate of hydrogen is also excellent. Therefore, it was confirmed that the catalyst according to the present invention can be applied to various polyols in the water phase reforming reaction. In addition, the use of the carrier according to the present invention in Example 15 and Comparative Examples 9 and 10 was confirmed that the conversion rate of the hydrogen gas and the production rate of hydrogen is superior to Comparative Examples 9 and 10.
Although the present invention has been described in detail through specific examples, this is for explaining the present invention in detail, and the novel water reforming catalyst and its preparation method according to the present invention are not limited thereto and are within the technical idea of the present invention. It will be apparent to those skilled in the art that modifications and variations are possible.
Simple modifications and variations of the present invention are all within the scope of the present invention, and the specific scope of protection of the present invention will be apparent from the appended claims.
Claims (13)
The metal component is a catalyst, characterized in that any one selected from the group consisting of platinum, rhodium, rhenium, palladium, ruthenium, and iridium.
The supported amount of the metal component is a catalyst, characterized in that 1 to 30% by weight based on the carrier.
Catalysts, characterized in that the specific surface area of the mesoporous carbon carrier is 1000 ~ 2000 m 2 / g.
The mesoporous carbon carrier has a pore size of 3.0 to 6.0 nm, characterized in that it has a uniform mesopore size.
A catalyst, characterized in that the pore volume of the mesoporous carbon carrier is 1.0 ~ 2.0 cm 3 / g.
The mesoporous carbon support is a catalyst, characterized in that the CMK-8 or CMK-9.
Pyrolyzing the polymerized carbon compound in the pores of the molecular sieve,
Preparing a mesoporous carbon carrier by removing the medium three-dimensional porous silica molecular sieve provided as a template, and
Impregnating the mesoporous carbon carrier with a precursor of any one metal component selected from the group consisting of Group VIIB and Group VIII metals,
The medium three-dimensional porous silica molecular sieve is any one selected from the group consisting of SBA-1, SBA-6, SBA-16, FDU-5, KIT-6, and MCM-48 Manufacturing method.
Impregnating the precursor is a method for producing a catalyst, characterized in that using the initial wetting method or impregnation method.
The precursors include hexachloro platinum extract (H 2 PtCl 6 ), platinum ammonium chloride (Pt (NH 3 ) 4 Cl 2 ), platinum ammonium nitrate (Pt (NH 3 ) 4 (NO 3 ) 2 ), perenic acid (HReO 4 ), rhenium chloride (ReCl 2 ), rhenium sulfide (ReS), rhodium nitrate (Rh (NO 3 ) 3 ), rhodium chloride (RhCl 3 ), or rhodium acetate dimer (Rh (CH 3 COO) 2 ] Method for producing a catalyst, characterized in that 2 .
The oxygen compound is any one selected from the group consisting of propylene glycol, ethylene glycol, glycerol, sorbitol, xylitol, mannitol, and erythritol.
The method is characterized in that carried out at a reaction temperature of 210 ~ 290 ℃, weight space velocity (WHSV) of the oxygen compound per hour catalyst weight of 1 ~ 10 h -1 .
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664930A (en) * | 2016-03-04 | 2016-06-15 | 重庆工商大学 | Load type mesoporous palladium catalyst for catalytic removal of low-concentration benzene and preparation method of load type mesoporous palladium catalyst |
| CN106955731A (en) * | 2017-03-29 | 2017-07-18 | 钦州学院 | A kind of preparation method for the catalyst that anthraquinone is prepared for anthracene oxidation |
| CN110479212A (en) * | 2019-09-12 | 2019-11-22 | 苏州科技大学 | A kind of preparation method and applications of unordered mesoporous carbon adsorbing material |
| CN114768818A (en) * | 2022-03-10 | 2022-07-22 | 天津大学 | Water-heat oxygen decoupling catalyst, preparation method and application |
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2012
- 2012-02-13 KR KR1020120014152A patent/KR20130092711A/en not_active Application Discontinuation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664930A (en) * | 2016-03-04 | 2016-06-15 | 重庆工商大学 | Load type mesoporous palladium catalyst for catalytic removal of low-concentration benzene and preparation method of load type mesoporous palladium catalyst |
| CN106955731A (en) * | 2017-03-29 | 2017-07-18 | 钦州学院 | A kind of preparation method for the catalyst that anthraquinone is prepared for anthracene oxidation |
| CN106955731B (en) * | 2017-03-29 | 2019-08-13 | 钦州学院 | A kind of preparation method for the catalyst preparing anthraquinone for anthracene oxidation |
| CN110479212A (en) * | 2019-09-12 | 2019-11-22 | 苏州科技大学 | A kind of preparation method and applications of unordered mesoporous carbon adsorbing material |
| CN114768818A (en) * | 2022-03-10 | 2022-07-22 | 天津大学 | Water-heat oxygen decoupling catalyst, preparation method and application |
| CN114768818B (en) * | 2022-03-10 | 2023-08-15 | 天津大学 | Hydrothermal oxygen decoupling catalyst, preparation method and application |
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