Monolith catalyst for carbon dioxide reforming reaction, preparation method for same, and preparation method for synthesis gas using same

Abstract

The present invention relates to a monolith catalyst for a carbon dioxide reforming reaction and to a preparation method for same, and more specifically the invention provides a preparation method for a monolith catalyst for a methane reforming reaction using carbon dioxide, the method comprising a step of mixing and impregnating a support in a metal precursor solution, coating a monolith substrate with the solution resulting from the mixing and impregnating, drying same and then calcining the monolith substrate coated with the solution resulting from the mixing and impregnating.

Claims

1. A monolith catalyst for a carbon dioxide reforming reaction comprising a support impregnating an active material represented by the following Formula 1 and a monolith substrate, wherein a weight ratio of the support impregnating the active material and the monolith substrate is 1:1:
a(X)−b(Zr)/Z  [Formula 1] where X is an active material of Ni, Z is a support of SiO.sub.2, a and b each represents parts per weight of X and Zr relative to component Z in order, and a is 5.0 to 30.0, and b is 1.0 to 30.0 relative to 100 parts by weight of the support (Z).

2. The monolith catalyst for a carbon dioxide reforming reaction as set forth in claim 1, wherein the shape of the monolith substrate is a honeycomb structure.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a graph for showing EDS analysis of a monolith substrate;

(2) FIG. 2 illustrates graphs on TGA analyses with respect to catalysts after performing reaction according to Example 3 and Comparative Example 3; and

(3) FIG. 3 illustrates graphs on carbon dioxide conversion ratio with respect to time as the results according to Examples 1 and 3 and Comparative Examples 1 and 3.

MODE FOR IMPREGNATING OUT THE INVENTION

(4) The present invention will be explained in more detail as follows.

(5) The present invention provides a monolith catalyst for a carbon dioxide reforming reaction including a support impregnating an active material represented by the following Formula 1 and a monolith substrate.
a(X)−b(Zr)/Z  [Formula 1]

(6) In the above Formula 1, X is an active material of Co or Ni, Z is a support of SiO.sub.2 or Al.sub.2O.sub.3, a and b each represents parts per weight of X and Zr relative to component Z in order, and a is 5.0 to 30.0, and b is 1.0 to 30.0 relative to 100 parts by weight of the support (Z).

(7) The present invention provides a monolith catalyst for a carbon dioxide reforming reaction, including one component selected from cobalt (Co) or nickel (Ni), an active metal catalyst including zirconium (Zr) and a support component selected from silica (SiO.sub.2) or alumina (Al.sub.2O.sub.3), where the amount of the active metal catalyst is optimized to satisfy Formula 1, and each metal precursor solution is carried in the support component selected from silica (SiO.sub.2) or alumina (Al.sub.2O.sub.3), and further including a monolith substrate.

(8) In the monolith catalyst of the present invention, the monolith catalyst support is provided for easy contact between a solid catalyst and a reaction gas to increase the surface area of the catalyst by impregnating the catalyst in a densely dispersed state. The monolith catalyst support may have, for example, a honeycomb structure, or a structure in which empty spaces with a rod shape are connected.

(9) The amount of cobalt or nickel (a) is 5 to 30 parts by weight relative to 100 parts by weight of the support (Z), and preferably, in a range of 5 to 20 parts by weight. In the case that the amount of the active component is less than 5 parts by weight, the conversion of the reaction material may be slow, and in the case that the amount is greater than 30 parts by weight, the life of the catalyst may decrease due to the rapid generation of carbon deposition phenomenon and deactivation of the catalyst.

(10) The amount of zirconium (b) is 1 to 30 parts by weight relative to 100 parts by weight of the support (Z), and preferably, in a range of 1 to 20 parts by weight. In the case that the amount of Zr is less than 1 part by weight, activation synergy effect may not be obtained, and in the case that the amount is greater than 30 parts by weight, the activity of the catalyst may be rather deteriorated.

(11) The preferable shape of the monolith substrate according to the present invention is a honeycomb structure.

(12) It is generally known that other transition metals such as cobalt and nickel are used as active components for producing a catalyst used for a methane and carbon dioxide reforming reaction, and alumina, silica, etc. are used as support components. Further studies on each ratio of the catalyst components are being actively conducted. Although a catalyst has excellent activity, a catalyst molding process is essential for the application to a practical process. However, a commonly used catalyst with a granule type has serious limitations concerning durability and stability due to rapid formation of cokes. In addition, the limitation of hard application to a system with a high flow rate is present due to large pressure drop. To solve the limitations, a monolith substrate with a honeycomb structure may be used. In a monolith catalyst in which empty spaces with a rod shape and a honeycomb structure are connected, heat may be easily transferred via walls, the temperature of the catalyst may become uniform, and the pressure drop may be small, thereby being provided as an appropriate shape for treating reactants with a high flow rate.

(13) In addition, the monolith catalyst has high surface area per unit volume because of the dense structure, and excellent abrasion-resistance. In the case that the monolith catalyst is applied to a carbon dioxide reforming reaction, low carbon deposition due to rapid mass transfer, reinforcement of catalyst durability due to high thermal stability, and process compatibilization due to the possibility of a high flow rate reaction, may be realized.

(14) A monolith catalyst is necessary for the conversion of a large amount of carbon dioxide in a short time because a reaction system with a high flow rate is required. In this case, the shape of the honeycomb structure may improve the strength of the support and may increase the catalyst activity due to high specific surface area.

(15) According to the present invention, there is provided a preparation method of a monolith catalyst for a carbon dioxide reforming reaction including a support impregnating an active material represented by the following Formula 1 and a monolith substrate, including the steps of:

(16) mixing and impregnating a metal precursor solution and a support Z of the following Formula 1 so as to meet the component ratio of the following Formula 1 (step 1);

(17) coating the monolith substrate with the mixed and impregnated solution in step 1 (step 2);

(18) drying the monolith substrate coated with the mixed and impregnated solution in step 2 (step 3); and

(19) calcining the dried monolith substrate after being coated with the mixed and impregnated solution in step 3 (step 4).
a(X)−b(Zr)/Z  [Formula 1]

(20) In Formula 1, X is an active material of Co or Ni, Z is a support of SiO.sub.2 or Al.sub.2O.sub.3, a and b each represents parts per weight of X and Zr relative to component Z in order, and a is 5.0 to 30.0, and b is 1.0 to 30.0 relative to 100 parts by weight of the support (Z).

(21) Hereinafter, the present invention will be explained step by step in detail.

(22) Step 1 according to the present invention is a step of mixing and impregnating a metal precursor solution with the support Z of Formula 1 so as to meet the component ratio in Formula 1 and is a step of providing an active metal catalyst including a component selected from cobalt (Co) or nickel (Ni), zirconium (Zr), and a support component selected from silica (SiO.sub.2) or alumina (Al.sub.2O.sub.3), where the content of the active metal catalyst is optimized to meet Formula 1, and each metal precursor solution is carried in and mixed with the support component selected from silica (SiO.sub.2) or alumina (Al.sub.2O.sub.3).
a(X)−b(Zr)/Z  [Formula 1]

(23) In Formula 1, X is Co or Ni, Z (support) is a support of SiO.sub.2 or Al.sub.2O.sub.3 coated with an active material, a and b each represents parts per weight of X and Zr relative to component Z in order, and a is 5.0 to 30.0, and b is 1.0 to 30.0 relative to 100 parts by weight of the support (Z).

(24) Methods for impregnating and adding a catalyst in a support selected from silica or alumina using zirconium, cobalt or nickel element for optimizing Formula 1 are not specifically limited. As the impregnating methods, various impregnating methods such as a heating impregnation method, an ambient impregnation method, a vacuum impregnation method, a normal pressure impregnation method, an evaporation to dryness method, a pore peeling method, and an incipient wetness method, an immersion method, a spray method or an ion exchange method may be applied.

(25) In addition, the precursor of each element in step 1 may be the following materials.

(26) As a cobalt precursor, a cobalt compound such as Co(NO.sub.3).sub.2 may be used, as a nickel precursor, a nickel compound such as Ni(NO.sub.3).sub.2 may be used, and as a zirconium precursor, a zirconium compound such as ZrCl.sub.2O may be used.

(27) The amount of cobalt or nickel (a) is 5 to 30 parts by weight relative to 100 parts by weight of the support (Z), and preferably in the range of 5 to 20 parts by weight. In the case that the amount of the active component is less than 5 parts by weight, conversion may be slow, and in the case that the amount is greater than 30 parts by weight, deactivation may occur due to the rapid carbon deposition of the catalyst, and the life of the catalyst may decrease.

(28) The amount of zirconium (b) is 1 to 30 parts by weight relative to 100 parts by weight of the support (Z), and preferably, in the range of 1 to 20 parts by weight. In the case that the amount of Zr is less than 1 part by weight, activation synergy effect may not be obtained, and in the case that the amount is greater than 30 parts by weight, the activity of the catalyst may be rather deteriorated.

(29) The preferable shape of the monolith substrate according to the present invention is a honeycomb structure.

(30) It is generally known that other transition metals such as cobalt and nickel are used as the active components for producing a catalyst used for a carbon dioxide reforming reaction, and alumina, silica, etc. are used as the support component. Further studies on each ratio of the catalyst components are being actively conducted. Although a catalyst has excellent activity, a catalyst molding process is essential for the application to a practical process. However, a commonly used catalyst with a granule type has serious limitations concerning durability and stability due to rapid formation of cokes. In addition, the limitation of hard application to a system with a high flow rate due to large pressure drop is present. To solve the limitations, a monolith substrate with a honeycomb structure may be used. In a monolith catalyst in which empty spaces with a rod shape and a honeycomb structure are connected, heat may be easily transferred via walls, the temperature of the catalyst may become uniform, and the pressure drop may be small, thereby being provided as an appropriate shape for treating reactants with a high flow rate. In addition, the monolith catalyst has high surface area per unit volume because of the dense structure and excellent abrasion-resistance. In the case that the monolith catalyst is applied to a carbon dioxide reforming reaction, low carbon deposition due to rapid mass transfer, reinforcement of catalyst durability due to high thermal stability, and process compatibilization due to the possibility of a high flow rate reaction, may be realized.

(31) A monolith catalyst is necessary for the conversion of a large amount of carbon dioxide in a short time because a reaction system with a high flow rate is required. In this case, the shape of the honeycomb structure may improve the strength of the support and may increase the catalyst activity due to high specific surface area.

(32) Step 2 according to the present invention is a step of coating the monolith substrate with the support carried in step 1 and is a step of impregnating and coating the monolith substrate with the mixed and impregnated solution in step 1.

(33) Step 3 according to the present invention is a step of drying the monolith substrate coated with the precursor solution in step 1, and is a step of drying the coated support in an oven at 110° C. for about 1 hour.

(34) Step 4 according to the present invention is a step of calcining the dried monolith substrate after being coated with the precursor solution at step 2, and the calcining may preferably be performed at 150 to 700° C. for 5 to 48 hours.

(35) In the case that the calcining temperature is less than 150° C., the physical properties of the catalyst may not be changed, and a dried state may be obtained, thereby not forming the chemical bond of the catalyst (bond between the catalyst components or between the catalyst component and the support). In the case that the temperature is greater than 700° C., the oxidation degree of the catalyst may be high, and the chemical bonds of some catalyst components may be broken, bonding with the catalyst activation components may not be maintained but may be separated therefrom at about 700° C. Thus, the above-mentioned range may be preferable.

(36) In this case, the preparation method is preferably performed by repeating from step 1 to step 3 so that the weight ratio of the support impregnating the active material and the monolith substrate may be greater than 0.8 to less than 1.2:1.

(37) In the case that the weight ratio is less than or equal to 0.8, the ratio of the catalyst activation components relative to the support is low, and the reaction may not be carried out smoothly, and in the case that the weight ratio is greater than or equal to 1.2, multiple layers of coating of the catalyst may be formed, and the catalyst components not participating in the reaction may increase. Thus, the catalyst component is not efficient, and the activity of the catalyst components may be deteriorated due to calcining phenomenon.

(38) In the case of using the monolith catalyst prepared by the above method in a production process for a synthesis gas including carbon monoxide and hydrogen, the activity of the catalyst may be maintained for a long time and the pressure drop may decrease when compared to a common granule type molded catalyst.

(39) Further, a preparation method for a synthesis gas from a gas including carbon dioxide using the monolith catalyst prepared by the above preparation method will be provided.

(40) Reactors for the reforming reaction of methane and carbon dioxide are not specifically limited to commonly used ones in the art, and particularly, a gas phase fixed bed reactor, a fluidized bed reactor, a liquid phase slurry bed reactor, etc., may be used.

(41) As preferable reaction conditions, the reaction temperature of 650° C. to 850° C., the pressure of 0.01 to 0.1 MPa, and the space velocity of 5,000 to 50,000 ml/gcat.Math.hr may be applied.

(42) In the case that the reaction temperature is less than 650° C., the reaction rate may be insufficient, and the conversion of reactants may not be sufficiently performed, and in the case that the reaction temperature is greater than 850° C., the carbonization of the catalyst may be initiated, thereby inducing early deactivation.

(43) In the case that the reaction pressure increases, the activity of the catalyst may be maintained stably, however the reaction pressure is not a considerably affecting variable. In the case that the pressure is greater than 0.1 MPa, the initial installation cost of the reactor may be large.

(44) In the case that the space velocity is less than 5,000 ml/gcat.Math.hr, productivity may be too low, and in the case that the space velocity is greater than 50,000 ml/gcat.Math.hr, contact hour of the reactants with the catalyst may decrease, thereby deteriorating the efficiency of a reforming reaction.

(45) The catalyst produced according to the present invention may be efficiently applied to the reforming reaction of methane and carbon dioxide, because the active metal is uniformly dispersed on the surface of the support through separately coating each active metal and calcining the catalyst. In addition, when compared to the activity of a reforming reaction of methane and carbon dioxide with a common granule type catalyst, high conversion ratio and stability may be obtained, pressure drop may decrease, and a reaction with a high flow rate may be conducted according to the present invention.

(46) Hereinafter, the present invention will be explained referring to exemplary embodiments, however the present invention is not limited to the following embodiments. The monolith catalyst prepared by the present invention may be applied to an oxygen-carbon dioxide-vapor tri-reforming reaction of methane, and a carbon dioxide reforming reaction using ethane, propane, etc. instead of methane, as well as a dry reforming reaction of methane and carbon dioxide.

EXAMPLES 1 TO 4

Preparation of Catalysts I to IV

(47) Co(NO.sub.3).sub.2.H.sub.2O or Ni(NO.sub.3).sub.2.H.sub.2O and ZrCl.sub.2O.H.sub.2O were dissolved in distilled water in a ratio shown in Table 1 (Examples 1 and 2: Co(NO.sub.3).sub.2.H.sub.2O, Examples 3 and 4: Ni(NO.sub.3).sub.2.H.sub.2O), followed by mixing with a silica (SiO.sub.2) or Al.sub.2O.sub.3 support (Examples 1 and 3: silica (SiO.sub.2), Examples 2 and 4: Al.sub.2O.sub.3). A monolith substrate was coated with the solution thus obtained in a weight ratio shown in Table 1, followed by drying in an oven at about 110° C. for 1 hour. The coating and drying were repeated many times to prepare a monolith catalyst so that the weight ratio of the monolith substrate and catalyst components became about 1:1. The monolith catalyst with the monolith substrate coated with the catalyst components was calcined at 400° C. for 6 hours to produce a monolith catalyst according to the present invention.

COMPARATIVE EXAMPLES 1 TO 4

Preparation of Catalysts I to IV

(48) Co(NO.sub.3).sub.2.H.sub.2O or Ni(NO.sub.3).sub.2.H.sub.2O and ZrCl.sub.2O.H.sub.2O were dissolved in distilled water in a ratio shown in Table 1 (Comparative Examples 1 and 2: Co(NO.sub.3).sub.2.H.sub.2O, Comparative Examples 3 and 4: Ni(NO.sub.3).sub.2.H.sub.2O), followed by mixing with a silica (SiO.sub.2) or Al.sub.2O.sub.3 support (Comparative Examples 1 and 3: silica (SiO.sub.2), Comparative Examples 2 and 4: Al.sub.2O.sub.3). The solution thus mixed was completely dried, followed by pulverizing to less than or equal to 80 mesh and mixing 15 wt % of microcrystalline cellulose and 85 wt % of a catalyst for molding. The mixture was mixed with colloidal silica as a binder (20 wt % relative to the solution), and a catalyst was prepared via a molder. The catalyst thus prepared was classified by size and was calcined at 400° C. for 6 hours to prepare a granule type molded catalyst.

COMPARATIVE EXAMPLES 5 AND 6

Preparation of Catalysts I to IV

(49) Ni(NO.sub.3).sub.2.H.sub.2O was dissolved in distilled water in a ratio shown in Table 1 and mixed with a silica (SiO.sub.2) support. A monolith substrate was coated with the solution thus obtained in a weight ratio shown in Table 1, followed by drying in an oven at about 110° C. for 1 hour.

(50) The coating and drying were repeated many times to prepare a monolith catalyst so that the weight ratio of the monolith substrate and catalyst components became about 0.8:1 (Comparative Example 1) and 1.2:1 (Comparative Example 2). The monolith catalyst with the monolith substrate coated with the catalyst components was calcined at 400° C. for 6 hours to produce a monolith catalyst.

EXPERIMENTAL EXAMPLE 1

Evaluation of Catalyst Performance I

(51) A reforming reaction of methane and carbon dioxide was performed according to the following method for comparing the performance of the catalysts prepared in Examples 1 to 4 and Comparative Examples 1 to 6, and the results are shown in Table 1. 1.0 g of each of the catalysts prepared in Examples 1 to 4 and Comparative Examples 1 to 6 was filled in a reactor, where catalysts having a size of 16 to 30 meshes were used in Comparative Examples 1 to 4. In this case, the weight of the catalyst was the weight of pure active catalysts represented by Formula 1 excluding monolith, binder, etc.

(52) As the reactor, a fixed bed tubular reactor equipped with an external heating system, having an inner diameter of 2 cm and being formed using a quartz material, was used. A mixture gas of methane/carbon dioxide in a molar ratio of 1:1 was supplied into the reactor in a space velocity of 20,000 ml/gcat.Math.hr to perform a catalyst reaction. In this case, the catalyst reaction was performed under an atmospheric atmosphere at the reaction temperature of 850° C., and exhausted gas after reaction was analyzed using a thermal conductivity detector of an online gas chromatography system.

(53) As shown in the following Table 1, the conversion ratio of CO.sub.2 was 84 to 98%, and the conversion ratio of CH.sub.4 was 72 to 94% when using the monolith catalysts prepared in Examples 1 to 4 according to the present invention. On the contrary, in the case of using the monolith or granule type catalysts according to Comparative Examples 1 to 6, the conversion ratio was decreased.

EXPERIMENTAL EXAMPLE 2

Evaluation of Catalyst Performance II

(54) Thermo gravimetric analyses and differential thermal analyses (TGA-DTA) were conducted to compare carbon deposition after the reactions of monolith (Example 3) and granule (Comparative Example 3) catalysts. Weight loss of each of the catalysts prepared in Example 3 and Comparative Example 3 with respect to the temperature was observed to 800° C. in a temperature elevation rate of 10° C./min using 2960 SDT V3.0F (TA Instruments, USA) under an air atmosphere. The results are shown in FIG. 2. In FIG. 2, rapid weight loss was found in a range between 500 and 700° C. in the granule catalyst when compared to the monolith catalyst, and it was found that the formation of carbon deposition was high in the granule catalyst.

EXPERIMENTAL EXAMPLE 3

Evaluation of Catalyst Performance III

(55) In order to compare the catalyst performance of the monolith catalyst and the granule catalyst, a reaction was performed under experimental conditions and methods explained in Experimental Example 1, and the conversion ratio of carbon dioxide with respect to time was calculated on the basis of the gas chromatography analysis data of the reactants for each of the catalysts prepared in Examples 1 and 3 and Comparative Examples 1 and 3, and the results are shown in FIG. 3. As shown in FIG. 3, when comparing the carbon dioxide conversion ratio at initial time and after about 40 hours of the reaction, the carbon dioxide conversion ratio in Examples 1 and 3 using the monolith catalyst was not much changed with respect to time, however the carbon dioxide conversion ratio in Comparative Examples 1 and 3 using the granule catalyst was rapidly decreased. The rapid decrease of the conversion ratio may be explained by the rapid formation of cokes in the granule type catalyst, and this phenomenon was common in both cobalt-based and nickel-based catalysts.

(56) From the results, the monolith catalyst including the components of Formula 1 showed high activity with the carbon dioxide conversion ratio of about 98% in the reforming reaction of methane and carbon dioxide and high stability with less carbon deposition when compared to the granule type molded catalyst.

(57) TABLE-US-00001 TABLE 1 Catalyst Components and ratios component:Monolith CH.sub.4 CO.sub.2 X Zr Catalyst substrate conversion conversion Division Components Amount a Amount b Support Z type (weight ratio) ratio (%) ratio (%) Example 1 Co 9 10 SiO.sub.2 Monolith 1:1 93 96 Example 2 Co 9 10 Al.sub.2O.sub.3 Monolith 1:1 72 84 Example 3 Ni 9 10 SiO.sub.2 Monolith 1:1 94 98 Example 4 Ni 9 10 Al.sub.2O.sub.3 Monolith 1:1 75 90 Comparative Co 9 10 SiO.sub.2 Granule — 72 80 Example 1 Comparative Co 9 10 Al.sub.2O.sub.3 Granule — 30 43 Example 2 Comparative Ni 9 10 SiO.sub.2 Granule — 77 84 Example 3 Comparative Ni 9 10 Al.sub.2O.sub.3 Granule — 47 60 Example 4 Comparative Ni 9 10 SiO.sub.2 Monolith 0.8:1   80 88 Example 5 Comparative Ni 9 10 SiO.sub.2 Monolith 1.2:1   85 91 Example 6 In a(X) − b(Zr)/Z, a and b represent parts by weight of active metal X and Zr relative to 100 parts by weight of a support Z.