WO2018048236A1 - Nickel-based catalyst molded body for steam methane reforming and use thereof - Google Patents

Nickel-based catalyst molded body for steam methane reforming and use thereof Download PDF

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WO2018048236A1
WO2018048236A1 PCT/KR2017/009853 KR2017009853W WO2018048236A1 WO 2018048236 A1 WO2018048236 A1 WO 2018048236A1 KR 2017009853 W KR2017009853 W KR 2017009853W WO 2018048236 A1 WO2018048236 A1 WO 2018048236A1
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catalyst
smr
ni
steam methane
methane reforming
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PCT/KR2017/009853
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French (fr)
Korean (ko)
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이동채
조성종
민준석
최상현
김초균
안지혜
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주식회사 에코프로
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Application filed by 주식회사 에코프로 filed Critical 주식회사 에코프로
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/10Solids characterised by their surface properties or porosity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/56Manufacturing of fuel cells

Abstract

The present invention relates to a Ni-based catalyst molded body for steam methane reforming (SMR), the catalyst molded body being obtained by compression molding a catalyst powder, in which a nickel precursor is immersed in and supported on boehmite, and then firing the catalyst powder. The catalyst for SMR of the present invention, by using boehmite as a supporter, can achieve high strength through pelletization and molding and can exhibit improved reaction characteristics.

Description

Nickel-based catalyst molded body for steam methane reforming and use thereof

The present invention relates to nickel-based catalyst shaped bodies for steam methane reforming and their use.

A fuel cell is an energy conversion device that converts chemical energy of a fuel directly into electrical energy by an electrochemical reaction. In particular, a solid oxide fuel cell (SOFC) uses a solid oxide as an electrolyte and operates at high temperatures. It has three characteristics. Fuels commonly used in fuel cells include hydrocarbon raw materials and hydrogen obtained by reacting oxidants or steam in a fuel reformer. The most commonly used hydrogen production method reacts methane (CH 4 ) with steam in the presence of a catalyst. Steam methane reforming (SMR) to convert hydrogen (H 2 ), carbon monoxide (CO), and carbon dioxide (CO 2 ).

Scheme 1

CH 4 + H 2 → 3H 2 + CO; ΔH θ = 206.1 kJ / mol

Steam Methane Reforming (SMR) for hydrogen production is strongly influenced by pressure due to the increased molar number. The biggest factor that increases the reaction pressure is due to the breakage of the catalyst, in order to prevent it, a high strength catalyst must be prepared.

Currently, a pellet-type ceramic support catalyst having Ni, Ru and other active materials supported on a relatively inexpensive ceramic support is used as a steam methane reforming (SMR) catalyst for hydrogen production. However, the pellet-type ceramic support catalyst is poor in impact resistance and easily breaks, causing a differential pressure in the reactor. In addition, the steam methane reforming process is a reaction in which the number of moles of the product is greater than the number of moles of the reactant, as shown in FIG. In addition, there was a disadvantage in that the energy (force for the catalyst to be activated: temperature) is insufficient and depends on the activation energy and the amount of the catalyst.

Accordingly, attempts have been made to compression-form nickel-based alumina into pellets or beads. In particular, 2mm pellets are very small in SMR catalysts and are suitable to be filled in specially manufactured reactors. However, when manufacturing by compression molding 2mm pellets using alumina-based powder, there is a problem that can not be manufactured due to damage to the molding module.

Under this background, the present inventors have made an effort to improve the strength of the catalyst through compression molding, and as a result, when nickel is carried on the boehmite, which is a preliminary step of alumina, and then compression molding, pellets can be produced without damaging the molding module. It was confirmed that the present invention was completed.

The present invention is to provide a nickel-based catalyst compact for steam methane reforming to improve the strength of the catalyst through compression molding.

A first aspect of the present invention provides a Ni-based catalyst molded product for steam methane reforming (SMR), wherein the catalyst powder supported by impregnating boehmite with a nickel precursor is pressed and calcined.

The second aspect of the present invention

1) preparing a nickel precursor solution;

2) impregnating boehmite into the solution of step 1) to impregnate the boehmite with a nickel precursor;

3) obtaining a catalyst powder having a nickel precursor supported on boehmite; And

It provides a method for producing a Ni-based catalyst molded body for steam methane reforming, including; 4) compression molding and calcining the powder of step 3).

A third aspect of the present invention provides a reactor which simultaneously performs a steam methane reforming process (SMR) and a hydrogen separation process, and uses the Ni-based catalyst shaped body of the first aspect as a catalyst for SMR.

A fourth aspect of the present invention provides a process for producing syngas or hydrogen gas from natural gas by performing steam methane reforming (SMR) and hydrogen separation in one reactor, wherein the SMR under the Ni-based catalyst shaped body of the first aspect It provides a method for producing syngas or hydrogen gas characterized in that the process is carried out.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have attempted to prepare 2 * 3 mm pellets, 2 mm pellets or bead type catalysts in order to fill the catalyst in the membrane for hydrogen production.

Pellet-type catalysts are generally known to be suitable for vacuum extrusion molding or compression molding.

Vacuum extrusion molding is a molding method in which the catalyst is kneaded through a binder and an additive to make it viscous, and then the vacuum is applied to the module to extract a desired shape.

Vacuum extrusion molding has the advantage of forming various types of catalysts by replacing the molding module in front of the molding apparatus. However, there is a disadvantage in that the operation of finding the conditions of the dough using a binder and other additives is required.

Compression molding is a method of producing a physically desired shape through the transverse motion of the module using catalyst powder. Compression molding has an advantage in that the manufacturing method is relatively simple compared to the vacuum extrusion that requires a process of kneading the catalyst powder.

In order to prepare pellet-shaped SMR catalysts, the present inventors introduced two preparation methods, compression molding and extrusion molding, to evaluate the strength of the catalyst. As a result, as shown in FIG. 3, it was confirmed that the preparation of the MgNiAl 2 O 3 catalyst through compression molding was superior in strength of the catalyst by about 2 times or more.

Therefore, the present inventors have attempted to prepare catalyst pellets through compression molding. Compression molding of the catalyst to which alumina is added requires high strength force. In particular, when molding into a 2mm pellet form using alumina was confirmed that the molding module is not sustained and damaged.

The present inventors found that when a pellet-type Ni-based catalyst was prepared using boehmite as a support, pelletization and catalyst molding were possible without breaking the molding module, unlike using an alumina (γ-Al 2 O 3 ) support. (See Figure 2).

Furthermore, even when the Ni-based catalyst was prepared using the boehmite as a support, it was confirmed that the calcination resulted in the same crystal phase and structure as γ-Al 2 O 3 , but the specific surface area and the acid point characteristics were excellent. The improvement was confirmed.

The present invention is based on this. Accordingly, the present invention is a Ni-based catalyst compact for steam methane reforming (SMR), characterized in that the catalyst powder supported by impregnating a boehmite with a nickel precursor is pressed and calcined.

Boehmite (Boehmite) is a hydroxyl group (-OH) is one individual first Ga γ-AlO (OH) as compared to high strength, high acidity, high alumina crystal growth and (Al 2 O 3) existing in the alumina (Al 2 O 3) to be. Boehmite is a good starting material for gamma / delta / theta / alpha Al 2 O 3 and has excellent thermal and structural properties. Since boehmite has various Al 2 O 3 phases according to heat treatment conditions and methods, it is possible to prepare an excellent Ni / Al 2 O 3 catalyst for SMR reaction through such adjustment.

In particular, boehmite is phase-converted to gamma alumina (γ-Al 2 O 3 ) at a high temperature of 500 ° C. or higher.

Boehmite can use a powder or a granule.

In the Ni-based catalyst for steam methane reforming (SMR) of the present invention, the boehmite support is immersed in a precursor solution in which a nickel precursor and optionally a promoter metal supply precursor are dissolved in a solvent according to the impregnation method to impregnate the catalyst precursor in the boehmite support. After compression molding, drying and firing can be prepared.

The nickel precursor may be in the form of nitrate (NO 3 ), acetate salt, halide salt (F, Cl, Br, I) or a mixture thereof, but is not limited thereto.

Preferably, the nickel precursor is selected from the group consisting of Nickel Nitrate Hexahydrate, Nickel Chloride Hexahydrate, Nickel Acetate Tetrahydrate, and Nickel Bromide Hydrate. It may be one or more selected.

More preferably, the nickel precursor is nickel, titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), aluminum (Al) ), Magnesium (Mg), zirconium (Zr) and boron (B) may be a composite precursor consisting of one or more metals selected from the group. Most preferably, the nickel-containing composite precursor comprises nickel and at least one metal selected from the group consisting of chromium (Cr), copper (Cu), aluminum (Al), magnesium (Mg) and boron (B). It may be a precursor.

Ni-based catalyst for steam methane reforming (SMR) of the present invention may be a Ni content of 20 to 40% by weight.

Meanwhile, a cocatalyst precursor may be added to the nickel precursor-containing solution as an additive.

Non-limiting examples of cocatalysts impregnated with Ni include Ag, La, Mg, Pd, Ru, but Ag has a low methane conversion of less than 80% at 600 ° C., and Ru and Ag have a methane conversion rate of The hydrogen production amount was very low.

Preferably at least one selected promoter from the group consisting of La, Mg and Pd may be added.

In general, coke produced in the reforming reaction deteriorates the catalytic activity and causes side effects of increasing the differential pressure in the reactor that breaks down the catalyst, so it is very important to suppress coke formation. Therefore, the Ni-based catalyst for SMR according to the present invention may include calcium oxide as a catalyst enhancer. Since calcium oxide has a strong basicity, carbon dioxide is strongly adsorbed, and the adsorbed carbon dioxide reacts with carbon produced in the catalyst and is converted into carbon monoxide. That is, since it assists the gasification of the coke or the coke precursor, it serves to suppress coke formation on the catalyst.

Examples of the precursor solvent include water and lower alcohols of C 1 to C 6 , and particularly preferably distilled water or deionized water.

The precursor solution may be prepared at 80 ~ 130 ℃. Drying process may be performed for 5 to 10 hours at 100 ~ 130 ℃. The drying method is not particularly limited and a rotary evaporator or oven may be used. When modifying the support or supporting the catalyst or catalyst enhancer, the number of times of supporting these precursor solutions is not limited. For example, the catalyst component may be supported by dividing it several times.

The present invention can optimize compression molding by controlling variables such as compressive strength, particle size, flowability of powder, viscosity, desorption degree and the like.

The present invention is characterized by controlling the mechanical strength of the catalyst by adjusting the compressive strength applied to the catalyst powder before compression molding.

The compressive strength may be 5 kN to 25 kN, specifically 10 kN to 20 kN, more specifically 13 kN to 17 kN, but is not limited thereto, and may be adjusted according to the dimensions of the pellets. If the compressive strength applied to the catalyst is abnormally high, it may cause damage to the molding module (Fig. 4 (a)).

The present invention is characterized in that the mechanical strength of the catalyst is controlled by adjusting the size of the catalyst powder before compression molding.

The size of the catalyst powder before compression molding is preferably 45 to 75 탆. If the size of the catalyst powder is less than 45㎛ can stick to the molding module may cause module damage. The strength of the pellets formed using the catalyst powder of 45 to 75 μm size was the best (FIG. 4 (b)). Uneven catalyst powder size can damage the molding module and reduce the strength of the pellets.

The present invention can optimize the compression molding by controlling the flowability and viscosity, and the degree of desorption of the catalyst powder before compression molding during compression molding.

The flowability of the catalyst powder can be a variable that determines the amount of catalyst filled in the molding module. The flowability of the catalyst powder can be controlled by controlling the size of the catalyst powder.

The present invention can increase the viscosity of the catalyst powder so that the catalyst has a formability. To this end, an additive may be added to the catalyst powder during compression molding.

As an example, PVA, talc, etc. can be added as a viscosity agent which provides the moldability of a catalyst.

In addition, talc, graphite, or the like may be added as a lubricant to minimize the powder sandwiched between module gaps during molding of the pellets.

In one embodiment of the present invention, a pellet-type catalyst was prepared by adding 5% each of PVA, MC binder, talc, and graphite as additives (FIG. 5).

The PVA or MC binder can provide the formability of the catalyst, but may cause the catalyst cracking to reduce the strength. Talc or graphite can minimize the powder sandwiched between module gaps when forming pellets, but can significantly reduce catalyst strength.

The firing temperature of the compression molded pellets in the present invention may be 500 ~ 1000 ℃, preferably 800 ~ 900 ℃, in particular may be 850 ℃.

Prepared by firing at the temperature of the catalyst is γ-Al 2 O 3 and have the same crystal phase and a structure and a rather γ-Al 2 O 3 a excellent in the specific surface area and acid site characteristics than the catalyst made of the starting material, the reaction There is an advantage that the characteristics are improved.

Ni-based catalyst for SMR according to the present invention may be a pellet having an average diameter of 2 to 3mm. Catalysts having a suitable filling rate should be used depending on the reactor size, with 2 mm pellets being preferred as the catalyst to be used in the reaction.

Ni-based catalyst molded article for SMR according to the present invention may have a mechanical strength of 8 to 20 kgf.

The Ni-based catalyst molded article for SMR according to the present invention may have a specific surface area of 50 to 200 m 2 / g, and preferably 75 to 150 m 2 / g.

Ni-based catalyst molded article for SMR according to the present invention may have an average pore diameter of 5 to 15 nm.

In the Ni-based catalyst molded body for SMR according to the present invention, the methane conversion rate in the steam methane reforming process (SMR) at 500 to 900 ° C., specifically 550 to 650 ° C., may be 80% or more compared to the equilibrium conversion rate.

 The Ni-based catalyst compact for SMR according to the present invention contains Ni species crystals even before the steam methane reforming reaction, and Ni peaks appear in the XRD of the catalyst after the reaction.

Non-limiting examples of the Ni species crystals include NiAl 2 O 3 and the like.

The steam methane reforming process for hydrogen production is strongly influenced by the pressure of increasing the number of moles of gas. The breakage of the catalyst may be a factor of decreasing the reaction efficiency by increasing the reaction pressure, the catalyst compact for pellet-type SMR according to the present invention can prevent this.

Therefore, the Ni-based catalyst compact for pellet-type SMR according to the present invention can be used in a reactor that simultaneously performs steam methane reforming process (SMR) and hydrogen separation process at 500 to 600 ° C. low temperature.

In another aspect, the present invention

1) preparing a nickel precursor solution;

2) impregnating boehmite into the solution of step 1) to impregnate the boehmite with a nickel precursor;

3) obtaining a catalyst powder having a nickel precursor supported on boehmite; And

It provides a method for producing a Ni-based catalyst molded body for steam methane reforming, including; 4) compression molding and calcining the powder of step 3).

Ni-based catalyst compact for pellet-type SMR according to the present invention may be prepared according to the above production method.

The nickel precursor may be in the form of nitrate (NO 3 ), acetate salt, halide salt (F, Cl, Br, I) or a mixture thereof, but is not limited thereto.

Specifically, the nickel precursor is selected from the group consisting of Nickel Nitrate Hexahydrate, Nickel Chloride Hexahydrate, Nickel Acetate Tetrahydrate, and Nickel Bromide Hydrate. It may be one or more.

More specifically, the nickel precursor is nickel, titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), aluminum (Al) It may be a composite precursor consisting of one or more metals selected from the group consisting of magnesium (Mg), zirconium (Zr) and boron (B). Most preferably, the nickel-containing composite precursor comprises nickel and at least one metal selected from the group consisting of chromium (Cr), copper (Cu), aluminum (Al), magnesium (Mg) and boron (B). It may be a precursor.

The nickel-containing composite precursor solution may be one containing a promoter metal supply precursor. Non-limiting examples of the promoter include Ag, La, Mg, Pd, Ru and the like. Specifically, the promoter may be one or more selected from the group consisting of La, Mg and Pd.

In step 4), calcium oxide may be added as a catalyst enhancer. Specifically, after the catalyst enhancer is mixed with the powder obtained in step 3), compression molding and baking may be performed.

Examples of the solvent of the nickel precursor include water and C 1 to C 6 lower alcohols, and it is particularly preferable to use distilled water or deionized water. The precursor solution may be prepared at 80 to 130 ° C.

Obtaining the catalyst powder in step 3) may be performed by drying the solution of step 2) in which boehmite is immersed, and drying may be performed at 100 to 130 ° C. for 5 to 10 hours. The drying method is not particularly limited and a rotary evaporator or oven may be used. When modifying the support or supporting the catalyst or catalyst enhancer, the number of times of supporting these precursor solutions is not limited. For example, the catalyst component may be supported by dividing it several times.

Step 3) may further comprise the step of screening or pulverizing and screening the catalyst powder obtained to a predetermined size to control the size of the catalyst powder before compression molding. The catalyst powder may have a size of 45 to 75 μm before compression molding. The present invention is characterized in that the mechanical strength of the catalyst is controlled by adjusting the size of the catalyst powder before compression molding. If the size of the catalyst powder is less than 45㎛ can stick to the molding module may cause module damage. The strength of the pellets formed using the catalyst powder of 45 to 75 μm size was the best (FIG. 4 (b)). Uneven catalyst powder size can damage the molding module and reduce the strength of the pellets.

Compression molding of step 4) may be 5 kN to 25 kN, specifically 10 kN to 20 kN, more specifically 13 kN to 17 kN, but is not limited thereto, and may be adjusted according to the dimensions of the pellets. The present invention is characterized by adjusting the mechanical strength of the catalyst by adjusting the compressive strength applied to the catalyst powder. If the compressive strength applied to the catalyst is abnormally high, it may cause damage to the molding module (Fig. 4 (a)).

The present invention can increase the viscosity of the catalyst powder so that the catalyst has a formability. For this purpose, an additive may be added to the catalyst powder during compression molding in step 4). As an example, PVA, talc, etc. can be added as a viscosity agent which provides the moldability of a catalyst. In addition, talc, graphite, or the like may be added as a lubricant to minimize the powder sandwiched between module gaps during molding of the pellets.

The firing temperature of the pellets compressed in the step 4) may be 500 to 1000 ° C, specifically 800 to 900 ° C, in particular 850 ° C.

The catalyst prepared according to the preparation method may be in the form of pellets, pellets having an average diameter of 2 to 3mm. Catalysts having a suitable filling rate should be used depending on the reactor size, with 2 mm pellets being preferred as the catalyst to be used in the reaction.

In another aspect, the present invention provides a reactor which performs a steam methane reforming process (SMR) and a hydrogen separation process at the same time, using a Ni-based catalyst compact for pellet-type SMR according to the present invention.

The reactor may further include a catalyst for water gas shift reaction.

In addition, the Ni-based catalyst molded body for SMR according to the present invention can be used in a method for producing syngas or hydrogen gas from natural gas by performing a steam methane reforming process (SMR) and a hydrogen separation process in one reactor.

The method may also perform a water gas shift reaction after the hydrogen separation process in the reactor.

In the reactor performing the steam methane reforming process (SMR) in the presence of a Ni-based catalyst molded body for SMR according to the present invention, since the separation structure having hydrogen permeability is high, the hydrogen permeability is higher than other gases. Can be selectively removed, and according to the LeChatlier principle, the forward reaction in the reforming reaction can be more predominant, so that a high methane conversion can be obtained even at a low temperature range.

As the separation structure used in the present invention, it is preferable to use a separation membrane having a high hydrogen permeability.

The separation structure is hydrogen selectivity in the synthesis gas, a ceramic containing silica, alumina, zirconia, YSZ, or a combination thereof; Or a metal composed of nickel, copper, iron, palladium, ruthenium, rhodium, platinum, or a combination thereof; Alternatively, the composite composition may be a mixture of the metal and the ceramic. The structure of the separation structure may vary, and non-limiting examples may be in the form of flat membrane, tube, hollow fiber membrane.

According to the present invention, a high-strength nickel-based catalyst molded body may be manufactured through compression molding and used in steam methane reforming process (SMR) at 500 to 600 ° C. low temperature.

The catalyst shaped body for SMR of the present invention is capable of high strength of the catalyst through pelletization and molding by using boehmite as a support, and can exhibit improved reaction characteristics.

Figure 1 shows the shrinkage expansion of the reactor according to (a) temperature and (b) equilibrium conversion rate according to the pressure.

2 is a photograph of (a) MgNiAl 2 O 3 powder catalyst, (b) compression molding pellet catalyst.

Figure 3 shows the compressive strength of the 2mm pellet catalyst according to the molding method.

Figure 4 shows the mechanical strength of the catalyst for each variable of compression molding ((a) by compressive strength, (b) by catalyst size).

Figure 5 shows the molding strength according to various additives (0 is a non-molding catalyst).

Figure 6 shows the methane conversion and the equilibrium conversion of methane conversion of the pellet forming catalyst.

Hereinafter, the present invention will be described in detail by the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited by the following examples.

Example  One

A nickel-containing composite precursor (MgNiAl 2 O 4 ) was dissolved in distilled water at 1.0 mol / L and ultrasonically dispersed for 1 hour to prepare a precursor solution in which metal was dispersed.

After dipping Boehmite (A) powder in the precursor solution, the mixture was stirred at 40 ° C. to 70 ° C. at 2 rpm and dried in a 100 ° C. dryer for 24 hours to obtain a catalyst powder.

Catalyst powders were selected by size (45-75 μm, 75-180 μm, 180-250 μm and 250-300 μm). Without using additives in the selected catalyst powders, 2 * 3 mm catalyst pellets were compression molded at a compression strength of 10, 15, or 20 kN at 850 ° C. Ni-based catalyst pellets for steam methane reforming were prepared by firing at 850 ° C. for 6 hours in an air atmosphere.

Experimental Example  1: compression Strength stars  Strength rating

Evaluation of the mechanical strength of the catalyst pellets according to the compressive strength of the compression molding applied when preparing the catalyst pellets according to Example 1 was carried out. The catalyst of Example 1 was prepared by compression molding the catalyst powder by applying a force of 10, 15 and 20 kN, respectively, and the mechanical strength of the prepared catalyst was measured and shown in FIG. 4 (a).

Experimental results showed that the mechanical strength of the catalyst pellets was the best at 1.8 kgf when 15 kN was added to form 2 * 3 mm pellets.

Experimental Example  2: catalyst powder By size  Strength rating

In preparing the catalyst pellets according to Example 1, mechanical strength evaluation of the catalyst pellets according to the size of the catalyst powder was carried out. The catalyst of Example 1 was prepared by compression molding catalyst powders having sizes of 45 to 75 μm, 75 to 180 μm, 180 to 250 μm, and 250 to 300 μm with a compressive strength of 15 kN, respectively. The mechanical strength of each was measured and shown in FIG. 4 (b).

As a result, the mechanical strength of the catalyst pellets formed using the catalyst powder of 45 ~ 75㎛ size was found to be the most excellent. In addition, when the size of the catalyst is 45㎛ or less, it was confirmed that the cause of module damage by sticking to the molding module.

Comparative example : Preparation of Catalysts by Extrusion and Evaluation of Their Strength

Catalyst pellets were prepared in the same manner as in Example 1 except that the extrusion pellets were used to prepare the catalyst pellets.

The mechanical strengths of the catalyst pellets and the catalyst pellets prepared according to Example 1 were measured and shown in FIG. 3. At this time, all of the catalyst powder used a size of 45 ~ 75㎛, the compression strength at the time of compression molding was 15kN.

Experimental Example  3: additive evaluation

In order to improve the moldability of the catalyst, PVA, MC binder, talc, graphite may be used as an additive during compression molding of the catalyst.

5 wt% of PVA, MC binder, talc, and graphite were added to the catalyst powder of 45-75 μm, respectively, and the strength of the pellet catalyst prepared by compression molding at 15 kN compression strength was measured. The results are shown in FIG. 5.

As shown in FIG. 5, the PVA or MC binder may act as a viscous agent to provide the formability of the catalyst, but may cause the catalyst to be cracked, thereby reducing the strength. In addition, talc or graphite as a lubricant can minimize the powder sandwiched between the module gaps when forming the pellets, it was found that the catalyst strength can be very low.

Experimental Example  4: activity evaluation

The 2 * 3mm pellet catalyst prepared in Example 1 was evaluated for the activity of steam methane reforming reaction under the ratio of steam to methane (S / C) = 3, SV = 10,000 / h, 600 ° C. It is shown in Table 1 and FIG. The catalyst of Example 1 was prepared by compression molding a catalyst powder of 45-75㎛ with a compressive strength of 15kN.

Figure PCTKR2017009853-appb-T000001

As shown in FIG. 6, the result of the steam methane reforming reaction showed that the catalyst pellets prepared according to the present example showed higher conversion of methane conversion and equilibrium conversion ratio than those of commercial catalysts based on nickel alumina (BSF's MCFC fuel reforming catalyst). You can see that.

In Table 1, both catalysts showed a surface shape without cracking, and the catalyst pellets of this example were confirmed to have a length and diameter similar to those of the commercial catalyst.

In addition, while the specific surface area of the commercial catalyst before the reaction was about twice as large as that of the catalyst pellet of the present embodiment, the specific surface area of the pellet catalyst of the present embodiment was reduced to 1/3 level after the reaction, whereas the specific surface area of the pellet catalyst of the present embodiment was 106 m 2 / g, after the reaction was found to slightly decrease to 91m 2 / g. It is believed that this is due to the difference in the catalyst components (commercial catalyst: 60 wt% nickel, catalyst according to Example 1 (MgNi / Al 2 O 3 ): 20 wt% nickel).

In addition, as shown in Table 1, it can be seen that the pellet catalyst of the present invention is much superior in mechanical strength than the commercial catalyst.

Claims (16)

  1. A Ni-based catalyst molded product for steam methane reforming (SMR), wherein the catalyst powder impregnated with boehmite is impregnated with a nickel precursor, followed by compression molding and baking.
  2. The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the pellets have an average diameter of 2 to 3 mm.
  3. The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the compression molding has a compressive strength of 5 kN to 25 kN.
  4. The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the mechanical strength is 8 to 20 kgf.
  5. The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the catalyst powder before compression molding has a size of 45 to 75 µm.
  6. The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the specific surface area is 50 to 200 m 2 / g, and the average pore diameter is 5 to 15 nm.
  7. The Ni-based catalyst molded product for steam methane reforming (SMR) according to claim 1, wherein the methane conversion in the steam methane reforming process (SMR) at 500 to 900 ° C. is 80% or more of the equilibrium conversion.
  8. The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the catalyst before the steam methane reforming reaction comprises Ni species crystals.
  9. The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 8, wherein the Ni crystal is NiAl 2 O 3 .
  10. The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the firing is performed at 500 to 1000 ° C.
  11. The Ni-based catalyst molded product for steam methane reforming (SMR) according to claim 1, further comprising a cocatalyst selected from the group consisting of La, Mg, and Pd.
  12. 1) preparing a nickel precursor solution;
    2) impregnating boehmite into the solution of step 1) to impregnate the boehmite with a nickel precursor;
    3) obtaining a catalyst powder having a nickel precursor supported on boehmite; And
    4) compressing the powder of step 3) and firing the powder; a method of manufacturing a Ni-based catalyst molded body for reforming steam methane, including.
  13. A reactor for simultaneously performing a steam methane reforming process (SMR) and a hydrogen separation process, wherein the reactor is characterized by using the Ni-based catalyst molded body according to any one of claims 1 to 11 as a catalyst for SMR.
  14. The reactor according to claim 13, further comprising a catalyst for water gas shift reaction.
  15. In a method for producing syngas or hydrogen gas from natural gas by performing steam methane reforming process (SMR) and hydrogen separation process in one reactor,
    A method for producing a syngas or hydrogen gas, characterized by performing an SMR process under the Ni-based catalyst molded body according to any one of claims 1 to 11.
  16. The method of claim 15, wherein a water gas shift reaction is also performed after the hydrogen separation process in the reactor.
PCT/KR2017/009853 2016-09-09 2017-09-08 Nickel-based catalyst molded body for steam methane reforming and use thereof WO2018048236A1 (en)

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KR10-2016-0116625 2016-09-09

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7108804B2 (en) * 2002-06-12 2006-09-19 National University Of Singapore Supported nickel catalyst for synthesis gas preparation
KR20070076439A (en) * 2006-01-16 2007-07-24 도다 고교 가부시끼가이샤 Porous carrier for steam-reforming catalysts, steam-reforming catalyst and process for producing reactive mixed gas
KR20100076138A (en) * 2008-12-26 2010-07-06 재단법인 포항산업과학연구원 Ni/MgO/AL2O3 CATALYST FOR SYNGAS PRODUCTION AND MANUFACTURING METHOD THEREOF AND MANUFACTURING METHOD OF SYNGAS
KR20140099472A (en) * 2011-11-09 2014-08-12 바스프 에스이 Catalyst composition for the steam reforming of methane in fuel cells
KR20140106793A (en) * 2013-02-27 2014-09-04 한국화학연구원 Method for the preparation of molded article of nickel-containing catalyst for mixed modification reaction of methane and the molded catalyst article thus obtained

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7108804B2 (en) * 2002-06-12 2006-09-19 National University Of Singapore Supported nickel catalyst for synthesis gas preparation
KR20070076439A (en) * 2006-01-16 2007-07-24 도다 고교 가부시끼가이샤 Porous carrier for steam-reforming catalysts, steam-reforming catalyst and process for producing reactive mixed gas
KR20100076138A (en) * 2008-12-26 2010-07-06 재단법인 포항산업과학연구원 Ni/MgO/AL2O3 CATALYST FOR SYNGAS PRODUCTION AND MANUFACTURING METHOD THEREOF AND MANUFACTURING METHOD OF SYNGAS
KR20140099472A (en) * 2011-11-09 2014-08-12 바스프 에스이 Catalyst composition for the steam reforming of methane in fuel cells
KR20140106793A (en) * 2013-02-27 2014-09-04 한국화학연구원 Method for the preparation of molded article of nickel-containing catalyst for mixed modification reaction of methane and the molded catalyst article thus obtained

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