KR101577432B1 - A platinum-based metal composite catalyst for aqueous phase reforming reaction of polyols, using mesoporous carbon carrier and manufacturing method of the same - Google Patents

Abstract

The present invention relates to a catalyst for an aqueous reforming reaction for producing hydrogen from oxygen-containing hydrocarbons, characterized in that a composite metal composed of platinum, iron and manganese is impregnated into the mesoporous carbon carrier as an active material. The catalyst for an aqueous reforming reaction for producing hydrogen from oxygen-containing hydrocarbons according to the present invention is characterized in that a mesoporous carbon support having increased specific surface area and pore volume is activated by treating spherical activated carbon with a carrier, It is excellent and easy to fill in the fixed bed reactor and uniformly fillable. In addition, the active material uses a composite metal in which iron and manganese are simultaneously contained in platinum. Accordingly, it is possible to solve the problem of excessive use of platinum, which is a typical noble metal conventionally used, There is an effect of exhibiting high efficiency and long life in the production of hydrogen through hydrogen.

Description

FIELD OF THE INVENTION The present invention relates to a catalyst for impregnating a mesoporous carbon carrier with a platinum-based composite metal for preparing hydrogen from an oxygen-containing hydrocarbon and a process for producing the same, and manufacturing method of the same}

The present invention relates to a catalyst impregnated with a platinum based composite metal on a mesoporous carbon carrier for hydrogen production by an aeration reforming reaction from an oxygen-containing hydrocarbon and a process for producing the same.

The water reforming reaction selectively produces hydrogen from polyols (glycerol, sorbitol, xylitol, etc.) which are derived from cellulose and hemicellulose, which are derived from biomass, and are various oxygenated hydrocarbons in aqueous solution . This aquatic reforming reaction was first proposed by JA Dumesic, Professor, USA (RD Cortright, RR Davda and JA Dumesic, Nature, 418 (2002) 964-967, JW Shabaker, GW Huber, RR Davda, RD Cortright, JA Dumesic, Catal. Lett. 88 (2003) 1-8), and many research groups are currently conducting research with interest in this response (HJ Park, H.-D. Kim, T Kim, K.-E. Jeong, H.-J. Chae, S.-Y. Jeong, Y.-M. Chung, Y.-K. Park and C.-U. Kim, ChemSusChem, 5 (2012) 629-633, Yong Guo, Xiaohui Liu, Muhammad Usman Azmat, Wenjie Xu, Jiawen Ren, Yanqin Wang, Guanzhong Lu., International Journal of Hydrogen Energy 37 (2012) 227-234, G. Wen, Y. Xu, H. Ma, Z. Xu, Z. Tian, Int. J. Hydrogen Energy. 33 (2008) 6657-6666).

In order to increase the selectivity of hydrogen in the production of hydrogen from deoxygenated hydrocarbons by the water reforming reaction, the carbon-carbon cleavage reaction must be maximized on the active catalytic metal surface, while the carbon- - The Tropsch reaction requires the selection of appropriate catalysts to control and the control of reaction parameters. Therefore, studies have been conducted on the activity of catalysts related to the active metal components, the feedstock to be fed, reaction conditions, and the catalyst carrier, and on the selectivity of hydrogen.

In recent years, metal oxides such as Al ₂ O ₃ , ZrO ₂ , SiO ₂ , CeO ₂ , ZnO, TiO ₂ and the like have been mainly used as a catalyst carrier in powder form. The reaction activity is drastically lowered in the aqueous reforming reaction because the pore is collapsed by the sintering of the catalyst carrier under the condition or the phase transition occurs in the form of reducing the specific surface area of the carrier in a wide range of meta stable phase Lt; / RTI > Therefore, a porous carrier having excellent hydrothermal stability during the reaction has been required. It is required that a porous carbon carrier having a large surface area, suitable pore volume, and mechanical and chemical stability capable of dispersing the active metal component to be impregnated and promoting the reaction in a liquid phase Have been developed, and many studies have been made on this.

However, the carriers used up to now are mostly in the form of powder in the form of micro-sized or nano-sized. Most of the reforming reaction is carried out in the fixed-bed reactor, and this powder type catalyst is suitable for laboratory catalyst screening Thus, there is a limitation in using such a powder type catalyst for a bench-scale and pilot-scale study in which the amount of the catalyst is several tens or hundreds of times that of the laboratory amount. Therefore, it must be molded over a certain size. That is, when a catalyst in the form of powder is used in a fixed-bed catalytic reactor, channeling phenomenon, which is a phenomenon in which a reactant flows through only one of the catalyst layers when the reactant passes through the catalyst layer, may occur. There is an increasing problem.

Therefore, since the catalyst has to be used as a forming catalyst which is granulated to a certain size or more, there is no commercial approach to the afore-mentioned aqueous reforming reaction. Therefore, prior studies and techniques using such a forming catalyst in a large amount are hardly known.

As an example of the application of the shaping catalyst, Korean Patent Laid-open No. 10-2011-0052570 discloses a method for producing a spherical shaped carbon having a commercially available granular silica bead form and a pore structure by impregnating spherical shaped carbon having a three- And a method for reforming oxygen-containing compounds using a catalyst is proposed. The carrier used in the above method is advantageous in that the reaction activity can be maintained at a very high level in a water phase reforming reaction which is a liquid phase reaction with a carbon carrier having mesopores having a three-dimensional structure. However, the step of impregnating the carbon precursor with the commercial silica as the template in the production of the carbon carrier, followed by drying and carbonization to obtain a silica / carbon composite, followed by removal of the silica from the carbon using hydrofluoric acid (HF) Since the production method is very complicated in several steps and hydrofluoric acid which is a super strong acid is used in manufacturing, there is a risk of exposure due to the handling of hydrofluoric acid, which is difficult to handle, and in particular, There is a limitation that it can cause environmental problems because it must be used excessively.

From the aspect of the active material to be impregnated in such a carbon carrier, it is known that any of the known impregnable active ingredients can be used either as a transition metal of group VIIIB or as a transition metal of group VIII. In particular, , Which is known to exhibit the best activity in terms of the conversion of oxygen-containing hydrocarbons, hydrogen selectivity and hydrogen production rate. However, the amount of platinum used in such an aqueous reforming reaction is usually in the range of 5 to 10% by weight based on the carrier, and thus the catalyst price is a big problem (WO 2007-075476, 10-2011-0052570).

Therefore, Korean Patent Laid-Open No. 10-2010-0029421 discloses a method of reducing CMK-3, which is a mesoporous carbon carrier in the form of powder, by adding platinum to rhenium, rhodium, iron, Cobalt and the like are added to the aqueous reforming reaction. Reaction activity is similar to platinum in terms of reaction activity. However, rhenium and rhodium are noble metals, which are similar to platinum, and iron and cobalt are low in value but have not significantly increased activity compared with platinum.

Accordingly, the present inventors have been studying a catalyst for an aquatic reforming reaction for producing hydrogen from an oxygen-containing hydrocarbon, in order to use a mesoporous carbon carrier as a carbon carrier and impart a selectivity to the mesoporous carbon carrier As the active material, there has been developed a catalyst impregnated with a composite metal containing iron and manganese based on platinum, thereby solving the problem of excessive use of platinum as a noble metal, confirming excellent catalytic activity, Completed.

Patent Document 1: Korean Patent Publication No. 2008-0078911 Patent Document 2: WO 2007-075476 Patent Document 3: Korea Patent Publication No. 2011-0109624 Patent Document 4: Korean Patent Publication No. 10-2011-0052570

Non-Patent Document 1: J.W. Shabaker, G.W. Huber, R.R. Davda, R.D. Cortright, J.A. Dumesic, Catal. Lett. 88 (2003) 1-8 Non-Patent Document 2: X. Wang, N. Li, L.D. Pfefferle, G.L. Haller, Catal. Today. 146 (2009) 160-165 Non-Patent Document 3: H.J. Park, H.-D. Kim, T.-W. Kim, K.-E. Jeong, H.-J. Chae, S.-Y. Jeong, Y.-M. Chung, Y.-K. Park and C.-U. Kim, ChemSus Chem, 5 (2012) 629-633 Non-Patent Document 4: Yong Guo, Xiaohui Liu, Muhammad Usman Azmat, Wenjie Xu, Jiawen Ren, Yanqin Wang, Guanzhong Lu., International Journal of Hydrogen Energy 37 (2012) 227-234 Non-Patent Document 5: G. Wen, Y. Xu, H. Ma, Z. Xu, Z. Tian, Int. J. Hydrogen Energy. 33 (2008) 6657-6666

An object of the present invention is to provide a catalyst impregnated with a platinum based composite metal on a mesoporous carbon carrier for hydrogen production by an aquatic reforming reaction from an oxygen-containing hydrocarbon and a process for producing the same.

In order to achieve the above object,

The present invention provides a catalyst for an aqueous reforming reaction for producing hydrogen from oxygen-containing hydrocarbons, characterized in that a composite metal consisting of platinum, iron and manganese is impregnated with an active substance in a mesoporous carbon carrier.

In addition,

Preparing a mesoporous carbon support and mixing it with an organic solvent to prepare a mixed solution (step 1); And

(Step 2) of injecting a platinum precursor, an iron precursor, and a manganese precursor into the mixed solution prepared in step 1 to impregnate the mesoporous carbon carrier with an active material (step 2). A method for producing a catalyst for reaction is provided.

Further,

There is provided a process for producing hydrogen from an oxygen-containing hydrocarbon through an aquatic reforming reaction using the above-mentioned catalyst for a water-reforming reaction.

The catalyst for an aqueous reforming reaction for producing hydrogen from oxygen-containing hydrocarbons according to the present invention is characterized in that a mesoporous carbon support having increased specific surface area and pore volume is activated by treating spherical activated carbon with a carrier, It is excellent and easy to fill in the fixed bed reactor and uniformly fillable. In addition, the active material uses a composite metal in which iron and manganese are simultaneously contained in platinum. Accordingly, it is possible to solve the problem of excessive use of platinum, which is a typical noble metal conventionally used, There is an effect of exhibiting high efficiency and long life in the production of hydrogen through hydrogen.

1 is a photograph of a catalyst for aquatic reforming reaction prepared in Example 1 according to the present invention by a scanning electron microscope (SEM)
FIG. 2 is a graph showing the rate of hydrogen production according to the reaction time in the aquatic reforming reaction of the aqueous reforming catalyst prepared in Example 1 and Comparative Example 1 according to the present invention.

The present invention

The present invention provides a catalyst for an aqueous reforming reaction for producing hydrogen from oxygen-containing hydrocarbons, characterized in that a composite metal consisting of platinum, iron and manganese is impregnated with an active substance in a mesoporous carbon carrier.

Hereinafter, the catalyst for aqueous reforming reaction for producing hydrogen from the oxygen-containing hydrocarbon according to the present invention will be described in detail.

The catalyst for an aqueous reforming reaction for producing hydrogen from oxygen-containing hydrocarbons according to the present invention is a water-reforming catalyst in which a composite metal consisting of platinum, iron and manganese is impregnated with an active substance as a mesoporous carbon carrier, Iron and manganese, which are low in price, are used together with the above platinum, without using only platinum, which is an active ingredient mainly used in the reaction, and the catalyst is greatly reduced in price and the catalytic activity of platinum is also increased.

In the catalyst for an aqueous reforming reaction for producing hydrogen from an oxygen-containing hydrocarbon according to the present invention, the mesoporous carbon support is preferably a spherical granular activated carbon support having mesopores.

The spherical granular activated carbon carrier may be spherical shaped activated carbon. The spherical granular activated carbon may be activated to increase the specific surface area to form a mesoporous structure.

The spherical granular activated carbon carrier preferably has a diameter of 0.3 to 2.0 mm. If the diameter of the spherical granular activated carbon carrier is less than 0.3 mm, it is difficult to fill the catalyst including the support in the fixed bed reactor and channeling phenomenon occurs in the catalyst layer. When the diameter exceeds 2.0 mm, There is a problem that the amount of the active material to be impregnated is insufficient and the activity of the catalyst is deteriorated.

As described above, the spherical granular activated carbon support having mesopores can be usefully used as a support for an aquatic reforming catalyst. Specifically, the aqueous reforming reaction is mainly carried out in a fixed-bed reactor. Since the particle size of the catalyst for the afore-mentioned reforming reaction is spherical and has a diameter of 0.3 to 2.0 mm, the catalyst can be easily filled in the fixed bed reactor , The channeling phenomenon occurring in the catalyst layer, which is a problem in filling the particulate particles in the form of powder particles, is remarkably reduced, and the problem that the pressure due to the particulate filling is greatly increased can be solved.

That is, the above-described problems are essentially accompanied by the application of powder particles to a reactor having a large capacity on a bench scale and a pilot scale. The catalyst for a water modification reaction according to the present invention can solve this problem, Due to the impregnation of a suitable active material, high efficiency and long life can be exhibited in the production of hydrogen by a water reforming reaction.

The mesoporous carbon support preferably has a specific surface area of 1,300 to 2,500 m ² / g, more preferably 1,500 to 2,000 m ² / g, Is most preferable. If the specific surface area of the mesoporous carbon support is less than 1,300 m ² / g, there is a problem that the active material impregnated in the carbon support is insufficient. When the specific surface area exceeds 2,500 m ² / g, have.

In the catalyst for an aqueous reforming reaction for producing hydrogen from an oxygen-containing hydrocarbon according to the present invention, the amount of the platinum is preferably 1 to 5 parts by weight based on 100 parts by weight of the mesoporous carbon support.

The content of iron and manganese is preferably in the range of 1 to 6 in terms of molar ratio with respect to the platinum content.

As described above, the catalyst for the aquatic reforming reaction according to the present invention uses iron and manganese which are inexpensive and costly, together with the platinum, without using only platinum, which is an active ingredient mainly used in the conventional water reforming reaction, And the activity of the catalytic reaction relative to platinum can also be increased.

In the catalyst for an aqueous reforming reaction for producing hydrogen from oxygen-containing hydrocarbons according to the present invention, the oxygen-containing hydrocarbon may be ethylene glycol, glycerol, propylene glycol, sorbitol, sucrose, sugar, sugar alcohol and xylitol.

In addition,

Preparing a mesoporous carbon support and mixing it with an organic solvent to prepare a mixed solution (step 1); And

(Step 2) of injecting a platinum precursor, an iron precursor, and a manganese precursor into the mixed solution prepared in step 1 to impregnate the mesoporous carbon carrier with an active material (step 2). A method for producing a catalyst for reaction is provided.

Hereinafter, a method for preparing a catalyst for an aquatic reforming reaction for producing hydrogen from an oxygen-containing hydrocarbon according to the present invention will be described in detail.

First, in the method of preparing a catalyst for an aquatic reforming reaction for producing hydrogen from the deoxygenated hydrocarbon according to the present invention, step 1 is a step of preparing a mesoporous carbon support and mixing it with an organic solvent to prepare a mixed solution.

In the step 1, a mesoporous carbon support is prepared to impregnate the active material, and the prepared mesoporous carbon support is mixed with an organic solvent to prepare a mixed solution.

Specifically, in preparing the mesoporous carbon support in step 1,

(Step a) by using a spherical granular activated carbon carrier at a temperature of 800 to 1000 DEG C for 6 to 10 hours under a mixed gas flow of water vapor and depressurized gas.

In order to prepare a catalyst suitable for an aquatic reforming reaction for producing hydrogen from oxygen-containing hydrocarbons, spherical shaped shaped activated carbon can be used as a carrier, and the spherical activated carbon is activated to increase the specific surface area It is preferable to form and use a mesoporous structure.

At this time, it is preferable that the spherical granular activated carbon carrier of step a has a diameter of 0.3 to 2.0 mm. If the diameter of the spherical granular activated carbon support in step (a) is less than 0.3 mm, it is difficult to fill the catalyst including the support in the fixed bed reactor, and channeling phenomenon occurs in the catalyst layer. , There is a problem that the specific surface area is small and the amount of the active material to be impregnated is insufficient, thereby deteriorating the activity of the catalyst.

If the activation temperature is lower than 800 ° C or the activation time is less than 6 hours in the step a, sufficient activation is not achieved and the specific surface area and pore volume can not be increased. If the activation temperature exceeds 1000 ° C When the activation time exceeds 10 hours, too much activation takes place, resulting in a decrease in the strength of the produced catalyst and a drastic decrease in the reaction activity.

As described above, the spherical granular activated carbon carrier having mesoporosity through the activation treatment in step a can be usefully used as a carrier of an aquatic reforming reaction catalyst. Specifically, the aqueous reforming reaction is mainly carried out in a fixed-bed reactor. Since the particle size of the catalyst for the afore-mentioned reforming reaction is spherical and has a diameter of 0.3 to 2.0 mm, the catalyst can be easily filled in the fixed bed reactor , The channeling phenomenon occurring in the catalyst layer, which is a problem in filling the particulate particles in the form of powder particles, is remarkably reduced, and the problem that the pressure due to the particulate filling is greatly increased can be solved.

That is, the above-described problems are essentially accompanied by the application of powder particles to a reactor having a large capacity on a bench scale and a pilot scale. The catalyst for a water modification reaction according to the present invention can solve this problem, Due to the impregnation of a suitable active material, high efficiency and long life can be exhibited in the production of hydrogen by a water reforming reaction.

The mesoporous carbon support of step 1 prepared as described above preferably has a specific surface area of 1,300 to 2,500 m ² / g, more preferably 1,500 to 2,000 m ² / g. If the specific surface area of the mesoporous carbon support is less than 1,300 m ² / g in the step 1, there is a problem that the active material impregnated in the carbon support is insufficient. When the specific surface area exceeds 2,500 m ² / g, There is an insufficient problem.

The organic solvent in step 1 may be an organic solvent that does not dissolve the carbon carrier. For example, acetone may be used.

Next, in the method of preparing a catalyst for an aquatic reforming reaction for producing hydrogen from an oxygen-containing hydrocarbon according to the present invention, Step 2 is a step of injecting a platinum precursor, an iron precursor and a manganese precursor into the mixed solution prepared in Step 1 Impregnating the mesoporous carbon carrier with the active material.

In the step 2, in order to impregnate the mesoporous carbon support prepared in the step 1 with the active material, a precursor of platinum, iron and manganese, which are active materials, is injected into the mixed solution containing the mesoporous carbon support prepared in the step 1 do.

Platinum, which is a typical active material used conventionally, is known as the most suitable metal in terms of activity, but it is not economical due to excessive use such as exceeding 5 parts by weight based on the weight of the carbon support. Therefore, in the present invention, a composite metal containing both iron and manganese, which are metal components in the platinum component, is used. When the mesoporous carbon carrier is impregnated with the active material, the active material is well dispersed to form an alloy, can do.

In this case, the impregnation of the active material in the step 2 may be performed by an impregnation method commonly used in the related art, but the incipient wetness method is preferable because it can uniformly disperse when the metal is dispersed in the carrier Do. In the initial wetting method, a solution in which a precursor of an active material is dissolved in a solvent is applied to a carrier, and in the case where the active material is a composite metal, a solution in which each precursor of the metal is dissolved in one solvent may be used .

For example, in the case of the active substance platinum, non-limiting examples of the platinum precursor include hexachloroplatinic acid (H ₂ PtCl ₆ 9H ₂ O), platinum ammonium chloride (Pt (NH ₃ ) ₄ Cl ₂ ), Platinum ammonium nitrate (Pt (NH ₃ ) ₄ (NO ₃ ) ₂ ), and the like.

Iron (III) nitrate nonahydrate, Fe (NO ₃ ) ₃ 9H ₂ O), manganese (II) nitrate, and iron (III) nitrate are used as iron and manganese precursors in the case of iron and manganese, Manganese (II) nitrate hydrate, and Mn (NO ₃ ) ₂ x H ₂ O).

Further, in step 2, the platinum precursor is preferably injected in an amount of 1 to 5 parts by weight based on 100 parts by weight of the mesoporous carbon support. If the platinum precursor is injected so that the platinum content is less than 1 part by weight with respect to 100 parts by weight of the mesoporous carbon support in the step 2, the loading amount of the active material is too small, When the catalyst is added in an amount exceeding 5 parts by weight, there is a problem that the active materials are mutually aggregated and the catalytic activity is not higher than the amount of expensive noble metal catalyst.

In the step 2, the platinum precursor, the iron precursor, and the manganese precursor are preferably injected such that iron and manganese in the active material have a molar ratio of 1 to 6, respectively, with respect to the platinum content. If the platinum precursor, the iron precursor and the manganese precursor in the step 2 are less than the molar ratio of iron and manganese to the platinum content in the active material, the impregnation amount of iron or manganese is small and the reaction activity is not affected, , Formation of platinum and alloys becomes difficult, and the dispersibility of the impregnated active material is reduced, thereby deteriorating reactivity.

As described above, the catalyst for the aquatic reforming reaction according to the present invention uses iron and manganese which are inexpensive and costly, together with the platinum, without using only platinum, which is an active ingredient mainly used in the conventional water reforming reaction, And the activity of the catalytic reaction relative to platinum can also be increased.

Further,

There is provided a process for producing hydrogen from an oxygen-containing hydrocarbon through an aquatic reforming reaction using the above-mentioned catalyst for a water-reforming reaction.

As a concrete example, the catalyst for water reforming reaction according to the present invention is filled in a fixed bed reactor, and then the catalyst for a water reforming reaction is reduced at a temperature of 200 to 400 ° C for 2 to 12 hours. Thereafter, hydrogen can be produced by supplying an impure oxygen hydrocarbon to the fixed bed reactor at a proper flow rate and allowing the reaction to proceed.

Herein, the oxygen-containing hydrocarbon may be variously used. Examples of the oxygen-containing hydrocarbon include ethylene glycol, glycerol, propylene glycol, sorbitol, sucrose, sugar, alcohol and xylitol But is not limited thereto.

The reaction for producing hydrogen from the oxygen-containing hydrocarbon may be performed at a temperature ranging from 200 to 400 ° C. When the reaction temperature is lower than 200 ° C, the reaction activity is too low. When the reaction temperature is higher than 400 ° C, the yield of hydrogen is lowered.

Further, the reaction for producing hydrogen from the oxygen-containing hydrocarbon is preferably performed at a rate of 0.1 to 100 cc / gcat.min Range And may be performed at a weight hour space velocity (WHSV).

Hereinafter, the present invention will be described in detail with reference to the following examples and experimental examples.

It should be noted, however, that the following examples and experimental examples are illustrative of the present invention, but the scope of the invention is not limited by the examples and the experimental examples.

≪ Preparation Example 1 &

The mesoporous carbon support was prepared by performing activation treatment under a mixed gas flow condition in which spherical shaped activated carbon (MP-AC, Japanese kureha spherical shaped activated carbon) was mixed with nitrogen and water vapor at a molar ratio of 1: 1. At this time, the activation temperature is 900 DEG C and the activation time is 6 hours.

≪ Preparation Examples 2 to 7 &

Carbon support was prepared in the same manner as in Preparation Example 1 except that the activation temperature was 600 to 1,000 ° C. and the activation time was 2 to 16 hours.

The experimental conditions and physical properties (specific surface area, pore volume) of the carbon support prepared in Production Examples 1 to 7 are shown in Table 1 below.

Particle shape Activation temperature
(° C) Activation time
(time) BET specific surface area (m ² / g) Pore volume
(cm < ³ > / g) Production Example 1 rectangle 900 6 1620 0.96 Production Example 2 rectangle 900 10 1680 1.01 Production Example 3 rectangle 800 10 1680 1.01 Production Example 4 rectangle 1000 6 1680 1.01 Production Example 5 rectangle 900 2 1210 0.70 Production Example 6 rectangle 900 16 1160 1.01 Production Example 7 rectangle 600 6 1280 0.63 MP-AC rectangle - - 1208 0.56 HG-AC Rod type - - 1430 0.31

Example 1 Preparation of Catalyst for Water Reforming Reaction 1

Step 1: 36.6 g of the mesoporous carbon support prepared in Preparation Example 1 was mixed with 3 L of acetone as an organic solvent to prepare a mixed solution.

Step 2: 7.3 g of platinum precursor hexachloroplatinic acid (H ₂ PtCl ₆ 9H ₂ O, MW = 518) (Pt content: 2.93 g, 0.015 6 g (Fe content: 0.84 g, 0.015 mol) of iron precursor iron (III) nitrate nonahydrate, Fe (NO ₃ ) ₃ 9H ₂ O, MW = 3.6 g (Mn content: 0.82 g, 0.015 mol) of manganese (II) nitrate hydrate, manganese (II) nitrate hydrate, Mn (NO ₃ ) ₂ 4H ₂ O, MW = 251)

Thereafter, a catalyst for an aqueous reforming reaction in which Pt-Fe-Mn was impregnated in a mesoporous carbon support while evaporating in a rotavapor was prepared.

At this time, the final catalyst for the aquatic reforming reaction is composed of platinum in an amount of 3 parts by weight based on 100 parts by weight of the carbon support, iron and manganese based on platinum content, platinum: iron: manganese = 1 : 1: 1 (molar ratio).

≪ Example 2 > Preparation of catalyst for aqueous reforming reaction 2

A catalyst for aqueous phase reforming reaction was prepared in the same manner as in Example 1 except that the mesoporous carbon support prepared in Preparation Example 2 was used in Step 1 of Example 1 above.

≪ Example 3 > Preparation of catalyst for aqueous reforming reaction 3

A catalyst for aqueous phase reforming reaction was prepared in the same manner as in Example 1 except that the mesoporous carbon support prepared in Preparation Example 3 was used in Step 1 of Example 1 above.

Example 4 Preparation of Catalyst for Water Reforming Reaction 4

A catalyst for aqueous phase reforming reaction was prepared in the same manner as in Example 1, except that the mesoporous carbon support prepared in Preparation Example 4 was used in Step 1 of Example 1 above.

Example 5 Preparation of Catalyst for Water Reforming Reaction 5

A catalyst for aqueous reforming reaction was prepared in the same manner as in Example 1 except that platinum precursor, iron precursor and manganese precursor were injected in different contents in Step 2 of Example 1 above.

At this time, the final catalyst for aquatic reforming reaction is composed of platinum in an amount of 1 part by weight based on 100 parts by weight of the carbon support, iron and manganese based on platinum content, platinum: iron: manganese = 1 : 1: 1 (molar ratio).

≪ Example 6 > Preparation of catalyst for aqueous reforming reaction 6

A catalyst for aqueous reforming reaction was prepared in the same manner as in Example 1 except that platinum precursor, iron precursor and manganese precursor were injected in different contents in Step 2 of Example 1 above.

At this time, the final catalyst for aqueous reforming reaction is composed of platinum in an amount of 5 parts by weight based on 100 parts by weight of the carbon support, iron and manganese based on platinum content, platinum: iron: manganese = 1 : 1: 1 (molar ratio).

Example 7 Preparation of Catalyst for Water Reforming Reaction 7

A catalyst for aqueous reforming reaction was prepared in the same manner as in Example 1 except that platinum precursor, iron precursor and manganese precursor were injected in different contents in Step 2 of Example 1 above.

At this time, the final catalyst for the aquatic reforming reaction is composed of platinum in an amount of 3 parts by weight based on 100 parts by weight of the carbon support, iron and manganese based on platinum content, platinum: iron: manganese = 1 : 2: 2 (molar ratio).

≪ Example 8 > Preparation of catalyst for aqueous reforming reaction 8

A catalyst for aqueous reforming reaction was prepared in the same manner as in Example 1 except that platinum precursor, iron precursor and manganese precursor were injected in different contents in Step 2 of Example 1 above.

At this time, the final catalyst for the aquatic reforming reaction is composed of platinum in an amount of 3 parts by weight based on 100 parts by weight of the carbon support, iron and manganese based on platinum content, platinum: iron: manganese = 1 : 1: 4 (molar ratio).

≪ Comparative Example 1 &

A catalyst for an aqueous reforming reaction was prepared in the same manner as in Example 1 except that the carbon support prepared in Preparation Example 5 was used in Step 1 of Example 1.

≪ Comparative Example 2 &

A catalyst for aqueous reforming reaction was prepared in the same manner as in Example 1, except that the carbon support prepared in Preparation Example 6 was used in Step 1 of Example 1.

≪ Comparative Example 3 &

A catalyst for aqueous reforming reaction was prepared in the same manner as in Example 1 except that the carbon support prepared in Preparation Example 7 was used in Step 1 of Example 1.

≪ Comparative Example 4 &

A catalyst for aqueous reforming reaction was prepared in the same manner as in Example 1 except that platinum precursor, iron precursor and manganese precursor were injected in different contents in Step 2 of Example 1 above.

At this time, the final catalyst for aqueous reforming reaction is composed of platinum in an amount of 0.1 part by weight based on 100 parts by weight of the carbon support, iron and manganese in terms of platinum, iron: manganese = 1 : 1: 1 (molar ratio).

≪ Comparative Example 5 &

A catalyst for aqueous reforming reaction was prepared in the same manner as in Example 1 except that platinum precursor, iron precursor and manganese precursor were injected in different contents in Step 2 of Example 1 above.

At this time, the finally prepared catalyst for the aquatic reforming reaction contains platinum in an amount of 10 parts by weight based on 100 parts by weight of the carbon support, iron and manganese based on platinum content, platinum: iron: manganese = 1 : 1: 1 (molar ratio).

≪ Comparative Example 6 >

A catalyst for aqueous reforming reaction was prepared in the same manner as in Example 1 except that platinum precursor, iron precursor and manganese precursor were injected in different contents in Step 2 of Example 1 above.

At this time, the final catalyst for the aquatic reforming reaction is composed of platinum in an amount of 3 parts by weight based on 100 parts by weight of the carbon support, iron and manganese based on platinum content, platinum: iron: manganese = 1 : 10: 7 (molar ratio).

≪ Comparative Example 7 &

A catalyst for aqueous reforming reaction was prepared in the same manner as in Example 1 except that platinum precursor, iron precursor and manganese precursor were injected in different contents in Step 2 of Example 1 above.

At this time, the final catalyst for the aquatic reforming reaction is composed of platinum in an amount of 3 parts by weight based on 100 parts by weight of the carbon support, iron and manganese based on platinum content, platinum: iron: manganese = 1 : 0.1: 0.1 (molar ratio).

≪ Comparative Example 8 >

A catalyst for aqueous phase reforming reaction was prepared in the same manner as in Example 1 except that spherical shaped activated carbon (MP-AC, Japanese kureha spherical shaped activated carbon) was used as a carrier in step 1 of Example 1 above .

≪ Comparative Example 9 &

The procedure of Example 1 was repeated except that the rod-shaped molded activated carbon (HG-AC, Korea-Japan Greentec rod-shaped shaped activated carbon) was used as a carrier in step 1 of Example 1, Catalyst.

≪ Comparative Example 10 &

The procedure of Example 1 was repeated except that the iron precursor and the manganese precursor were not injected in the step 2 of Example 1 to prepare a catalyst for an aqueous reforming reaction.

At this time, the finally prepared catalyst for the water-reforming reaction contains 3 parts by weight of platinum in the active material with respect to 100 parts by weight of the carbon support.

≪ Comparative Example 11 &

12.17 g (Pt content: 4.88 g, 0.025 mol) of hexachloroplatinic acid (H ₂ PtCl ₆ 9 H ₂ O, MW = 518) was injected as a platinum precursor in Step 2 of Example 1, Except that the precursor and the manganese precursor were not injected into the reaction system.

At this time, the finally prepared catalyst for aqueous reforming reaction contains 5 parts by weight of platinum in the active material, based on 100 parts by weight of the carbon support.

<Experimental Example 1> Scanning electron microscopic observation

In order to confirm the shape of the catalyst for aqueous phase reforming reaction according to the present invention, the catalyst for aqueous phase reforming reaction prepared in Example 1 was observed with a scanning electron microscope (SEM) .

As shown in Fig. 1, the shape of the catalyst for aqueous phase reforming according to the present invention, which was spherical, was found to be about 1 mm in diameter.

EXPERIMENTAL EXAMPLE 2 Evaluation of Catalyst Performance by Aqueous Modification Reaction 1

In order to evaluate the catalytic performance of the catalyst for an aquatic reforming reaction according to the present invention, the catalysts for aquatic reforming reaction prepared in Examples 1 to 8 and Comparative Examples 1 to 11 were tested for hydrogen yield and hydrogen The production rate was measured.

Specifically, a fixed bed reactor having a diameter of 1.0 inch and a length of 60 cm was mounted in a fixed bed catalytic reaction system to perform an austenitic reforming reaction. The amount of catalyst used was 30 g. After the catalyst was reduced for 6 hours at a temperature of 260 ° C under hydrogen flow prior to the reaction, a 10 wt% aqueous solution of ethylene glycol was added to the whole aqueous solution at 10 cc / min To the reactor. As the other reaction conditions, the weight hour space velocity (WHSV) was fixed to 10 cc / g cat.min and the aqueous reforming reaction was carried out from the polyol aqueous solution while keeping the temperature and pressure at 250 ° C. and 45 atm. &Lt; / RTI &gt;

The gaseous products produced after the water reforming reaction were GC-TCD and FID equipped with carboxen 1000 packed column and GS-GASPRO microporous column, respectively, using nitrogen as an internal standard. . The yield of hydrogen from the polyol on the basis of the carbon component in the reaction material was calculated by using the following Equation 1 and the rate of hydrogen production was determined by quantifying the amount of hydrogen detected in the TCD of GC based on the internal standard substance of nitrogen The rate of generation of hydrogen per gram of post catalyst was calculated and the results are shown in Table 2 below.

In this case, for example, in the case of ethylene glycol, the reaction formula is (CH ₂ ) ₂ (OH) ₂ + 2H ₂ O → 2CO ₂ + 5H ₂ to be.

[Equation 1]

division
carbon
carrier
Kinds Carbon carrier contrast
Platinum content The composition (molar ratio) of iron and manganese relative to impregnated platinum Reaction activity results platinum iron manganese Of hydrogen
yield(%) Hydrogen production rate
(cc / gcat.min) Example 1 Production Example 1 3 parts by weight 1.0 1.0 1.0 61.3 44.1 Example 2 Production Example 2 3 parts by weight 1.0 1.0 1.0 69.2 45.1 Example 3 Production Example 3 3 parts by weight 1.0 1.0 1.0 62.3 41.4 Example 4 Production Example 4 3 parts by weight 1.0 1.0 1.0 58.3 45.7 Example 5 Production Example 1 1 part by weight 1.0 1.0 1.0 51.3 47.1 Example 6 Production Example 1 5 parts by weight 1.0 1.0 1.0 59.2 48.1 Example 7 Production Example 1 3 parts by weight 1.0 2.0 2.0 52.3 41.4 Example 8 Production Example 1 3 parts by weight 1.0 1.0 4.0 58.3 25.7 Comparative Example 1 Production Example 5 3 parts by weight 1.0 1.0 1.0 47.1 27.3 Comparative Example 2 Production Example 6 3 parts by weight 1.0 1.0 1.0 49.7 28.5 Comparative Example 3 Production Example 7 3 parts by weight 1.0 1.0 1.0 42.7 21.5 Comparative Example 4 Production Example 1 0.1 part by weight 1.0 1.0 1.0 48.6 25.3 Comparative Example 5 Production Example 1 10 parts by weight 1.0 1.0 1.0 41.5 27.3 Comparative Example 6 Production Example 1 3 parts by weight 1.0 10 7.0 44.4 28.2 Comparative Example 7 Production Example 1 3 parts by weight 1.0 0.1 0.1 42.3 21.1 Comparative Example 8 MP-AC 3 parts by weight 1.0 1.0 1.0 48.6 25.3 Comparative Example 9 HG-AC 3 parts by weight 1.0 1.0 1.0 34.7 25.4 Comparative Example 10 Production Example 1 3 parts by weight - - - 41.9 34.2 Comparative Example 11 Production Example 1 5 parts by weight - - - 37.5 30.7

As shown in Table 2, although Examples 1 to 4 and Comparative Examples 1 to 3 were examined, although the same amount of the active material was loaded, the yield of hydrogen and the rate of hydrogen generation differed depending on the type of the carbon carrier Can be confirmed.

Specifically, in the case of Comparative Examples 1 to 3, which are catalysts for water-reforming reaction produced using a carbon carrier having no mesoporosity, the yield of hydrogen was 42.7 to 49.7%, the rate of hydrogen generation was 21.5 to 28.5 cc / gcat .min. &lt; / RTI &gt; On the other hand, in Examples 1 to 4, which are catalysts for aquatic reforming reaction produced using the mesoporous carbon support according to the present invention, the yield of hydrogen was 58.3 to 69.2%, the rate of hydrogen generation was 41.4 to 45.7 cc / gcat .min. &lt; / RTI &gt;

In the case of controlling the content of platinum or the content of iron and manganese in the case of Example 1, Examples 5 to 8 and Comparative Examples 4 to 7, although the same mesoporous carrier was used, It can be confirmed that the yield of hydrogen and the production rate of hydrogen are different.

Specifically, in the case of Comparative Example 4 and Comparative Example 5 in which the content of platinum was 0.1 or 10 parts by weight based on 100 parts by weight of the carbon carrier in the active material, the yields of hydrogen were 48.6 and 41.5%, respectively, and the hydrogen production rates were 25.3 And 27.3 cc / gcat.min, while in the case of Examples 1, 5 and 6 in which the content of platinum is 1 to 5 parts by weight relative to 100 parts by weight of the carbonaceous carrier in the active material, The yield of hydrogen was 51.3 to 61.3%, and the rate of hydrogen generation was 44.1 to 48.1 cc / gcat.min, which was very excellent.

In the case of Comparative Example 6 where platinum: iron: manganese = 1: 10: 7 and platinum: iron: manganese = 1: 0.1: 0.1 in molar ratio with respect to the platinum content, the yields of hydrogen were 44.4 and 42.3 %. On the other hand, in Example 1 where platinum: iron: manganese = 1: 1: 1 and platinum: iron: manganese = 1: 2: 4, the yield of hydrogen was 61.3%, 52.3% and 58.3%, respectively.

Further, in the case of Comparative Example 10 in which 3 parts by weight of the catalyst was supported on 100 parts by weight of platinum alone carbon support and Comparative Example 11 in which 5 parts by weight of catalyst was carried, the yields of hydrogen were respectively 41.9% and 37.5% Were 34.2 and 30.7 cc / gcat.min, respectively.

As described above, since the catalyst for aqueous phase reforming according to the present invention has an effect of further improving the yield of hydrogen and the rate of formation of hydrogen, it can be advantageously used as a catalyst for an aqueous reforming reaction for producing hydrogen from oxygen- Could know.

<Experimental Example 3> Evaluation of catalyst performance by aqueous reforming reaction 2

In order to evaluate the catalytic performance of the catalyst for aqueous phase reforming according to the present invention, the same experiment as in Experimental Example 2 was conducted on the catalyst for aqueous phase reforming prepared in Example 1, The yield of hydrogen and the rate of formation of hydrogen were measured. The results are shown in Table 3 below.

The type of catalyst used
The polyol used
Type of aqueous solution
Reaction activity results The yield of hydrogen
(%) Hydrogen production rate
(cc / gcat.min) Example 1 Propylene glycol 58.1 43.2 Example 1 1,3-propylene glycol 55.8 40.4 Example 1 Glycerol 50.4 38.2 Example 1 Sorbitol 51.6 36.5 Example 1 Xylitol 51.5 36.6

As shown in Table 3, Example 1, which is a catalyst for an aquatic reforming reaction in which a composite metal of platinum, iron and manganese was impregnated as an active material into a mesoporous carbon support according to the present invention, Stable hydrogen yield of more than 50% and high hydrogen production rate of 35 cc / gcat.min were confirmed.

Therefore, it was confirmed that the catalyst for aqueous modification reaction according to the present invention can be applied to various polyols in a water reforming reaction.

<Experimental Example 4> Long life test of the catalyst for aqueous reforming reaction

In order to confirm the longevity of the catalyst for aqueous reforming reaction according to the present invention, the catalyst for aeration reforming prepared in Example 1 and Comparative Example 1 was reacted with the same reactant for 900 hours under the reaction conditions, And the results are shown in Fig.

As shown in FIG. 2, in the case of Example 1 in which the mesoporous carbon support according to the present invention is a catalyst for an aquatic reforming reaction in which a composite metal of platinum, iron and manganese is impregnated with an active material as an active material, In contrast, in the case of Comparative Example 1 in which the active material is impregnated into the carbon carrier having no mesoporosity, the deactivation is steadily generated, and the hydrogen production rate tends to decrease gradually.

As described above, it was confirmed that the catalyst for aqueous phase reforming according to the present invention exhibits excellent performance even with a long life.

Claims (10)

Wherein a composite metal consisting of platinum, iron and manganese is impregnated into a spherical granular activated carbon carrier having mesopores as an active material. The catalyst for an aqueous reforming reaction for producing hydrogen from an oxygen-containing hydrocarbon.
delete The method according to claim 1,
Wherein the support has a specific surface area of 1,300 to 2,500 m ² / g. The catalyst for an aqueous reforming reaction for producing hydrogen from an oxygen-containing hydrocarbon.
The method according to claim 1,
Wherein the amount of the platinum is 1 to 5 parts by weight based on 100 parts by weight of the carrier.
The method according to claim 1,
Wherein the content of iron and manganese is in the range of 1 to 6 in molar ratio with respect to the content of platinum, respectively.
The method according to claim 1,
Wherein the oxygen-containing hydrocarbon is at least one selected from the group consisting of ethylene glycol, glycerol, propylene glycol, sorbitol, sucrose, sugar, sugar alcohol and xylitol. catalyst.
Preparing a spherical granular activated carbon carrier having mesopores and mixing with an organic solvent to prepare a mixed solution (step 1); And
(Step 2) of injecting a platinum precursor, an iron precursor, and a manganese precursor into the mixed solution prepared in step 1 to impregnate a spherical granular activated carbon carrier having mesopores with an active material (step 2). Wherein the catalyst is prepared by a method comprising the steps of:
8. The method of claim 7,
In preparation of the spherical granular activated carbon support having mesopores in the step 1,
(Step a) using a spherical granular activated carbon carrier at a temperature of 800 to 1000 DEG C for 6 to 10 hours under a mixed gas flow of water vapor and depressurized gas. Of the catalyst for an aqueous reforming reaction.
8. The method of claim 7,
Wherein the platinum precursor, the iron precursor, and the manganese precursor in the step 2 are injected such that iron and manganese in the active material have a molar ratio of 1 to 6, respectively, with respect to the platinum content. (2).
A process for producing hydrogen from an oxygen-containing hydrocarbon through an aquatic reforming reaction using the catalyst for aqueous reforming reaction according to claim 1.

Images