KR101636005B1 - A nickel catalyst chemically immobilized on mesoporous alumina support, preparation method thereof and production method of hydrogen gas by steam reforming of liquefied natural gas using said catalyst - Google Patents
A nickel catalyst chemically immobilized on mesoporous alumina support, preparation method thereof and production method of hydrogen gas by steam reforming of liquefied natural gas using said catalyst Download PDFInfo
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- KR101636005B1 KR101636005B1 KR1020140181396A KR20140181396A KR101636005B1 KR 101636005 B1 KR101636005 B1 KR 101636005B1 KR 1020140181396 A KR1020140181396 A KR 1020140181396A KR 20140181396 A KR20140181396 A KR 20140181396A KR 101636005 B1 KR101636005 B1 KR 101636005B1
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Abstract
The present invention relates to a nickel catalyst chemically immobilized on an alumina carrier, a process for producing the same, and a process for producing hydrogen gas by a steam reforming reaction of a liquefied natural gas (LNG) using the catalyst, An anionic nickel-based composite ion obtained by chelating a nickel precursor by applying a positive charge on an alumina carrier is used for producing hydrogen gas by the steam reforming reaction of natural gas (LNG) And the nickel loading is 5 to 50% by weight. The nickel catalyst chemically immobilized on the alumina support, the preparation method thereof, and the catalyst To a method for producing hydrogen gas by steam reforming reaction of liquefied natural gas (LNG). According to the present invention, it is possible to prepare a catalyst having improved physical properties and an active nickel surface area as compared with a nickel catalyst supported on an alumina support by a common impregnation method, and to apply it to the steam reforming reaction of liquefied natural gas (LNG) High-purity hydrogen gas can be efficiently produced over a long period of time.
Description
The present invention relates to a nickel catalyst for use in a hydrogen gas production process through steam reforming reaction of liquefied natural gas (LNG), and more particularly, to a nickel catalyst chemically immobilized on an alumina carrier, The present invention relates to a method for producing hydrogen gas by the steam reforming reaction of liquefied natural gas (LNG) using a catalyst.
The development of new clean energy sources has been actively researched to improve the existing energy supply method as the problem of fossil fuel limitations and various environmental pollution problems arise. In this trend, hydrogen is attracting attention as a next-generation energy medium that can effectively replace existing energy supply and demand. Hydrogen is known to have a very high energy content per unit mass, and it has the advantage that it does not contain carbon and therefore does not emit carbon dioxide during combustion. In addition, when hydrogen is applied to an engine or a fuel reforming apparatus, emissions of sulfur oxides (SO x ) and nitrogen oxides (NO x ), which are atmospheric pollutants, can be effectively reduced. In addition, hydrogen can be applied to various fields such as ammonia synthesis and hydrogenation process as well as a device based on a fuel cell (Fuel Cell), and its use value is expected to surge in the future. However, in order to stably supply such hydrogen, the development of a catalyst system for allowing the reforming reaction to occur actively on the fuel reforming apparatus must be preliminarily determined. Various reforming catalysts have been studied for this purpose.
The fuel reforming reaction is carried out using raw materials such as hydrocarbons such as methane and ethane, alcohol, acid, ether, glycerol and other biomass, Steam reforming, partial oxidation, auto-thermal reforming, and dry reforming are known as reactions. Among these reforming reactions, the reaction is relatively simple and the steam reforming reaction, which has the highest ratio of hydrogen to carbon monoxide, is most suitable for producing high purity hydrogen. In addition, the steam reforming reaction is currently the most widely used commercially, and it is believed that there is an advantage in terms of infrastructure that the results of the related technology can be applied immediately. In particular, methane is used as the main raw material for steam reforming reaction. Methane is richly contained in Liquefied Natural Gas (LNG), and it is easily supplied to hydrogen stations and residential complexes through gas pipes Can be supplied. Therefore, in this patent, a new catalyst was designed to stably supply hydrogen at a high concentration through the steam reforming reaction of liquefied natural gas.
A noble metal-based catalyst such as Rh (non-patent document 1), Pd (non-patent document 2), Ru (non-patent document 3) Has been studied. The noble metal-based catalysts have a high modifying reaction activity and a high resistance to inactivation, but they are not used in commercial processes because they are disadvantageous from the economical point of view. Therefore, nickel-based inexpensive noble metal catalysts have been widely used for steam reforming. However, these nickel-based catalysts have the disadvantage that they can be inactivated by sintering in a high temperature steam reforming reaction or by carbon deposited during the reaction (Non-Patent Document 6). Therefore, a series of studies have been conducted to improve the activity of the nickel-based catalyst and to secure the stability in the long-term reaction.
As a physico-chemical improvement method of nickel-based catalysts, a method of supporting nickel on various metal oxides has been studied. In the case of a catalyst prepared by supporting nickel on a cerium-added zirconia carrier (Patent Document 1), it was found that the steam reforming reaction of methane showed 95% methane conversion and 112% hydrogen yield, o It has a disadvantage of using zirconia which is high in C and high in manufacturing cost. In addition, the catalyst preparation process is roughly divided into three steps from the zirconia production step to the cerium addition step and the nickel impregnation step, which is not easy because the production process is complicated and the necessary metal precursors and chemicals are required.
A steam reforming reaction on a catalyst prepared by adding nickel to a lanthanide metal and silver by using various metal oxides such as alumina, silica and magnesia has been studied (Patent Document 2). The catalyst exhibited a hydrogen composition ratio of about 71% in the reaction product at a steam-to-carbon ratio of 3 and a reaction temperature of 830 ° C, but the disadvantage was that the reaction temperature was higher than that of the commercial process and the ratio of water vapor to carbon was high .
Studies on nickel catalyst supported on silica, alumina and zirconia carrier as a steam reforming catalyst composed of only nickel and a carrier component have been carried out (Non-Patent Document 7). The study was carried out at a very low temperature of 500 o C, and the amount of nickel supported as the active phase was set at as low as 20 wt%. However, the conversion rate of methane remained low at the level of 20%, and the results showed that the zirconia-supported nickel catalyst showed the highest activity. Catalysts supported on silica or alumina, which are relatively economical catalysts, showed a generally low methane conversion of less than 20%.
Alkoxide precursor-based sol-gel methods and nickel-alumina Aerogel catalysts prepared by carbon dioxide supercritical drying have been reported to show high activity in steam reforming reactions of liquefied natural gas Patent Document 3, Non-Patent Document 8). The catalyst showed a liquefied natural gas conversion of 70% or more at a reaction temperature of 600 ° C, and the particle size of the active nickel was small, less than 10 nm. However, the supercritical drying method is disadvantageous in that it is difficult to operate and at the same time mass production is not easy, and the alkoxide precursor based sol-gel method used in the patent is undesirable from the viewpoint of using an expensive and unstable alkoxide precursor.
LaAlO 3, LaFeO 3, SrTiO 3 and BaTiO 3 have a variety of perovskite (Perovskite) supported nickel on the oxide form by performing the steam reforming reaction of methane which information is reported, such as (non-patent reference 9), the In this study, it was aimed to improve the stability of the catalyst by improving the resistance to carbon deposition compared with commercial Ni / Al 2 O 3 catalyst by supporting nickel on perovskite. However, since the reaction temperature is very high at 800 ° C and the pressure is about 10 atm, it is pointed out that the reaction condition is not mild. It was also reported that the particle size of the supported nickel is very large, over 60 nm, and the dispersity of active nickel is very low, less than 2%.
As described above, the nickel-based catalysts developed to date have improved their physico-chemical properties and activity in steam reforming reactions through various production methods. In this study, the catalyst was prepared by uniformly dispersing nickel through alumina carrier with chemical immobilization, and the catalytic activity in the steam reforming reaction of liquefied natural gas was further enhanced compared to the nickel catalyst produced by the commercial impregnation method .
The present invention provides a method for preparing a nickel catalyst that is chemically immobilized on an alumina carrier for the production of hydrogen gas by steam reforming reaction of liquefied natural gas (LNG).
Another object of the present invention is to provide a method for efficiently producing hydrogen gas of high purity from steam reforming reaction of liquefied natural gas (LNG) using the catalyst.
In order to accomplish the above object, the present invention provides a process for producing hydrogen gas by the steam reforming reaction of liquefied natural gas (LNG), which comprises adding an anion obtained by chelation of a nickel precursor, Wherein the nickel-based composite ion is chemically immobilized on the alumina support, characterized in that the nickel-based composite ion is immobilized by bonding to the positive charge on the surface of the acid-treated alumina support and then dried and calcined, and the loading amount of nickel is 5 to 50 wt% By weight of nickel catalyst.
The present invention also provides a process for preparing a nickel precursor solution, comprising: i) dissolving a nickel precursor in a solvent to obtain a nickel precursor solution; Ii) dissolving a chelating agent in a solvent to obtain a chelating agent solution; Iii) mixing a chelating agent solution in step ii) with a nickel precursor solution in step i) to conduct a chelation reaction; Iv) dispersing the alumina carrier in a dispersion medium and acid-treating the surface of the alumina carrier with an acid; V) mixing the alumina support dispersion of step iv) with the chelated nickel precursor solution of step iii); (Vi) drying and heat-treating the mixed solution of the step (v), wherein the alumina support is chemically immobilized on the alumina support.
The nickel precursor may also be selected from the group consisting of Nickel Nitrate Hexahydrate, Nickel Chloride Hexahydrate, Nickel Acetate Tetrahydrate and Nickel Bromide Hydrate, Wherein the catalyst is chemically immobilized on an alumina support.
The present invention also relates to a method for producing a chelating agent, wherein the chelating agent is selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA) Wherein the alumina carrier is at least one selected from the group consisting of trans-1,2-diaminocyclohexanetetraacetic acid (DCTA) and ethyleneglycoltetraacetic acid (EGTA). Of the present invention.
The present invention also relates to a process for the preparation of a mixed gas having a volume ratio of liquefied natural gas / water vapor in the range of 1/10 to 1/1 at a reaction temperature of 450-900 ° C in the presence of a nickel catalyst chemically immobilized on the alumina support, Wherein the reforming reaction is carried out while flowing the hydrogen gas at 500,000 ml / h · g-catalyst.
According to the present invention, the nickel catalyst chemically immobilized on the alumina carrier not only exhibits enhanced activity as compared with the nickel catalyst produced by the commercial impregnation method in the hydrogen gas production reaction by the steam reforming reaction of the liquefied natural gas (LNG) And the surface area of active nickel after reduction.
1 is a graph showing the relationship between the amount of X (Ni / AS) of a nickel catalyst (Ni / AS) chemically immobilized on an alumina support according to Example 1 of the present invention and the nickel catalyst (Ni / AS) supported on an alumina support by a common impregnation method according to Comparative Example 1 - line diffraction analysis graph
2 is a graph showing the relationship between the temperature of a nickel catalyst (NiE / AS) chemically immobilized on an alumina support according to Example 1 of the present invention and the nickel catalyst (Ni / AS) supported on an alumina support by a common impregnation method according to Comparative Example 1 Temperature-programmed Reduction Result Graph
FIG. 3 is a graph showing the results of the reduction of a nickel catalyst (Ni / AS) chemically immobilized on an alumina support according to Example 1 of the present invention and a nickel catalyst (Ni / AS) supported on an alumina support by a common impregnation method according to Comparative Example 1 Post Transmission Electron Microscopy (Transmission Electron Microscopy)
FIG. 4 is a graph showing the results of a comparison between the nickel catalyst (NiE / AS) chemically immobilized on the alumina support according to Example 1 of the present invention and the alumina support (Comparative Example 1) Changes in LNG conversion (left) and hydrogen yield (right) on nickel catalyst (Ni / AS)
Hereinafter, the present invention will be described in detail.
The nickel catalyst chemically immobilized on the alumina support of the present invention is used for producing hydrogen gas by the steam reforming reaction of liquefied natural gas (LNG).
The nickel catalyst chemically immobilized on the alumina support preferably has a loading amount of nickel of 5 to 50% by weight in view of catalyst activity and economy. When the loading amount of nickel is less than 5% by weight, nickel, which is an active phase, is excessively diluted in an alumina support to lower its concentration, and is disadvantageous in surface exposure, so that it is difficult to obtain a visible effect in the production of hydrogen gas. An excessive amount of nickel is likely to be sintered into large particles, which is not only ineffective in the course of the reaction, but also undesirable in view of the economics of metal utilization.
The alumina carrier used in the present invention may be prepared by a co-precipitation method, a templating method, a hydrothermal method, and an epoxide-driven sol-gel method Although epoxide induced sol-gel processes are preferred for making alumina carriers. For example, the preparation of an alumina support through the method comprises: i) dissolving an aluminum precursor in an aqueous alcohol solution to hydrate; Ii) introducing an epoxide-based compound into the solution to cause hydroxyl group in hydrated aluminum ion and to conduct a condensation reaction to obtain a wet gel; Iii) aging and drying the wet gel at room temperature; Iv) heat treating the dried wet gel.
In addition, the nickel catalyst chemically immobilized on the alumina support of the present invention comprises the steps of: i) dissolving a nickel precursor in a solvent to obtain a nickel precursor solution; Ii) dissolving a chelating agent in a solvent to obtain a chelating agent solution; Iii) mixing a chelating agent solution in step ii) with a nickel precursor solution in step i) to conduct a chelation reaction; Iv) dispersing the alumina carrier in a dispersion medium and acid-treating the surface of the alumina carrier with an acid; V) mixing the alumina support dispersion of step iv) with the chelated nickel precursor solution of step iii); (Vi) drying and heat-treating the mixed solution of step (v).
In this case, the solvent for dissolving the nickel precursor and the chelating agent is not particularly limited as long as the solvent can dissolve the nickel precursor and the chelating agent. Examples of the solvent include water, alcohols, ketones, aldehydes, Two or more mixed solvents may be used, but water is preferable from an economic point of view as well as from an environmental point of view.
The nickel precursor may include one selected from the group consisting of Nickel Nitrate Hexahydrate, Nickel Chloride Hexahydrate, Nickel Acetate Tetrahydrate, and Nickel Bromide Hydrate. Or more, and it is more preferable to use Nickel Nitrate Hexahydrate.
Examples of the chelating agent include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), trans-1,2-diamino It is preferable to use at least one selected from the group consisting of trans-1,2-diaminocyclohexanetetraacetic acid (DCTA) and ethyleneglycoltetraacetic acid (EGTA). Ethylenediaminetetraacetic acid (EDTA) Is more preferably used.
In addition, the nickel catalyst chemically immobilized on the alumina support preferably has a molar ratio of the chelating agent / nickel precursor of 0.5 to 3. When the molar ratio of the chelating agent / nickel precursor is less than 0.5, the nickel is sufficiently chelated When the amount is larger than 3, an excessive amount of chelating agent is used, which is not economically efficient, and the chelating agent may interfere with the immobilization of nickel on the alumina support surface.
In the surface treatment step of the alumina support, at least one selected from the group consisting of nitric acid, hydrochloric acid, diluted sulfuric acid, carbonic acid and acetic acid, .
In addition, the present invention provides a process for producing a mixed gas in which a liquefied natural gas and water vapor are mixed at a volume ratio ranging from 1/10 to 1/1 at a reaction temperature of 450-900 ° C in the presence of a nickel catalyst chemically immobilized on the alumina support, A method for producing hydrogen gas from liquefied natural gas while flowing at a rate of 1,000 to 500,000 ml / h 占 촉매 -catalyst. In the steam reforming reaction, the reaction is carried out while allowing the liquefied natural gas and steam to flow together with nitrogen while maintaining the temperature of the reactor at 450-900 ° C. When the reaction temperature is lower than 450 ° C, the temperature is too low, Sufficient catalytic activity can not be expected since sufficient energy is not supplied for the reaction to proceed. If it exceeds 900 o C, deactivation phenomenon occurs due to sintering of nickel, which is an active phase, at high temperature, which is not preferable. If the volume ratio of the liquefied natural gas / steam is less than 1/10, it is preferable that the liquefied natural gas / Is too small to evaluate the catalytic activity. When the volume ratio is more than 1/1, the amount of liquefied natural gas relative to steam is large, which is not efficient.
The hydrogen gas producing method preferably includes a pretreatment step of reducing a nickel catalyst chemically immobilized on the alumina carrier filled in the reactor before the reaction with a mixed gas of nitrogen and hydrogen. In general, in the steam reforming reaction of liquefied natural gas (LNG), since the active phase is a reduced nickel species rather than an oxidized species of nickel, it is preferable that all nickel-based catalysts undergo a pretreatment for reduction using hydrogen before performing the reaction. Particularly, the mixed gas used in the pretreatment process preferably has a volume ratio of hydrogen / nitrogen of 1/10 to 1/2. When the volume ratio is less than 1/10, the amount of hydrogen required for reduction of nickel is small, It is difficult to expect high activity, and if it is larger than 1/2, the amount of hydrogen required for reduction is lowered and the economical efficiency is lowered, which is not preferable.
Hereinafter, the present invention will be described in more detail with reference to Examples. These embodiments are only for illustrating the present invention, and thus the scope of the present invention should not be construed as being limited by these embodiments.
< Manufacturing example : Alumina Carrier Manufacturing>
Ethanol (manufactured by Fisher) was used as a raw material of an aqueous alcohol solution to prepare an alumina carrier, aluminum nitride nitrate nonahydrate (Aldrich product) was used as an aluminum precursor, and epoxide compound Propylene oxide (Propylene Oxide, product of Acros) was used.
First, 1.7 ml of distilled water and 11.4 g of aluminum precursor were added to 80 ml of an ethanol solvent, followed by stirring for 20 minutes. Then 21.4 ml of propylene oxide (Acros product) was slowly added to the solution to induce a condensation reaction between the metal ions. The solution was further stirred for 20 minutes to obtain a white opaque wet gel, The wet gel thus obtained was aged at room temperature for 2 days. Thereafter, the aged gel was placed in an oven at 70 ° C. and dried for 48 hours to obtain a gel (Xerogel) by alumina control. The obtained alumina-controlled gel was heat-treated at 700 ° C for 5 hours in an air atmosphere using an electric furnace, and finally the alumina carrier was obtained and designated as AS.
< Example 1> alumina On the carrier Preparation of chemically immobilized nickel catalysts
Nickel nitrate hexahydrate (Aldrich) was used as the nickel precursor, and ethylenediaminetetraacetic acid (EDTA, Aldrich) was used as the chelating agent.
First, 1 g of the nickel precursor was dissolved in 1 ml of distilled water, followed by stirring for 20 minutes. Then, 1 g of the chelating agent was dispersed in 10 ml of distilled water, ammonia water (manufactured by Aldrich) was added, and the pH of the solution was adjusted to 8 to completely dissolve the chelating agent. The nickel precursor solution was then added to the chelating agent solution and the pH of the mixed solution was maintained at 8. Meanwhile, 1 g of the alumina carrier (AS) prepared in the above Preparation Example was dispersed in 10 ml of distilled water, nitric acid (Nitric Acid, product of Aldrich) was added to adjust the pH to 4, and the mixture was stirred for 1 hour. A mixed solution of the nickel and the chelating agent was added to the dispersion of the support, and the resulting opaque slurry of blue was heated to finally obtain a blue solid. The resulting solid was dried at 100 ° C. for 24 hours and then heat-treated at 700 ° C. for 5 hours in an air atmosphere using an electric furnace. Finally, a chemically immobilized nickel catalyst was prepared on the alumina support. Respectively. The amount of nickel supported on the catalyst was calculated to be 40 wt%.
< Comparative Example 1> commercial On impregnation By alumina On the carrier Supported Preparation of nickel catalyst
Nickel nitrate hexahydrate (product of Aldrich) was used as the nickel precursor in Comparative Example 1. The alumina support used was the same alumina support as in Example 1.
First, 1 g of the nickel precursor was dissolved in 21 ml of distilled water, followed by stirring for 20 minutes. 1 g of the alumina support was added to this solution, and then the resulting opaque green slurry was heated to finally obtain a green solid. The solid thus obtained was dried at 100 ° C for 24 hours and then heat-treated at 700 ° C for 5 hours in an air atmosphere using an electric furnace. Finally, a nickel catalyst supported on an alumina carrier was prepared by a commercial impregnation method. / AS. The amount of nickel supported on the catalyst was calculated to be 40 wt%.
Table 1 shows the physical properties of the alumina support (AS) prepared in Preparation Example, the NiE / AS catalyst according to Example 1 and the Ni / AS catalyst according to Comparative Example 1. Table 1 shows that the NiE / AS catalyst chemically immobilized on alumina support (AS) has a higher specific surface area (188 m 2 g -1 ), a pore volume (0.36 cm 3 g -1 ) and an average pore size (7.6 nm). This is a result of the fact that the nickel precursor was chemically immobilized on the alumina support and dispersed evenly in Example 1.
(Production example)
(Example 1)
(Comparative Example 1)
FIG. 1 is a graph showing the results of X-ray diffraction analysis of a NiE / AS catalyst according to Example 1 and a Ni / AS catalyst according to Comparative Example 1. FIG. Both catalysts showed diffraction peaks corresponding to nickel-aluminate (NiAl 2 O 4 ) phase and nickel oxide (NiO) phase, indicating that some of the nickel species in the heat- Which is a mixed phase. It was also found that the Ni / AS catalyst showed diffraction peaks of nickel oxide phase more clearly than NiE / AS catalyst, which suggests that NiO / AS catalyst nickel oxide paper is more uniformly dispersed.
FIG. 2 is a graph showing temperature-programmed reduction results of a NiE / AS catalyst according to Example 1 and a Ni / AS catalyst according to Comparative Example 1. FIG. Both catalysts showed reduction peaks due to the nickel and nickel-aluminate crystal phases interacting strongly with the carrier at 691 ° C and 728 ° C, respectively. However, in the case of Ni / AS catalyst, the reduction peak due to the single nickel oxide phase was further observed at a low temperature region of 382 ° C. This means that the average metal-carrier interaction force of the nickel species present in the Ni / AS catalyst is weaker do. That is, the NiE / AS catalyst chemically immobilized on the alumina of the present invention was found to be more resistant to sintering in the reduction and reaction process than the Ni / AS catalyst.
Table 2 shows the active nickel surface area obtained by the hydrogen temperature-programmed desorption analysis of the NiE / AS catalyst according to Example 1 and the Ni / AS catalyst according to Comparative Example 1. Both catalysts were subjected to a reduction treatment at 700 ° C for 3 hours before performing the analysis. As a result, NiE / AS catalyst showed higher hydrogen adsorption amount and active nickel surface area than Ni / AS catalyst. This is because NiE / AS catalyst was resistant to sintering during the reduction process . In other words, it can be said that the NiE / AS catalyst is superior to the Ni / AS catalyst in terms of the dispersibility of active nickel. These results can be confirmed by transmission electron microscopy (FIG. 3) of the two reduced catalysts (FIG. 3). It was found that the nickel particles were more evenly dispersed on the NiE / AS catalyst than the Ni / AS catalyst.
(μmol-H 2 / g)
(m 2 / g-Ni)
< Experimental Example > Alumina On the carrier Steam Reforming Characteristics of Liquefied Natural Gas (LNG) Using Chemically Immobilized Nickel Catalysts
The hydrogen gas production reaction by the steam reforming reaction of liquefied natural gas (LNG) composed of a mixed gas of methane and ethane using the two catalysts (NiE / AS and Ni / AS catalysts) prepared in Example 1 and Comparative Example 1 Respectively. The liquefied natural gas used in this experiment was composed of 92 vol% methane and 8 vol% ethane. A catalyst (20 mg) was charged in a quartz reactor to activate the catalyst prior to the steam reforming reaction of liquefied natural gas. A mixed gas of nitrogen (30 ml / min) and hydrogen (3 ml / min) Respectively. The temperature during the reduction process was set at 700 ° C and maintained for 3 hours. Thereafter, the temperature of the reactor was lowered to 550 ° C., and the steam reforming reaction was performed by passing the reacted natural gas and steam through the catalyst layer. At this time, the volume ratio of liquefied natural gas and water vapor was kept at 1/2, and the total flow rate of the reactant in terms of the catalyst mass was maintained at 138,964 ml / h · g-catalyst. In this experimental example, the conversion and the hydrogen yield of liquefied natural gas were calculated by the following equations (1) and (2), respectively.
(1)
(2)
FIG. 4 is a graph showing the relationship between a nickel catalyst (NiE / AS) chemically immobilized on alumina according to Example 1 of the present invention and a nickel catalyst (Ni / AS) supported on an alumina support by a common impregnation method according to Comparative Example 1 (Left) and the change in hydrogen yield (right). As can be seen from the figure, the two catalysts produced showed stable reaction activity without inactivation in the liquefied natural gas reforming reaction for 15 hours. Also, it can be seen that the NiE / AS catalyst according to Example 1 exhibits a higher liquefied natural gas conversion and hydrogen yield than the Ni / AS catalyst according to Comparative Example 1. This indicates that Ni / As compared with the AS catalyst, the nickel is uniformly dispersed on the carrier and the resistance to sintering is increased during the reduction process. In other words, the NiE / AS catalyst prepared through the chemical immobilization of nickel has a higher active nickel surface area than the Ni / AS catalyst prepared by the commercial impregnation method, and has more active sites necessary for the conversion reaction of liquefied natural gas . In conclusion, the nickel catalyst (NiE / AS) chemically immobilized on the alumina support produced by the present invention has improved physical properties and active nickel surface area compared to the nickel catalyst (Ni / AS) supported on the alumina support by the commercial impregnation method , It shows higher efficiency in hydrogen gas production reaction through steam reforming reaction of liquefied natural gas.
The embodiments of the present invention described above should not be construed as limiting the technical idea of the present invention. The scope of protection of the present invention is limited only by the matters described in the claims, and those skilled in the art will be able to modify the technical idea of the present invention in various forms. Accordingly, such improvements and modifications will fall within the scope of the present invention as long as they are obvious to those skilled in the art.
Claims (5)
I) dissolving a nickel precursor in a solvent to obtain a nickel precursor solution;
Ii) dissolving a chelating agent in a solvent to obtain a chelating agent solution;
Iii) mixing a chelating agent solution in step ii) with a nickel precursor solution in step i) to conduct a chelation reaction;
Iv) dispersing the alumina carrier in a dispersion medium and acid-treating the surface of the alumina carrier with an acid;
V) mixing the alumina support dispersion of step iv) with the chelated nickel precursor solution of step iii);
(Vi) drying and heat-treating the mixed solution of step (v).
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| WO2020040380A1 (en) * | 2018-08-21 | 2020-02-27 | 한국과학기술연구원 | Composite body having nanoparticles uniformly dispersed in nano-sized pores in support, and method for producing same |
| KR20200021677A (en) * | 2018-08-21 | 2020-03-02 | 한국과학기술연구원 | Composite Body in which Nanoparticles are uniformly dispersed in nanosized Pores of a Support and Method of manufacturing the same |
| KR102407233B1 (en) | 2018-08-21 | 2022-06-10 | 한국과학기술연구원 | Composite Body in which Nanoparticles are uniformly dispersed in nanosized Pores of a Support and Method of manufacturing the same |
| US11801501B2 (en) | 2018-08-21 | 2023-10-31 | Korea Institute Of Science And Technology | Composite body having nanoparticles uniformly dispersed in nano-sized pores in support, and method for producing same |
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