KR101337743B1 - Modified nickel-based catalysts for steam reforming, method for fabricating the same and hydrogen production method using the catalysts - Google Patents
Modified nickel-based catalysts for steam reforming, method for fabricating the same and hydrogen production method using the catalysts Download PDFInfo
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- KR101337743B1 KR101337743B1 KR1020110040771A KR20110040771A KR101337743B1 KR 101337743 B1 KR101337743 B1 KR 101337743B1 KR 1020110040771 A KR1020110040771 A KR 1020110040771A KR 20110040771 A KR20110040771 A KR 20110040771A KR 101337743 B1 KR101337743 B1 KR 101337743B1
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Abstract
Provided is a nickel catalyst for steam reforming reaction, a method for preparing the same, and a method for producing hydrogen gas using the same. The catalyst includes a composite represented by the formula M1 2 - x M2 x / 2 Ti y O z and a porous carrier supported on nickel, where M1 and M2 represent alkali metals and alkaline earth metals, respectively, 2-x, x / 2, y and z represent molar ratios of M1, M2, Ti and O, respectively, x is 0.0 to 2.0, y is 1.0 to 10 and z has a range of 2.0 to 20. According to this, it is possible to effectively improve the activity and life of the catalyst by improving the resistance to deactivation in the steam reforming reaction of the nickel catalyst.
Description
The present invention relates to a catalyst, a method for producing the same, and an application thereof, and more particularly, to a nickel catalyst used for steam reforming of a hydrocarbon, a method for preparing the same, and a method for producing hydrogen gas from a hydrocarbon raw material using the same.
Recently, as interest in discovering clean alternative energy technologies and using hydrogen energy is increasing, attempts have been made to use hydrogen as fuel for fuel cells. However, when pure hydrogen is used as an energy source, there is a problem in production cost and storage property, and thus research is being conducted to convert hydrogen into hydrogen through reforming of hydrocarbons. Hydrogen is produced in three ways: Steam reforming, Partial oxidation, and Autothermal reforming with the appropriate combination of steam reforming and partial oxidation reforming. A steam reforming reaction that can be easily obtained and has a relatively good yield for hydrogen is the most widely used.
In particular, the steam reforming process from natural gas is known to be most suitable for the production of hydrogen for fuel cells. This is because natural gas has a lot of reserves all over the world, but it is mainly composed of low-grade gas such as methane and ethane, so it is considered that it is not added value by itself because it has no useful value except for heating purposes.
Catalysts most widely used in steam reforming of hydrocarbons are divided into noble metal catalysts such as Pd, Pt and Ir and non-noble metal catalysts such as Ni and Co. Although noble metal catalysts show higher activity and stability than non noble metal catalysts, non-noble metal catalysts to replace them are attracting attention due to their low price competitiveness due to limited reserves on the earth. In fact, almost all nickel-based catalysts are commercialized in steam reforming.
Among the non-noble metal catalysts, the nickel-based catalyst shows high activity as well as inferior to the noble metal catalyst. As a conventional methane steam reforming catalyst, Ni / Al 2 O 3 [Numaguchi, T., Ind. Eng. Chem. Res., 30 (1991) 447-453. However, such a catalyst has been pointed out that the problem of deactivation due to carbon deposition or catalyst sintering is very serious.
To date, several research teams have tried various methods to develop catalysts that inhibit inactivation. A zirconia-supported nickel catalyst added with cobalt is known to make a catalyst that performs better than a conventional nickel-based steam reforming catalyst [US Pat. No. 4,026,823], and a catalyst in which iridium is supported on a mixed carrier of zirconia and alumina has also been known. [US Pat. No. 4,240,934]. In addition, a catalyst in which a metal, such as lanthanum and cerium, and silver is added to a nickel catalyst as a cocatalyst in an appropriate ratio is supported on alumina, silica, magnesia, zirconia, and the like as a general carrier (US Pat. No. 4,060,498).
However, they have a problem of deactivation or catalyst deactivation when applied to a high space velocity steam reforming reaction, so that they can be used for steam reforming to maintain the activity at high temperature and thermal stability at high gas space velocity. There is a need for improvement in catalyst composition.
The technical problem to be solved by the present invention is to provide a catalyst and an improved method for improving the activity and stability of the steam reforming reaction of hydrocarbons.
Another technical problem to be solved by the present invention is to provide a method for producing hydrogen gas using the catalyst in steam reforming reaction of a hydrocarbon.
One aspect of the present invention to achieve the above technical problem provides a catalyst for steam reforming of hydrocarbons. The catalyst includes a composite represented by the following Chemical Formula 1 and a nickel-supported porous carrier.
≪ Formula 1 >
M1 2 - x M2 x / 2 Ti y O z
Wherein M1 and M2 each represent an alkali metal and an alkaline earth metal,
2-x, x / 2, y and z represent the molar ratios of M1, M2, Ti and O, respectively,
x ranges from 0.0 to 2.0, y ranges from 1.0 to 10 and z ranges from 2.0 to 20.)
The alkali metal may be any one selected from potassium, sodium, and lithium, and the alkaline earth metal may be any one selected from calcium and magnesium.
The porous carrier may be zirconia, yttria stabilized zirconia (YSZ) or alumina.
The composite may be supported by 0.5 to 30% by weight based on the total weight of the composite and the porous carrier.
The nickel may be supported in 5.0 to 30% by weight based on the total weight of the catalyst.
Another aspect of the present invention to achieve the above technical problem provides a method for producing a catalyst for steam reforming of hydrocarbons. The method includes preparing a mixed aqueous solution of a porous carrier, an alkali metal precursor, an alkaline earth metal precursor, and titanium oxide; Drying and calcining the aqueous solution to prepare a porous carrier carrying the complex represented by Chemical Formula 1; And impregnating, drying and firing the nickel precursor in the porous carrier on which the composite is supported.
Firing in the step of preparing the porous carrier carrying the composite may be performed for 3 to 9 hours at a temperature of 600 to 1000 ℃.
Another aspect of the present invention to achieve the above technical problem provides a method for producing hydrogen gas. The process uses a catalyst as described above to conduct a steam reforming reaction of hydrocarbons under reaction conditions having a reaction temperature of 600 to 950 ° C., a space velocity of 1,000 to 300,000 h −1 , and a molar ratio of carbon to steam of 1: 0.5 to 5.0. May include performing.
The catalyst according to an embodiment of the present invention has superior activity than conventional nickel-supported catalysts in performing steam reforming reaction of hydrocarbons and exhibits the ability to prevent deactivation due to long-term operation. In other words, by producing a modified nickel catalyst by combining a complex consisting of alkali metal or alkaline earth metal and titanium oxide in the nickel catalyst, it improves the resistance to deactivation in the steam reforming reaction of the nickel catalyst to effectively improve the activity and life of the catalyst can do.
In addition, by using a non-noble metal nickel catalyst, which is economical compared to the previous noble metal catalyst, it secures a price competitiveness, and a nickel-based catalyst shown in the prior art by forming a complex by adding some non-noble metal components with a simple manufacturing method. It has the advantage of increasing resistance to catalyst deactivation by coking and sintering, which is a weak point of.
However, the effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned can be clearly understood by those skilled in the art from the following description.
1 is a graph showing the durability results for long-term operation of the catalyst according to an embodiment of the present invention and the catalyst according to a comparative example.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
According to one embodiment of the present invention, a catalyst for steam reforming of a hydrocarbon is provided.
The catalyst includes a composite represented by the following Chemical Formula 1 and a nickel-supported porous carrier.
≪ Formula 1 >
M1 2 - x M2 x / 2 Ti y O z
Wherein M1 and M2 each represent an alkali metal and an alkaline earth metal,
2-x, x / 2, y and z represent the molar ratios of M1, M2, Ti and O, respectively,
x ranges from 0.0 to 2.0, y ranges from 1.0 to 10 and z ranges from 2.0 to 20.)
That is, the catalyst according to the present embodiment means a material in which at least one of an alkali metal and an alkaline earth metal and a titanium oxide are supported on a porous carrier together with nickel as an active metal.
The alkali metal may be any one selected from, for example, potassium, sodium, and lithium, and the alkaline earth metal may be any one selected from, for example, calcium and magnesium. Preferably, the alkali metal may be potassium, and the alkaline earth metal may be calcium.
In addition, the complex may be present in a crystalline phase having a single or various composition ratio selected within the numerical range of the x, y and z. For example, the complex K 2 Ti 2 O 5, K 2 Ti 4 O 9, K 2 TiO 3, CaTi 2 O 5, CaTi 4 O 9, CaTiO 3,
The composite may be supported by 0.5 to 30% by weight based on the total weight of the composite and the porous carrier, preferably 5.0 to 20% by weight, more preferably 5.0 to 10.0% by weight. When the composite is supported on the porous carrier in less than 5.0% by weight, it is difficult to exhibit sufficient deactivation resistance of the catalyst, and when it is loaded in excess of 30% by weight, the exposed area of nickel, the active metal, is reduced, thereby substantially reducing the active site. Because it can.
The porous carrier may support various kinds of carriers known in the art as a material supporting the composite and the nickel and providing a wide specific surface area. In addition, the carrier may be provided in the form of a metal oxide, wherein the metal oxide is zirconia (ZrO 2 ), modified zirconia such as yttria-stabilized zirconia (YSZ), alumina (alumina, Al 2) O 3 ) and activated alumina may be at least one selected from the group consisting of. Specifically, it is preferable to use γ-alumina or YSZ in view of reaction activity and thermal resistance.
The nickel serves as an active metal, and may be supported at 0.5 to 30% by weight based on the total weight of the catalyst (ie, the total weight of the composite, nickel and the porous carrier), preferably 5 to 15 It may be supported in weight percent. If the nickel content is less than 0.5% by weight, it is difficult to maintain the activity of the hydrocarbon as a catalyst for the steam reforming reaction, and when it exceeds 30% by weight, it is not preferable in terms of efficient dispersibility because aggregation occurs between the active metal particles. Because.
In addition, according to another embodiment of the present invention, a method for preparing a catalyst for steam reforming of a hydrocarbon is provided. The method may include the following steps.
First, a mixed aqueous solution of a porous carrier, an alkali metal precursor, an alkaline earth metal precursor, and titanium oxide is prepared.
The porous carrier is as described above, the alkali metal precursor or the alkaline earth metal precursor is provided in the form of metal salts such as carbonates, phosphates, nitrates and acetates of alkali or alkaline earth metals, or oxides of alkali or alkaline earth metals. It may be provided in the form. For example, the alkali metal precursor may be K 2 CO 3 , and the alkaline earth metal precursor may be CaO.
Next, the aqueous solution is dried and calcined to prepare a porous carrier carrying the composite represented by Chemical Formula 1.
The drying may be performed in at least one of a reduced pressure drying using a rotary evaporator and a heating drying using an electric furnace and the like. In addition, the firing may be performed for 3 to 9 hours at a temperature of 600 to 1000 ℃.
In particular, the composite of Chemical Formula 1 composed of alkali metal, alkaline earth metal and titanium oxide may be more strongly bonded to the porous carrier through the firing process. Therefore, it is possible to prevent volatilization and loss of the composite during use of the finally prepared catalyst in the hydrocarbon reforming process, thereby improving the durability of the catalyst.
Finally, a nickel precursor is impregnated in the porous carrier on which the composite is supported, dried and calcined to prepare a catalyst for steam reforming of a desired hydrocarbon.
The nickel precursor may be provided in the form of nitrate or acetate salt of nickel, nickel chloride and nickel hydroxide, or may be provided in the form of a hydrate. For example, the nickel precursor may be Ni (NO 3 ) 2 .6H 2 O.
As described above, the drying may be performed by a common drying method such as vacuum drying and heat drying, and the firing may be performed at a temperature of 400 to 800 ° C. for 2 to 4 hours.
On the other hand, according to another embodiment of the present invention, there is provided a method for producing hydrogen gas through the steam reforming reaction of a hydrocarbon using the catalyst described above. The steam reforming reaction of the hydrocarbon may use hydrocarbon raw materials such as methane, ethane, propane, butane, diesel and gasoline.
In particular, the hydrogen gas production method according to the present embodiment can perform the steam reforming reaction of the lower hydrocarbons, to maintain the activity of the catalyst even under reaction conditions that are prone to deactivation of the catalyst, it is possible to enable the stable production of hydrogen gas have. The steam reforming reaction may be applied, for example, to fields such as high temperature fuel cells and fuel reformers for less than 5 kW class fuel cells.
In the hydrogen gas production method, the reactant used for the hydrocarbon reforming reaction may be a molar ratio of carbon: water vapor 1: 0.5 to 5.0, preferably a molar ratio of carbon: water vapor may be 1: 0.5 to 2.0. If the mole ratio of carbon to carbon is less than 0.5, it proceeds similarly to the pyrolysis of hydrocarbons. Therefore, it does not take advantage of the steam reforming reaction to obtain abundant hydrogen gas. If the molar ratio of carbon to carbon exceeds 5.0, carbon formation is suppressed but energy is reduced. There is a disadvantage that the cost increases.
In addition, the hydrocarbon reforming reaction may be carried out at a space velocity of 1,000 to 300,000 h −1 at a reaction temperature of 600 to 950 ° C.
Hereinafter, preferred examples for the understanding of the present invention will be described. It should be understood, however, that the following examples are intended to aid in the understanding of the present invention and are not intended to limit the scope of the present invention.
Manufacturing example 1 to 7
A nickel catalyst for steam reforming of hydrocarbons was prepared through the following process.
After mixing γ-Al 2 O 3 , K 2 CO 3 , CaO and TiO 2 in distilled water at a constant ratio and mixing well, distilled water was slowly evaporated using a rotary evaporator, and the recovered powder was dried in an electric furnace at 120 ° C. for 12 hours. It baked for 6 hours at the temperature of 800 degreeC in air atmosphere. In the obtained fired product, for example, x in K 2 - x Ca x / 2 Ti 2 O 5 is 2.0, K 2 - x Ca x / 2 Ti 2 O 5 is 20% by weight, Al 2 O 3 Is 80% by weight of "K 2 - x Ca x / 2 Ti 2 O 5 (20) -Al 2 O 3 (80), x = 2.0" is shown in Table 1 below.
Using the calcined product as a carrier, the Ni (NO 3 ) 2 .6H 2 O precursor was impregnated to support a predetermined amount of nickel. First, the nickel precursor was dissolved in distilled water, and the calcined product was added and stirred. The obtained mixed liquid was removed by distilled water using a rotary evaporator, dried in an electric furnace at 120 ° C. for 12 hours, and then heated at a temperature of 600 ° C. in an air atmosphere. It was calcined for 3 hours. The content of supported nickel was fixed at 10% by weight to prepare a nickel catalyst for steam reforming of hydrocarbons.
Comparative Example One
In the same manner as in Preparation Examples 1 to 7 to prepare a nickel catalyst for steam reforming of hydrocarbon, γ-Al 2 O 3 Instead, it was prepared using SiO 2 .
Comparative Example 2
A nickel supported catalyst was prepared by impregnation using γ-Al 2 O 3 as a carrier and Ni (NO 3 ) 2 .6H 2 O as a nickel precursor. First, the nickel precursor was dissolved in distilled water and stirred by adding γ-Al 2 O 3 , and the obtained mixed liquid was removed by distilled water using a rotary evaporator and then dried in an electric furnace at 120 ° C. for 12 hours, and then heated at a temperature of 600 ° C. in an air atmosphere. It was calcined for 3 hours. The content of supported nickel was 10% by weight to prepare a nickel catalyst for steam reforming of hydrocarbons.
Experimental Example 1: Evaluation of Catalytic Activity for Steam Reforming of Methane Gas
In the atmospheric fixed bed reactor produced in the laboratory to measure the catalytic activity, the catalyst prepared according to Preparation Examples 1 to 7 and Comparative Examples 1 and 2 was filled with 10% hydrogen-90% helium gas at 100 ccm while flowing at 100 ccm. Reduction pretreatment for 2 hours at.
The reactant was injected into the reactor by adjusting the molar ratio of methane to water vapor to 1: 2.5. The temperature of the reactor was heated to 750 ° C. through an electric furnace and a PID temperature controller, and hydrogen was produced by continuously supplying a mass flow controller and a micropump so that the space velocity was 15,000 h −1 . The gas composition before and after the reaction was analyzed by gas chromatograph connected to the reactor to measure the catalytic activity.
Methane conversion and hydrogen selectivity were calculated by the following equations (1) and (2), respectively. In particular, the result of Equation 2 is a water vapor conversion reaction (CO + H 2 O → H 2 + CO 2 ), which is a reaction simultaneously with the steam reforming reaction (CH 4 + H 2 O → CO + 3H 2 ) It represents the degree of actual hydrogen production relative to the theoretical maximum hydrogen production that can be produced.
&Quot; (1) "
Methane Gas Conversion Rate (%)
= Moles of methane reacted / moles of methane fed × 100
&Quot; (2) "
Hydrogen selectivity
= (3 x moles of reacted methane + moles of carbon dioxide produced) / moles of reacted methane
Table 1 below summarizes the results of the reaction after 600 minutes by applying the catalysts prepared according to Preparation Examples 1 to 7 and Comparative Examples 1 to 2 to steam reforming of hydrocarbons.
(%)
Ni / K 2 - x Ca x / 2 Ti 2 O 5 -Al 2 O 3 according to an embodiment of the present invention In the case of the catalyst, the conversion rate of methane was 1.0 to 7.2% higher than that of the nickel catalyst (Comparative Example 2) supported on the alumina carrier, regardless of the content of K 2 - x Ca x / 2 Ti 2 O 5 or the value of x. It can be seen that it appears. Hydrogen selectivity, which means the amount of hydrogen produced, also increased by 0.1-0.4. This is K 2 - x Ca x / 2 Ti 2 O 5 It means that the nickel catalyst including a complex such as has a high activity in the steam reforming reaction.
The methane conversion of Comparative Example 1, which is a nickel catalyst having alumina-substituted silica, was found to be very low at 34.8%, but rapidly decreased after 250 minutes of reaction time, thereby losing activity. This result disproves the need for alumina, a suitable carrier for nickel catalysts.
Comparison of the reaction activities of Preparation Examples 1 to 4 shows that the nickel catalyst when x is 0.1 to 0.0 is excellent. In other words, when a small amount of alkaline earth metal is added, it is presumed to promote the steam reforming reaction. The results of Preparation Examples 3 and 5 to 7 showing the effect on the content of K 2 - x Ca x / 2 Ti 2 O 5 is less than 30% by weight of K 2 - x Ca x / 2 Ti 2 O 5 It is confirmed that the addition has a positive effect on the reactivity.
Experimental Example 2: Long-term durability evaluation of the catalyst according to the reaction time
Long-term stability of the catalyst with respect to the reaction time (100 hours) using the catalyst prepared according to Preparation Example 1 and Comparative Example 2 at the reaction conditions of water vapor: carbon = 1: 1, space velocity 200,000 h -1 , reaction temperature 800 ℃ And durability against deactivation was evaluated. Other reaction test method was evaluated in the steam reforming reaction activity of methane in the same manner as in Experimental Example 1 and the measurement results are shown in Table 2 below.
(%)
Looking at the results of the steam reforming activity shown in Table 2 and FIG. 1, Comparative Example 2 has a low initial reaction activity, and a significant decrease in activity after 100 hours. On the other hand, according to the preparation of the present invention, the modified nickel catalyst composite (Preparation Example 1) including a composite composed of alkali metal, alkaline earth metal and titanium oxide improves the catalytic performance by about 8.4% in the steam reforming reaction of hydrocarbon. Improved resistance to carbon deposition and catalyst sintering
As mentioned above, although the preferred embodiment of this invention was described in detail, this invention is not limited to the said embodiment, A various deformation | transformation and the said by those of ordinary skill in the art within the technical idea and the scope of the present invention. Changes will be possible.
Claims (8)
≪ Formula 1 >
M1 2-x M2 x / 2 Ti y O z
Wherein M1 and M2 each represent an alkali metal and an alkaline earth metal,
2-x, x / 2, y and z represent the molar ratios of M1, M2, Ti and O, respectively,
x is greater than 0.0 and up to 2.0, y is 1.0 to 10 and z is in the range of 2.0 to 20.
M1 is any one selected from potassium, sodium, and lithium,
M2 is a catalyst for steam reforming of a hydrocarbon which is any one selected from calcium and magnesium.
The porous carrier is a catalyst for steam reforming of a hydrocarbon which is zirconia, yttria stabilized zirconia (YSZ) or alumina.
The complex is a catalyst for steam reforming of a hydrocarbon supported by 0.5 to 30% by weight based on the total weight of the complex and the porous carrier.
The nickel is a catalyst for steam reforming of a hydrocarbon is supported by 5.0 to 30% by weight based on the total weight of the catalyst.
Drying and calcining the aqueous solution to prepare a porous carrier having a composite represented by the following Chemical Formula 1; And
Method for producing a catalyst for steam reforming of a hydrocarbon comprising the step of impregnating, drying and calcining a nickel precursor on the porous carrier carrying the composite:
≪ Formula 1 >
M1 2 - x M2 x / 2 Ti y O z
Wherein M1 and M2 each represent an alkali metal and an alkaline earth metal,
2-x, x / 2, y and z represent the molar ratios of M1, M2, Ti and O, respectively,
x ranges from 0.0 to 2.0, y ranges from 1.0 to 10 and z ranges from 2.0 to 20.
Firing in the step of preparing the porous carrier on which the composite is supported is a catalyst for steam reforming of a hydrocarbon is carried out for 3 to 9 hours at a temperature of 600 to 1000 ℃.
A method for producing a hydrogen gas, which performs a steam reforming reaction of a hydrocarbon under reaction conditions having a reaction temperature of 600 to 950 ° C., a space velocity of 1,000 to 300,000 h −1 , and a molar ratio of carbon to steam of 1: 0.5 to 5.0.
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| KR20190101254A (en) | 2018-02-22 | 2019-08-30 | 부경대학교 산학협력단 | A method for the production of hydrogen by a steam reforming reaction of hydrothermal liquefaction liquid from macro algae using a catalyst of perovskite composite structure |
| KR102376875B1 (en) | 2021-11-24 | 2022-03-18 | 부경대학교 산학협력단 | Method for producing hydrogen by steam reforming and hydrogenation reaction of biomass-derived oils on a nickel-based catalyst |
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| KR101634946B1 (en) | 2015-06-30 | 2016-07-01 | 한국에너지기술연구원 | Methane steam reforming, using nickel/alumina nanocomposite catalyst or nickel/silica-alumina hybrid nanocomposite catalyst |
| WO2018186513A1 (en) * | 2017-04-04 | 2018-10-11 | 부경대학교 산학협력단 | Catalyst for steam reforming reaction of seaweed-derived hydrothermal liquefaction material, and method for producing hydrogen by using same |
| CA3194179A1 (en) | 2020-10-13 | 2022-04-21 | Changmin Chun | Catalyst systems for reforming in cyclic flow reactors, preparation and use thereof |
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| KR20090118776A (en) * | 2008-05-14 | 2009-11-18 | 포항공과대학교 산학협력단 | Additives for preventing catalyst deactivation by coke formation during catalytic hydrocarbon reforming |
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| KR20090118776A (en) * | 2008-05-14 | 2009-11-18 | 포항공과대학교 산학협력단 | Additives for preventing catalyst deactivation by coke formation during catalytic hydrocarbon reforming |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190101254A (en) | 2018-02-22 | 2019-08-30 | 부경대학교 산학협력단 | A method for the production of hydrogen by a steam reforming reaction of hydrothermal liquefaction liquid from macro algae using a catalyst of perovskite composite structure |
| KR102376875B1 (en) | 2021-11-24 | 2022-03-18 | 부경대학교 산학협력단 | Method for producing hydrogen by steam reforming and hydrogenation reaction of biomass-derived oils on a nickel-based catalyst |
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