JP2010179254A - Catalyst for producing synthesis gas and method for producing synthesis gas by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for producing synthesis gas, which has a small pressure loss and the performance of which can be restrained from being deteriorated owing to the pressure loss, and to provide a method for producing synthesis gas by using the catalyst for producing synthesis gas. <P>SOLUTION: The catalyst for producing synthesis gas is obtained by depositing nickel on a carrier 10 which comprises a spiral cylindrical material 11 wound spirally at predetermined intervals and a supporter 12 joined to the spiral cylindrical material 11 along the axial direction thereof and which is based on magnesia spinel. The method for producing synthesis gas comprises a step of reacting hydrocarbons with steam in the presence of the catalyst for producing synthesis gas. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a synthesis gas production catalyst useful for industrial production of synthesis gas and a synthesis gas production method using the same.

Conventionally, a mixed gas containing hydrogen and carbon monoxide has been used as a raw material gas for industrial hydrogen, ammonia, methanol, hydrocarbon liquid fuel (GTL), dimethyl ether, medium and high calorie gas production for city gas, etc. Yes. Such a mixed gas containing hydrogen and carbon monoxide is generally referred to as “synthesis gas”. For example, a hydrocarbon reforming method (SR method) using hydrocarbons such as methane gas, natural gas, LPG, and naphtha as raw materials. ), An autothermal reforming method (ATR method), a composite reforming method combining these, and the like. In these reforming methods, for example, when the hydrocarbon is methane, a mixed gas (synthetic gas) containing hydrogen and carbon monoxide is obtained by a reaction (steam reforming reaction) represented by the following formula (1). .
_{CH 4 + H 2 O → CO} + 3H 2 (1)

  In the steam reforming reaction for producing synthesis gas, it is known that a nickel-based catalyst is necessary. From now on, there has been a synthesis gas production catalyst in which nickel is supported as a catalyst component on an alumina carrier. It has been proposed (Patent Documents 1 to 3). Furthermore, in order to suppress carbon deposition that is likely to occur in such a catalyst using alumina as a support, a catalyst for producing synthesis gas in which nickel is supported on a magnesium oxide support as a catalyst component has also been proposed (Patent Document 4).

Special table 2006-501982 gazette JP 2002-338206 A JP 2007-69151 A JP 2003-284949 A

  However, since the synthesis gas production described above is generally performed by a method in which a catalyst is filled in a reaction tube such as a fixed bed reactor and gaseous raw materials (for example, methane gas and water vapor) are passed through the reaction tube. During the reaction, a pressure difference, that is, a pressure loss may occur between the inlet and the outlet of the reaction tube. When such a pressure loss occurs, the catalyst performance inherent in the catalyst is the conventional catalyst for syngas production. There has been a problem that (catalytic activity, selectivity, catalyst life) cannot be fully exhibited.

  Therefore, an object of the present invention is to provide a synthesis gas production catalyst that has a small pressure loss and can suppress a decrease in catalyst performance due to the pressure loss, and a synthesis gas production method using the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors made magnesia spinel having the advantage of high thermal shock resistance as a main component of a carrier for supporting nickel, and the shape of this magnesia spinel carrier was determined as predetermined. For the coiled cylindrical material that is spirally wound with an interval of, it is possible to effectively reduce the pressure loss if the shape is provided with the support along the axial direction, and the performance inherent in the catalyst can be reduced. The present invention has been completed by finding that it can be fully expressed.

That is, the present invention has the following configuration.
(1) A coiled cylindrical member wound spirally at a predetermined interval and a support joined along the axial direction of the coiled cylindrical member, and a carrier mainly composed of magnesia spinel, nickel A catalyst for synthesis gas production, characterized in that is supported.
(2) The synthesis gas production catalyst according to (1), wherein the carrier includes a plurality of support columns.
(3) The catalyst for syngas production according to (1) or (2), wherein the supported amount of nickel is 0.1 to 50% by weight of the total weight of the catalyst.
(4) The carrier has a total pore volume of 0.20 mL / g or more and a pore radius of 0.01 μm or more and 0.05 mL / g or more in pore volume measurement by mercury porosimetry. The catalyst for syngas production according to any one of (1) to (3), which is a catalyst.
(5) The catalyst for syngas production according to any one of (1) to (4), wherein the carrier has a specific surface area of 1 m ² / g or more in a specific surface area measurement by a nitrogen adsorption one-point method.
(6) The catalyst for syngas production according to any one of (1) to (5), further including a platinum group element.
(7) The catalyst for syngas production according to (6), wherein the platinum group element is one or more elements selected from the group consisting of rhodium, ruthenium, iridium, palladium, and platinum.
(8) The catalyst for syngas production according to (6) or (7), wherein the platinum group element content is 0.1 to 10% by weight based on the total weight of the catalyst.
(9) A method for producing a synthesis gas, comprising reacting a hydrocarbon with water vapor in the presence of the synthesis gas production catalyst according to any one of (1) to (8).

  ADVANTAGE OF THE INVENTION According to this invention, the catalyst for synthesis gas manufacture which can suppress the fall of the catalyst performance by pressure loss with small pressure loss can be provided. In addition to having a small pressure loss, the catalyst of the present invention also has an advantage of having an appropriate strength while having a large surface area. From these viewpoints, high catalyst performance can be expected. is there. By using such a catalyst of the present invention for a hydrocarbon steam reforming method or the like, an effect of efficiently producing synthesis gas can be obtained.

(A) is a side view showing an embodiment of the carrier in the present invention, (b) is a top view of the carrier of (a) as seen from above, and (c) is shown in the top view. It is sectional drawing in a xx line. (A) is an expanded sectional view which shows the extrusion hole part in one Embodiment of the extruder which manufactures the support | carrier in this invention, (b) is a schematic sectional drawing which shows the extruder of (a). .

(Catalyst for synthesis gas production)
The catalyst for producing synthesis gas of the present invention comprises nickel supported on a carrier having a specific shape mainly composed of magnesia spinel.
The carrier in the catalyst of the present invention has a shape including a coiled cylindrical member wound spirally at a predetermined interval and a support joined along the axial direction of the coiled cylindrical member.

  Hereinafter, the shape of the carrier in the catalyst of the present invention will be described in detail with reference to the drawings. FIG. 1 (a) is a side view showing an embodiment of the carrier in the catalyst of the present invention, and FIG. 1 (b) is a top view of the carrier of FIG. (C) is sectional drawing in the xx line shown to the said top view.

A carrier 10 shown in FIG. 1 includes a coiled cylindrical member 11 and a support column 12.
The coiled cylindrical member 11 is formed by elongating a carrier material into a single string shape so as to be spirally wound at a predetermined interval, and has a hole (through hole) 13 penetrating in the cylindrical direction. The cross-sectional shape of the string-like object that forms the coiled tubular member 11 is not particularly limited, and may be any of a semicircular shape, a circular shape, a triangular shape, and the like. Further, the thickness is not particularly limited as long as the adjacent ones can maintain a predetermined interval when they are wound spirally. Although the predetermined interval said here is not specifically limited, Usually, 0.1-10 mm, Preferably about 0.5-5 mm is good. Note that this spacing need not be the same in all parts of the helix.

  The dimensions of the coiled cylindrical material 11 are not particularly limited. For example, the length (the height of the cylinder) is 1 to 50 mm, preferably about 3 to 30 mm, and the diameter (the outer diameter of the entire cylinder). Is about 1 to 50 mm, preferably about 3 to 30 mm. The diameter of the through hole 13 is about 0.1 to 49 mm, preferably about 0.2 to 48 mm.

  In the case of the carrier 10 shown in FIG. 1, the coiled cylindrical member 11 has a single-spiral shape in which a single string-like object is wound, but other embodiments of the carrier in the catalyst of the present invention. In, the shape of the double helix in which two string-like objects were wound may be sufficient, and the shape of the multiple helix in which three or more string-like objects were wound may be sufficient. However, in that case, it is desirable that the string-like objects are wound spirally in parallel with a predetermined interval so as not to contact each other.

  Four struts 12 are joined to the coiled tubular member 11 along the axial direction (cylinder direction). At this time, the support columns 12 are provided around the coiled cylindrical member 11 at substantially the same interval. The number of the support columns 12 is four in the case of the carrier 10 shown in FIG. 1, but is not particularly limited in other embodiments of the catalyst carrier in the present invention. However, in order to ensure sufficient strength, the carrier preferably includes a plurality of support columns 12.

  The cross-sectional shape of the support column 12 is not particularly limited, and may be any of (substantially) semicircular shape, circular shape, triangular shape, etc. In order to ensure the joining with the coiled tubular material 11, for example. For example, a shape that can sufficiently secure a bonding area with the coiled tubular member 11 is preferable, such as a substantially semicircular shape as shown in FIG.

  Although the dimension of the support | pillar 12 is not restrict | limited in particular, For example, length is 1-50 mm, Preferably about 3-30 mm is good, and the thickness is a radius of 0. The thickness is about 1 to 12 mm, preferably about 0.2 to 11 mm.

  In addition, the support | pillar 12 is joined along the axial direction of the coiled cylindrical material 11, and in the case of the support | carrier 10 shown in FIG. In other embodiments, it is not always necessary to be joined vertically, and the coiled tubular member 11 may be inclined slightly as long as it is provided so as to pass through a plurality of gaps in the axial direction. There is no problem.

  In the case of the carrier 10 shown in FIG. 1, the support column 12 is provided facing the outer periphery of the coiled cylindrical material 11. In another embodiment of the carrier in the catalyst of the present invention, the coiled cylindrical material is used. The support column 12 may be provided so as to face the inner periphery of the motor 11 (that is, inside the through hole 13).

  The carrier having the above shape is, for example, an extrusion provided with a first die having a groove on the outer peripheral surface, and a ring-shaped second die having the first die fitted therein and a groove on the inner peripheral surface. Using a molding machine, the carrier material can be produced by an extrusion method in which only one of the first die and the second die is rotated. Hereinafter, the extrusion molding method and the extruder used in the method will be described in detail with reference to the drawings. However, the carrier molding method in the present invention is of course not limited to the method.

FIG. 2A is an enlarged cross-sectional view showing an extrusion hole portion in an embodiment of an extrusion molding machine for producing a carrier in the present invention, and FIG. 2B shows the extrusion molding machine of FIG. It is a schematic sectional drawing shown.
An extrusion molding machine 20 shown in FIG. 2 includes a first die 21 having a groove 21a on the outer peripheral surface, and a ring-shaped second die having the first die 21 fitted therein and four grooves 22a on the inner peripheral surface. 22. Specifically, the first die 21 and the second die 22 are both attached to the front surface of the extrusion molding machine 20 with the first die 21 fitted into the second die 22. The carrier material is continuously extruded from the groove 21a of the die 21 and the groove 22a of the second die 22.

  The dimensions of the first die 21 and its groove 21a, the second die 22 and its groove 22a are not particularly limited. For example, the outer diameter of the first die 21 is preferably 0.6 to 49 mm. Is about 1.6 to 29 mm, and the depth of the groove 21 a is about R0.2 to R12 mm, preferably about R0.7 to R7 mm. The outer diameter of the second die 22 is 1 to 150 mm, preferably about 2 to 100 mm, the inner diameter is 0.6 to 49 mm, preferably about 1.6 to 29 mm, and the depth of the groove 22a is R0.2 to R12 mm, preferably about R0.7 to R7 mm. In the embodiment shown in FIG. 2, the number of grooves 22a is four. However, the number of grooves 22a is not limited to this. 12, the number of string-like objects forming the coiled tubular member 11, and whether the support column 12 is disposed on the outer peripheral surface or the inner peripheral surface of the coiled tubular member 11. It is what is done.

  Further, the extrusion molding machine 20 also includes a rotating means 23 that rotates only one of the first die 21 and the second die 22. The rotation means 23 is not particularly limited, and a normal rotation means such as a motor may be employed. Specifically, in the embodiment shown in FIG. 2, the first die 21 is rotated by rotationally driving a rotating shaft 23 a fixed to the first die 21 with a motor 23 b. In this case, the coiled cylindrical member 11 is formed by the carrier material extruded from the groove 21 a of the first die 21, and the support column 12 is formed by the carrier material extruded from the four grooves 22 a of the second die 22. Thus, as shown in FIG. 1, the obtained carrier is one in which the support 12 is provided on the outer peripheral surface of the coiled tubular material 11.

  In contrast to the embodiment shown in FIG. 2, when the rotating means 23 rotates the second die 22, the support column 12 is made of the carrier material extruded from the groove 21 a of the first die 21. The coiled tubular material 11 is formed by the carrier material formed and extruded from the groove 22a of the second die 22, and the obtained carrier is the inner peripheral surface of the coiled tubular material 11 (that is, the through hole 13). Inner) is provided with a support 12.

In addition, the extruder 20 also has a cutting means 24 for cutting the carrier material extruded from the first and second dies 21 and 22. By cutting into a predetermined length by the cutting means 24, the carrier 10 can be obtained continuously. The cutting means 24 is not particularly limited, and for example, a conventionally known cutting means that drives a cutter knife or a wire (piano wire, etc.) stretched between two guide rollers with a motor or the like may be employed. That's fine.
The extrusion molding machine for producing the carrier in the present invention may be provided with a flow rate control valve (not shown) in order to control the extrusion speed of the carrier material extruded from the groove 21a and the groove 22a. .

In the present invention, the carrier is made of a porous refractory material mainly composed of magnesia spinel, and specifically, 90% by weight or more of the total weight of the carrier material is preferably magnesia spinel. Here, the magnesia spinel (MgAl ₂ O ₄ ) as the main component of the carrier may contain one or both of magnesium oxide (MgO) and α-alumina (α-Al ₂ O ₃ ).

  The carrier has a total pore volume of 0.20 mL / g or more and a pore having a pore radius of 0.01 μm or more and 0.05 mL / g or more in pore volume measurement by mercury porosimetry. Is preferred. If the total pore volume is less than 0.20 mL / g, or pores having a pore radius of 0.01 μm or more are less than 0.05 mL / g, sufficient catalytic activity may not be obtained.

The carrier preferably has a specific surface area of 1 m ² / g or more in the specific surface area measurement by the nitrogen adsorption one-point method. More preferably, it is 2-100 m < ² > / g. If the specific surface area of the support is less than 1 m ² / g, it may be difficult to support a sufficient amount of catalyst components (such as nickel), and at the same time, the contact efficiency between the active site of the catalyst and the raw material during synthesis gas production may be reduced. Since it becomes low, there exists a tendency for catalyst activity to become inadequate.

The catalyst of the present invention is obtained by supporting nickel as a catalyst component on the above-described carrier.
The amount of nickel supported is preferably 0.1 to 50% by weight based on the total weight of the catalyst. More preferably 1 to 40% by weight. More preferably, it is 2 to 30% by weight. If the supported amount of nickel is less than 0.1% by weight, sufficient catalytic activity may not be obtained. On the other hand, if it exceeds 50% by weight, nickel agglomeration may occur, leading to a decrease in catalytic activity. is there. The supported nickel usually exists in the form of an oxide (nickel oxide) on the support, and the supported amount is the weight as nickel oxide.

  The method for supporting nickel on the carrier is not particularly limited. For example, a method in which a nickel solution in which a nickel salt, compound or complex (such as nickel nitrate) is dissolved in an appropriate solvent is contacted or impregnated with the carrier is employed. do it. What is necessary is just to set suitably the nickel density | concentration of a nickel solution, and the frequency | count of a contact or an impregnation process so that a predetermined amount of nickel may be carry | supported finally. For example, when a solution of nickel nitrate is brought into contact with or impregnated into the support, nickel nitrate can be converted into nickel oxide by drying and firing as necessary.

The catalyst of the present invention preferably further contains a platinum group element in order to increase the catalytic activity. In particular, it is particularly preferable to contain at least one element selected from the group consisting of rhodium, ruthenium, iridium, palladium and platinum as the platinum group element.
The platinum group element content is not particularly limited, but is preferably 0.1 to 10% by weight based on the total weight of the catalyst.

  In order to contain the platinum group element, for example, a method of contacting or impregnating a support with a platinum group element-containing solution in which a salt, a compound, a complex, or the like containing a desired element is dissolved in an appropriate solvent, as in nickel. Should be adopted. At this time, the treatment for contacting or impregnating the support with the platinum group element-containing solution may be performed on the support before supporting nickel, or may be performed simultaneously with supporting nickel, or supporting nickel. Although it may be carried out on the carrier after being formed, it is generally preferred to carry out simultaneously with the loading of nickel.

In the case where there are a plurality of platinum group elements, a platinum group element-containing solution can be prepared for each element and sequentially contacted or impregnated with the support. Preferably, platinum in which a plurality of elements are present in one solvent is used. A group element-containing solution is preferably used. Furthermore, it is preferable that a platinum group element is contained in the nickel solution and all of nickel and the platinum group element are brought into contact with or impregnated into the support.
The supported platinum group element is preferably present in the form of an oxide, hydroxide, metal, etc. in a depth region within 1 mm from the surface of the carrier in an amount of 60% or more.

  The catalyst of the present invention may be subjected to a calcination treatment as necessary. The firing treatment may be appropriately performed according to a conventional method, for example, at a stage where a carrier material is formed into a carrier having a specific shape, or a nickel solution or a platinum group element-containing solution is contacted or impregnated on the carrier.

(Method for producing synthesis gas)
The method for producing a synthesis gas of the present invention is to obtain a synthesis gas (mixed gas containing carbon monoxide and hydrogen) by reacting hydrocarbons with water vapor in the presence of the catalyst of the present invention. For example, when the hydrocarbon is methane, carbon monoxide and hydrogen are generated by the steam reforming reaction such as the above-described formula (1). The specific method that can be adopted in the synthesis gas production method of the present invention is not particularly limited as long as it is a method based on the steam reforming reaction of the above-described formula (1). Examples thereof include a thermal reforming method or a combined reforming method combining these. Regardless of which method is used, the catalyst of the present invention has an appropriate strength while having a small pressure loss and a large surface area when filled in a reactor or vessel and used for the production of synthesis gas. In addition, the catalyst performance is high and the synthesis gas can be generated efficiently.

  The hydrocarbons are suitably selected according to the composition of the synthesis gas to be obtained (ratio of carbon monoxide to hydrogen) from one or more of methane, ethane, propane, butane, naphtha, etc. There is no particular limitation, and for example, methane gas, natural gas (usually methane is the main component), LPG (usually propane or pentane is the main component), naphtha, or the like can be used.

The synthesis gas production method of the present invention can be carried out in accordance with a conventional method except that the catalyst of the present invention is used, and the reaction conditions and the like are not particularly limited. For example, when the steam reforming method is applied, a heating furnace type reactor or the like is used as a reaction apparatus, the reaction temperature is usually 400 to 1,200 ° C., preferably 500 to 1,100 ° C., and the reaction pressure is Usually, 10 to 70 bar, preferably 15 to 60 bar. When the reaction is carried out in a fixed bed reaction system, the space velocity is typically, 1,000~10,000hr ^-1 (STP), it preferably to 2,000~8,000hr ^-1 (STP) Can do.

DESCRIPTION OF SYMBOLS 10 Support | carrier 11 Coiled cylindrical material 12 Support | pillar 13 Through-hole 20 Extruder 21 First die 21a First die groove 22 Second die 22a Second die groove 23 Rotating means 23a Rotating shaft 23b Motor 24 Cutting Means 25 Flow path

Claims (9)

  A coiled cylindrical member wound spirally at a predetermined interval and a support joined along the axial direction of the coiled cylindrical member, nickel supported on a carrier mainly composed of magnesia spinel A synthesis gas production catalyst characterized by comprising:   The catalyst for syngas production according to claim 1, wherein the carrier includes a plurality of support columns.   The catalyst for syngas production according to claim 1 or 2, wherein the supported amount of nickel is 0.1 to 50% by weight of the total weight of the catalyst.   The carrier has a total pore volume of 0.20 mL / g or more and a pore radius of 0.01 μm or more and 0.05 mL / g or more in pore volume measurement by mercury porosimetry. The catalyst for syngas production in any one of Claims 1-3. The catalyst for syngas production according to any one of claims 1 to 4, wherein the carrier has a specific surface area of 1 m ² / g or more in a specific surface area measurement by a nitrogen adsorption one-point method.   The catalyst for syngas production according to any one of claims 1 to 5, further comprising a platinum group element.   The catalyst for syngas production according to claim 6, wherein the platinum group element is one or more elements selected from the group consisting of rhodium, ruthenium, iridium, palladium and platinum.   The catalyst for syngas production according to claim 6 or 7, wherein the platinum group element content is 0.1 to 10 wt% with respect to the total weight of the catalyst.   A method for producing a synthesis gas, comprising reacting a hydrocarbon with water vapor in the presence of the synthesis gas production catalyst according to any one of claims 1 to 8.

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