Patent Application
20120277091
This application claims the benefit of Korean Patent Application No. 10-2011-0040645, filed with the Korean Intellectual Property Office on Apr. 29, 2011, the disclosure of which is incorporated herein by reference in its entirety.
1. Technical Field
The present invention relates to a method of preparing a catalyst using alkali metal and/or alkaline earth metal components inherently contained in natural cellulose fibers as a dispersant and a co-catalyst of catalytic metal particles, and more particularly, to a method of preparing a catalyst using alkali metal and alkaline earth metal components such as Ca, Mg, K, etc., which are inherently contained in the structure of natural cellulose fibers, as a dispersant and a performance improver.
2. Description of the Related Art
Recently, in the main research trends of catalyst fields, a first interesting development is the preparation of a support that is physically and chemically stable and has a large surface area with a uniform pore distribution adapted for a specific reaction, and a second interesting development is the preparation of a catalyst that exhibits the greatest activity at the lowest cost by supporting catalyst particles in a state of being highly dispersed while being minimized to a nanoscale.
Particularly in the case where a metal nanocatalyst is applied to a high-temperature catalytic reaction, most metal particles may agglomerate. Even when the dispersibility of catalyst particles that were first prepared is very high, the catalyst rapidly agglomerates and becomes undesirably deactivated at the same time when being exposed to the high-temperature reaction.
As the price of precious metal catalysts has increased considerably in recent years, catalysts for fuel cells and for H2 preparation using precious metal catalysts such as Au and Pt are problematic in terms of being deactivated because of the agglomeration of metal. With the goal of overcoming such problems, a variety of attempts are being made to disperse a metal having no reaction activity in order to impart steric hindrance between metal particles, or to strengthen the interactions between the metal and the support to thereby prevent the transfer and agglomeration of the catalyst upon high-temperature catalytic reaction. However, satisfactory research results have not yet been reported to date.
Vizcaino et al. (Catalysis Today 146 (2009) 63-70) prepared a catalyst that is effective in a water vapor reforming reaction of ethanol by adding Mg and Ca to a Cu—Ni/SBA-15 catalyst. They also reported that the added Ca and Mg components improve the dispersibility of a CuNi catalyst, enhance the interaction between the support and the metal catalyst to increase catalytic performance, and lower the deactivation due to coke formation. Research results regarding improvements in catalytic performance and durability owing to the addition of alkaline earth metals were published in many reports in addition to the above paper (Cortright et al., Nature 418 (2002) 964; Pol el al. Carbon 42 (2004)111). However, methods of artificially adding an alkali metal and an alkaline earth metal to a catalyst for a reforming reaction have been studied. Research results for techniques for utilizing components such as, for example, Ca and Mg inherently contained in natural cellulose fibers have not yet been published.
Therefore, the present inventors continued research into preparation of catalysts having improved catalytic performance and durability without performing the artificial addition of alkali metal and alkaline earth metal components, leading to the development of a method of using highly dispersed alkali metal and alkaline earth metal nanoparticles that are inherently present in the structure of natural cellulose fibers as a dispersant and a performance improver.
Accordingly, an object of the present invention is to provide a method of preparing a catalyst using an alkali metal or an alkaline earth metal in natural cellulose fibers as a co-catalyst and a dispersant.
In order to accomplish the above object, the present invention provides a method of preparing a catalyst using an alkali metal or an alkaline earth metal in natural cellulose fibers as a co-catalyst and a dispersant, comprising thermally treating natural cellulose fibers to remove impurities from the natural cellulose fibers and to disperse the alkali metal or the alkaline earth metal in the form of nanoparticles in and on the fibers, chemically treating the thermally treated natural cellulose fibers with an acidic solution to introduce a functional group onto the surface of the fibers, thus preparing a cellulose support, and supporting metal catalyst nanoparticles on the surface of the chemically treated cellulose support using chemical vapor deposition or impregnation.
The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
According to the present invention, there is provided a method of preparing a catalyst using an alkali metal or an alkaline earth metal in natural cellulose fibers as a co-catalyst and a dispersant, comprising thermally treating natural cellulose fibers to remove impurities from the natural cellulose fibers and to disperse the alkali metal or the alkaline earth metal in the form of nanoparticles in and on the fibers, chemically treating the thermally treated natural cellulose fibers with an acidic solution to introduce a functional group onto the surface of the fibers, thus preparing a cellulose support, and supporting metal catalyst nanoparticles on the surface of the chemically treated cellulose support using chemical vapor deposition (CVD) or impregnation.
Below is a detailed description of the method of preparing the catalyst according to the present invention.
In the present invention, a natural cellulose material that is capable of obtaining a large surface area without performing a specific pretreatment process such as activation is used. Also even without performing artificial addition of a dispersant and a co-catalyst, alkali metal or alkaline earth metal components such as K, Ca and Mg inherently contained in the cellulose structure are used as a dispersant and a performance improver. Thereby, activity and durability of a catalyst used for the high-temperature reaction may be remarkably improved.
Conventionally, in the case where a metal-supported catalyst is used for a high-temperature catalytic reaction, an alkali metal and/or an alkaline earth metal such as K, Ca, Mg, etc., are artificially added, as well as the catalytic metal, in order to prevent the dispersibility of metal particles from decreasing with an increase in the reaction temperature, suppress the sintering and agglomeration of metal particles, and decrease the deactivation due to deposition of reaction by-products in the course of the reaction. That is, the alkali metal and/or the alkaline earth metal are used as a co-catalyst.
In the present invention, a natural cellulose material, which inherently contains alkali metal and/or alkaline earth metal components without the need to perform the artificial addition as mentioned above, is used. These alkali metal and/or alkaline earth metal components were confirmed to be inherently present in the form of highly dispersed nanoparticles in natural cellulose even without additional treatment. Also, according to the present invention, when natural cellulose fibers are thermally treated, impurities having a low boiling point such as wax or pectin are removed from the natural cellulose, and thus the alkali metal and/or alkaline earth metal components present in the fibers are exposed to the inside and outside the porous fibers and the crystallinity of the metal is increased. Hence, carbonized natural cellulose fibers are intended to be utilized as a high-performance catalytic support and a catalyst.
In the case where a variety of metal catalyst particles are supported on the surface of the cellulose structure, the dispersibility of metal catalyst particles is increased and the interaction between the metal and the support is enhanced thanks to the effects of alkali metal and/or alkaline earth metal components. Furthermore, the agglomeration and sintering of metal catalyst particles that are regarded as problematic upon high-temperature catalytic reaction may be retarded, ultimately considerably increasing the durability of the catalyst.
Conventionally, in order to retard the agglomeration and sintering of metal catalyst particles and improve durability of the catalyst, the alkali metal and/or alkaline earth metal components are artificially added. However, in the case of a catalytic support using the natural cellulose material according to the present invention, it is advantageous because metal nanoparticles are inherently highly dispersed in the cellulose fibers and may thus be directly used as a dispersant and a performance improver.
The kind of natural cellulose usable in the present invention is not limited. Any natural cellulose biomass may be used as a material of the present invention. For example, natural cellulose may be selected from the group consisting of henequen fibers, kenaf, abaca, bamboo, hemp, flax, jute, pineapple, ramie, sisal, rice straw, barley straw, wheat straw, rice husk and mixtures thereof, but is not necessarily limited thereto.
In the method according to the present invention, thermally treating the natural cellulose fibers is performed to remove impurities such as wax and pectin from the natural cellulose fibers and increase the surface area and porosity. Also, the thermal treatment may increase crystallinity of alkali metal and/or alkaline earth metal components in the natural cellulose fibers, wherein such alkali metal or alkaline earth metal components are uniformly dispersed in the form of nanoparticles in the cellulose fibers.
Any alkali metal and alkaline earth metal may be used so long as they are widely known in the art. For example, the alkali metal is selected from the group consisting of Li, Na, K and mixtures thereof, and the alkaline earth metal is selected from the group consisting of Ca, Mg and mixtures thereof, but the alkali metal and the alkaline earth metal are not necessarily limited thereto.
According to an embodiment of the present invention, the natural cellulose fibers are separated into thin fibers of tens to hundreds of μm, and such fine fibers are cut to short fibers having a length of 1˜2 mm in liquid nitrogen. Thereafter, the natural cellulose fibers thus cut are heated to 500˜1800° C. at a heating rate of 5˜20° C./min in an atmosphere of H2 and N2 at 1:1, and then maintained at 500˜1800° C. for 0.5˜2 hr thus obtaining carbonized cellulose. Also, in the case of a high-temperature catalytic reaction such as a reforming reaction, the stability of a support may increase at a high temperature of at least 1100° C., making it suitable to apply the support to the catalytic reaction. In this procedure, impurities are removed from the natural cellulose fibers, and thus the thickness of the wall of the fibers is decreased, and the space that has been occupied by impurities (composed mainly of wax and fat components) may be kept in the form of inner pores. In the case of cellulose fibers treated at a temperature higher than 1100° C., the pores become large and the pore volume is decreased and simultaneously the surface area is drastically reduced due to high-temperature treatment. As the carbonization temperature increases, the ratio of metal content relative to the carbon content of a sample may change, and the carbonization temperature may be set depending on the end uses of carbonized materials.
Subsequently, in order to introduce a functional group onto the surface of the thermally treated natural cellulose fibers, such fibers are chemically treated with an acidic solution, thus preparing the cellulose support. More specifically, the surface of the thermally treated natural cellulose fibers is chemically treated with the acidic solution so that a functional group such as CO—, CH—, O—C═O, CO2, CO3, etc., is imparted thereon, thus obtaining the cellulose support.
According to an embodiment of the present invention, the chemical treatment of the natural cellulose fibers with the acidic solution to impart the surface thereof with a functional group is carried out by immersing the thermally treated natural cellulose fibers in a 0.1˜0.5 mol sulfuric acid aqueous solution and then performing 10˜60 treatments at a sweep rate of 50 mV/s in the voltage range of −0.15˜1.3 V. Thereafter, immersion in a 30% nitric acid solution (or a 14 N nitric acid solution) at 100˜150° C. and treatment for 10 min˜20 hr may be carried out, or the natural cellulose fibers may be immersed in a mixture solution of nitric acid (14 M, 50 ml) and sulfuric acid (98%, 50 ml) or a mixture solution of 98% sulfuric acid and 70% nitric acid at a volume ratio of 3:1 and then treated for 5 min˜6 hr while being refluxed at 50˜70° C. The natural cellulose fibers thus treated are sufficiently washed with distilled water, filtered, and dried at 110° C. for 12 hr, thus obtaining the cellulose support to be used as a final catalytic support.
Subsequently, metal catalyst nanoparticles are supported on the surface of the chemically treated cellulose support using CVD or impregnation.
The metal catalyst nanoparticles supported on the surface of the cellulose support may include Pt, Au, Ag, Ni, Co, Ru, Pd or Mo nanoparticles. As such, CVD or impregnation may be applied in order to support the metal catalyst nanoparticles on the surface of the cellulose support.
According to an embodiment of the present invention, supporting the metal catalyst nanoparticles on the surface of the cellulose support using CVD may be performed through the following procedures. Specifically, the cellulose support obtained by being dispersed in the form of nanoparticles and then being chemically treated is positioned at the center of a quartz tube installed at the center of a furnace, maintained at 100˜120° C. at a pressure of 6˜10 torr for 30˜120 min to remove impurities from the inside of the quartz tube, and then maintained for 1 hr or longer while allowing nitrogen (50˜300 sccm) to flow thereto. In order to treat the metal catalyst nanoparticles using CVD, the inner temperature of the quartz tube is changed to 80˜300° C. at a heating rate of 10° C./min, and a gaseous metal precursor material begins to flow at the point of time at which the inner temperature of the tube reaches the reaction temperature, so that metal catalyst nanoparticles are supported on the surface of the catalytic support. The metal precursor is placed in an evaporator of an oven in advance before use. For example, in the case of a Pt precursor (MeCpPtMe3), when the reactor is heated to 60˜80° C. to reach the reaction temperature, the cock of the connection pipe is opened so that the gaseous metal precursor is transferred to the cellulose support in the reactor. The cellulose support is maintained at the reaction temperature (80˜300° C.) for 30 min˜24 hr. As the reaction time increases, the amount of metal catalyst nanoparticles supported on the surface of the cellulose support is increased.
A Pt precursor for supporting the Pt particles on the surface of the cellulose support may be selected from the group consisting of methyltrimethylcyclopentadiethyl platinum (MeCpPtMe3), Pt(Me)3(Cp), Pt(Tfacac)2, Pt(Me)(CO)(Cp), Pt(Me)2(COD), [PtMe3(acac)]2 (acac; acetylacetonato ligand), PtCl2(CO)2, Pt(PF3)4, Pt(acac)2 and Pt(C2H4)3, but is not necessarily limited thereto.
In addition, the metal precursor may include a Ru compound such as ruthenium chloride (RuCl3), ruthenium acetylacetonate (Ru(CH3COCHCOCH3)3), bisethylcyclopentadienyl ruthenium ((C6H5)2Ru) or bis(2,4-dimethylpentadienyl)ruthenium (II) (Ru[(CH3)2C5H5]2), an Ag compound such as a silver 2,2-dimethylbutyrate complex (Ag2(CH3CH2C(CH3)2COO)2(PMe3)2), a Pd compound such as palladium diacetate (CH3COO)2Pd, a Ni compound such as nickel nitrate (Ni(NO3)2) or nickel carbonyl (Ni(CO)4), a Co compound such as dicarbonylcyclopentadienyl cobalt, Co(CO)3NO or Co(NO3)2, and a Mo compound such as Mo(CO)6.
The CVD used in the present invention is advantageous because, even when the reaction time is lengthened, the size of metal catalyst nanoparticles is not increased or the dispersibility thereof is not lowered and a predetermined nanoscale may be maintained and only the supported amount may be effectively increased.
According to an embodiment of the present invention, supporting the metal catalyst nanoparticles on the surface of the cellulose support using impregnation may be performed through the following procedures. As such, the above-mentioned metal precursor may be used as a metal precursor suitable for supporting metal catalyst nanoparticles on the cellulose support chemically treated with the acidic solution. The cellulose support is immersed in the metal precursor aqueous solution (0.1˜1 mol) and ultrasound is then applied thereto for 5 min˜3 hr, after which the state of the cellulose support being immersed is maintained for 12 hr. The slurry solution having the cellulose support immersed therein is filtered, dried in an oven at 100˜120° C. for 12 hr or longer, and then burned in a furnace at 400˜600° C. in a N2 atmosphere for 2˜6 hr, finally obtaining a catalyst supported on the surface of the cellulose support.
In the case where Pt catalyst nanoparticles are supported on the surface of the cellulose support, the resulting catalyst is effective at hydrogenation of tetralin or benzene, oxidation of methanol, ethanol and phenol, etc.
In the case where Pt catalyst nanoparticles are supported on the surface of the cellulose support and a co-catalyst such as Ru or Co is additionally supported thereon, the resulting catalyst may be very usefully applied to decrease poisoning caused by CO in a fuel cell electrode reaction or to promote the oxygen reduction reaction.
In the case where Pd nanoparticles are supported on the surface of the cellulose support, the resulting catalyst is favorable in terms of selective hydrogenation of hydrocarbons and fuel cell electrode reaction, in lieu of the Pt catalyst.
In the case where Ag nanoparticles are supported on the surface of the cellulose support, the resulting catalyst is very useful as an adsorbent. Also, when it is used as a co-catalyst of another precious catalyst (Pd, etc.), it is useful for selective hydrogenation of hydrocarbons and may be applied to a variety of reactions, including oxidation of CO, dehydrogenation of propane, reduction of nitrogen oxide (NOx), oxidation of benzylalcohol, etc.
In the case where Ni catalyst nanoparticles are supported on the surface of the cellulose support, the resulting catalyst is considerably effective at a reforming reaction for H2 preparation, and may also be very useful in desulfurization, denitrilization, demetalization, etc.
In the case where Mo catalyst nanoparticles are supported on the surface of the cellulose support, the resulting catalyst is very effective at desulfurization, denitrilization, demetalization, etc.
In the case where Co catalyst nanoparticles are supported on the surface of the cellulose support, the resulting catalyst may be used as a co-catalyst for desulfurization, denitrilization and demetalization, and may also be utilized as a co-catalyst of a platinum catalyst for a fuel cell, and additionally, as a catalyst for a Fisher-Tropsch reaction, a catalyst for oxidation and partial oxidation of hydrocarbon, a catalyst for reforming and amination of ethanol, a catalyst for hydrogenation, a catalyst for substitution of aqueous gas, etc.
The following examples that are set forth to illustrate but are not to be construed as limiting the present invention may provide a better understanding of the present invention, and those skilled in the art will appreciate that a variety of modifications and variations are possible within the scope and spirit of the present invention and such modifications and variations belong to the attached claims.
(1) Thermal Treatment of Natural Henequen Fibers Under Specific Conditions
In order to remove impurities from natural henequen fibers and increase the surface area and porosity thereof, natural henequen fibers were thermally treated under specific conditions. Henequen fibers were separated into thin fibers of tens˜hundreds of μm, which were then cut into short fibers having a length of 1˜2 mm in liquid nitrogen. The henequen fibers thus cut were heated to 500˜1500° C. at a heating rate of 5˜20° C./min in a N2 gas mixture atmosphere containing 5˜50% H2, and then maintained at 500˜1500° C. for 1 hr so that the henequen fibers were carbonized.
(2) Introduction of Functional Group on the Thermally Treated Henequen Fibers Using Chemical Treatment to Facilitate the Supporting of Metal Nanocatalyst
The henequen fibers thermally treated in (1) were immersed in a 0.5 mol sulfuric acid aqueous solution and then treated 10˜60 times at a sweep rate of 50 mV/s in the voltage range of −0.15˜1.3 V. The henequen fibers were immersed in a mixture solution of nitric acid (14 M, 50 ml) and sulfuric acid (98%, 50 ml) at a volume ratio of 3:1 and then treated for 10 min while being refluxed at 60° C. The treated sample was sufficiently washed with distilled water, filtered, and dried at 110° C. for 12 hr, thus obtaining a cellulose support useful as a final catalytic support.
(3) Supporting of Metal Nanocatalyst on the Surface of the Cellulose Support Obtained by Pretreatments (1) and (2) Using CVD
In order to support a Ni nanocatalyst on the surface of the cellulose support obtained by (1) and (2) in sequence using impregnation, carbonized cellulose subjected to surface treatment was prepared, and nickel nitrate (Ni(NO3)2) as a Ni precursor was dissolved in distilled water thus preparing a 1 mol precursor aqueous solution. The Ni aqueous solution was added so that the carbonized cellulose was sufficiently immersed, and applying ultrasound for 30 min was repeated 2˜5 times, whereby the aqueous solution was efficiently transferred to the inside of pores of the support. Subsequently, the carbonized cellulose was allowed to stand for 12˜24 hr in a state of being immersed in the Ni aqueous solution, filtered using filter paper, dried in an oven at 110° C. for 12 hr or more and then burned in a furnace at 450° C. for 4 hr in a N2 atmosphere, finally obtaining a cellulose catalyst having Ni particles supported thereon.
A cellulose support was prepared in the same manner as in Example 1, with the exception that kenaf was used as a support source instead of henequen fibers, and a Ni nanocatalyst was prepared using such a catalytic support.
A cellulose support was prepared in the same manner as in Example 1, with the exception that rice straw was used as a support source instead of henequen fibers, and a Ni nanocatalyst was prepared using such a catalytic support.
(1) Supporting of Ni Precursor on γ-Al2O3 Via Incipient Impregnation
γ-Al2O3 (97%, Strem) was used as a support, and nickel nitrate (Ni(NO3)2) as a Ni precursor was dissolved in distilled water thus preparing a 1 mol precursor aqueous solution. Thereafter, Al2O3 dried in an oven at 110° C. for 12 hr or longer was used, and incipient impregnation was applied, thus obtaining a Ni/Al2O3 catalyst.
(2) Preparation of Metal Catalyst in Oxide Form Via Drying and Burning
The catalyst having the Ni precursor supported using incipient impregnation was dried in an oven at 110° C. for 12 hr or more and treated in a furnace at 450° C. for 4 hr in a N2 atmosphere, finally obtaining a Ni/Al2O3 catalyst in oxide form.
Changes in properties, components and metal contents of cellulose fibers in proportion to an increase in thermal treatment temperature, the distribution of alkali metal and alkaline earth metal present in the carbonized cellulose, and the interaction between the metal and the carbonized fibers were analyzed. The catalysts comprising the cellulose support treated at different temperatures and the Ni particles supported thereon were tested in CO2 reforming of CH4. The results are summarized as below.
In (1) of Example 1, the natural henequen fibers were thermally treated at different temperatures, and the resulting samples were analyzed using SEM. The results are shown in
In (1) of Example 1, the natural henequen fibers were thermally treated at different temperatures, and the properties of the resulting carbonized samples were analyzed using Raman spectroscopy. The results are shown in
As shown in
In (1) of Example 1, the natural henequen fibers were thermally treated at different temperatures, and the components of the resulting samples were analyzed using thermo-gravimetric analysis (TGA) and energy dispersive X-ray fluorescence (ED-XRF). Specifically, the remaining metal contents were analyzed using TGA (air atmosphere, heating to 20˜1000° C.), and the qualitative analysis (content ratio) of metal components was conducted using ED-XRF, and thus accurate quantitative and qualitative analysis of metal components in the cellulose fibers was performed. The results are shown in Table 1 below.
aEach sample was carbonized in H2/N2 flow (H2/N2 = 1:4 vol. ratio) for 2 hr, then treated by a mixture solution of sulfuric acid (98% H2SO4, 50 ml) and nitric acid (14M HNO3, 50 ml) at 60° C. for 3 hr.
As is apparent from Table 1, the structure of carbonized cellulose support contained a variety of kinds of alkaline earth metals such as Ca, Mg, etc., and the amounts of these metal components were increased in proportion to an increase in the thermal treatment temperature (carbonization temperature). The carbonized cellulose was converted from an amorphous structure at low temperature into a hard graphite structure having increased crystallinity at raised carbonization temperature.
In (1) of Example 1, the natural henequen fibers were thermally treated at different temperatures, and the structure of the resulting samples was analyzed using transmission electron microscopy (TEM) and the composition of the surface thereof was analyzed using energy-dispersive X-ray analysis (EDAX). The results are shown in
In (1) of Example 1, the natural henequen fibers were thermally treated at different temperatures, and the resulting samples were supported with the Ni catalyst and then used for CO2 reforming of CH4 for 168 hr. The catalysts before/after the reaction were recovered and analyzed via XRD. The results are summarized in
In (1) of Example 1, the henequen fibers were thermally treated at 1100° C. thus obtaining the carbonized henequen the surface of which was then supported with Ni catalyst, and the resulting catalyst was used for CO2 reforming of CH4 for 168 hr. The catalysts before/after the reaction were recovered and then analyzed using X-ray photoelectron spectroscopy (XPS). The results are shown in
In the case of the Ni/Al2O3 catalyst shown in (i) of
Each of the catalysts of Example 1 and Comparative Example 1 was used for CO2 reforming of CH4. The results are shown in
In
As mentioned above, this is because the alkaline earth metal particles such as Ca or Mg inherently contained in the henequen support impart a stronger catalyst-support interaction (SMSI), and thus the Ni catalyst particles do not agglomerate but are maintained in a state of being highly dispersed upon extended catalytic reaction.
Using each of the catalysts of Example 1 and Comparative Example 1, the CO2 reforming of CH4 was performed, and the catalysts before and after the reforming reaction were recovered to perform elemental analysis (EA), and thus the amount of coke formed by the reforming reaction using each catalyst was estimated. The results are shown in Table 2 below.
acellulose was carbonized at 1100° C. for 2 hr in the flow of H2/N2 (H2:N2 = 1:1 volume ratio)
In Table 2, the ratio of C contents measured before/after the reforming reaction was increased by 0.3% in the carbonized cellulose but was increased by 7.5% in the catalyst supported on commercially available Al2O3. The formation of coke in the cellulose support was remarkably decreased.
Consequently, the Ni catalyst supported on henequen can exhibit much more durability in the high-temperature catalytic reaction compared to the conventional Ni/Al2O3 catalyst. Most of the cellulose materials including henequen according to the present invention can be very effectively used as a catalytic support for a variety of reactions.
The BET surface area, SEM image and inherent metal components of the carbonized kenaf of Example 2 were analyzed using ED-XRF.
The BET surface area of kenaf fibers are shown in Table 3 below. As is apparent from Table 3, the surface area of the carbonized fibers is gradually increased in proportion to an increase in the thermal treatment temperature. This is because impurities (wax or pectin) are removed from the structure of cellulose fibers as mentioned above.
The BET surface area, SEM image and inherent metal components of carbonized rice straw of Example 3 were analyzed using ED-XRF.
The BET surface area of the carbonized rice straw is shown in Table 4 below. As is apparent from Table 4, the surface area of the carbonized fibers is gradually increased in proportion to an increase the thermal treatment temperature. This is because impurities (wax or pectin) are removed from the structure of cellulose fibers as mentioned above. However, in the case of the rice straw treated at 1100° C., the surface area was decreased. This is considered to be due to the properties of rice straw wherein the rice straw easily structurally breaks upon treatment at a high temperature of at least 1100° C. and also part of the pores thereof may break, thus decreasing the surface area.
As shown in
As described hereinbefore, the present invention provides a method of preparing a catalyst using an alkali metal or an alkaline earth metal in natural cellulose fibers as a co-catalyst and a dispersant. According to the present invention, the catalyst can be prepared using alkali metal and/or alkaline earth metal components as a co-catalyst and a dispersant, thus increasing the dispersibility of catalytic components and enhancing the interaction between the catalyst and the support to thereby retard agglomeration and increase the durability of the catalyst.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2011-0040645 | Apr 2011 | KR | national |
