JP2001146401A - Lamination type reformer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lamination type reformer capable of ensuring a high reforming ratio even when a remarkable temperature distribution is caused in a reforming cell. SOLUTION: This lamination type reformer is equipped with partition plates 30 for turning back a reforming raw material gas entering from a reforming raw material gas feed hole 11 four times in a plane of the reforming cell 50 and then discharging the reforming raw material gas from a reformed gas discharging hole 12 in the plane of the reforming cell 50.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to a reformer that reforms alcohols such as ME (dimethyl ether), city gas, butane, alcohols, ethers, and hydrocarbons and converts the reformed gas into a reformed gas containing hydrogen as a main component. More specifically, the present invention relates to a stacked reformer in which reforming cell units and heating cell units are alternately stacked.

[0002]

2. Description of the Related Art A conventional laminated reformer is disclosed in Japanese Patent Application Laid-Open No. 5-319801 filed by the present applicant (Patent No. 2).
No. 672923) is known. FIG. 8 is a side view of the stacked reformer disclosed in the publication. In addition, although this lamination type reformer is also provided with a holding plate, an inlet / outlet port for various gases, etc., only the reforming cell unit and the heating cell unit are shown for simplification. In the drawing, reference numeral 4 denotes a plate-shaped heating cell unit having an oxidation catalyst, and reference numeral 3 denotes a plate-shaped reforming cell unit having a reforming catalyst. Reference numeral 11 denotes a reforming material gas supply hole formed on one end side of the stacked type reformer for guiding the reforming material gas into the plane of the reforming cell 5;
Is a reformed gas discharge hole formed on the other end side of the stacked reformer to discharge the reformed gas in the plane of the reforming cell 5 to the outside of the reformer.

FIG. 9 is a plan view of the reforming cell 5 of FIG. Reference numeral 6 denotes a filling portion in which a pellet or a plate-like reforming catalyst is filled in a concave portion of a reformed gas separation plate which is a constituent member of the reforming cell 5. The filling section may be filled with a reforming catalyst composed of corrugated metal fins. Reference numeral 13 denotes an oxidizing gas supply hole formed on the side of the reformed gas discharge hole 12 of the stacking type reformer and guides the oxidizing gas into the heating cell unit 4, and 14 denotes a heating cell unit 4 formed on the side of the reforming material gas supply hole 11. An oxidizing gas discharge hole for discharging the oxidizing gas therein, a fuel gas supply hole 15 formed between the reforming material gas supply hole 11 and the oxidizing gas discharge hole 14 to guide the fuel gas into the heating cell unit 4; Reference numeral 16 denotes a fuel gas discharge hole formed between the reformed gas discharge hole 12 and the oxidizing gas supply hole 13 to discharge the fuel gas in the heating cell unit 4 to the outside;
Are inlet manifolds provided at one end of the filling section 6, 2
1 is a communication path connecting the reforming material gas supply hole 11 and the inlet manifold 22, 23 is an outlet manifold provided at the other end of the filling section 6, and 24 is an outlet manifold 23 and the reforming gas discharge hole 12. It is a connected communication path. In addition, 2
Reference numerals 6 and 27 denote sampling ports for collecting the reformed gas in the plane of the reforming cell 5.

In the conventional laminated reformer having the above-described structure, the reforming cell 5 is connected to the reforming material gas supply hole 11 through the communication path 21.
Is reformed into a reformed gas containing hydrogen as a main component in the reforming cell 5. The reformed gas flows parallel to the reformed gas discharge hole 12 in the plane of the reforming cell 5 and is discharged from the reformed gas discharge hole 12 to the outside. In addition,
Arrow A in the figure indicates the gas flow direction. In this stacked reformer, the reforming cell unit 3 and the heating cell unit 4 are alternately stacked, and the heat absorption by the reforming of the reforming material gas in the reforming cell unit 3 and the heating cell unit 4 The heat generated by the combustion of the fuel gas is balanced, the heat radiation is small as a whole, the reforming rate is high in the steady state, and the compactness is advantageous.

[0005] However, it has been found that in the above-mentioned stacked reformer, when the combustion amount and the reforming amount largely change due to the load fluctuation of the fuel cell, the reforming rate may temporarily decrease greatly. Stacked reformers are considered to be used for portable power sources and electric vehicles due to their compact performance.However, in such applications, the load fluctuates greatly, and even if the reforming rate is reduced temporarily, the fuel efficiency is significantly reduced. This can cause fuel starvation in the cell, leading to the worst case of fuel cell corrosion.

The inventor of the present application inserts thermocouples into nine sites 25 in the plane of the reforming cell 5 sandwiched between the two heating cell units 4 to thereby obtain a temperature distribution in the plane of the reforming cell 5. Is measured, and reformed gas is sampled from the gas sampling ports 26 and 27 other than the reformed gas discharge hole 12. When the combustion amount and the reformed amount change greatly, the reforming rate is greatly reduced even temporarily. The cause was investigated. As a result of the investigation, immediately after the amount of reforming in the reforming cell unit 3 and the amount of combustion in the heating cell unit 4 change significantly, the amount of fuel gas supplied from the fuel gas supply hole 15 changes greatly.
The heat distribution of the fuel gas in the heating cell unit 4 is not uniform inside, and the low temperature part 28 and the high temperature part 29 in the surface of the reforming cell 5 are not uniform.
And the reforming rate of the reforming raw material gas downstream of the high temperature section 29 is as high as 99%, whereas the low temperature section 2
8, the reforming rate of the raw material gas on the downstream side is as low as 69%,
It was found that the reformed gas discharge hole 12 had an intermediate value of 85%. This means that the reforming material gas flowing into the reforming cell 5 from the reforming material gas supply hole 11 through the communication path 21 passes through the reforming catalyst in the reforming cell 5, but passes through the high temperature section 29. Although the reformed raw material gas is almost reformed, the reformed raw material gas that has passed through the low-temperature section 28 does not proceed reforming due to the low temperature, and reaches the reformed gas discharge hole 12 without being sufficiently reformed. It was found that the reforming rate remained unacceptably low. In a steady state where the amount of reforming in the reforming cell unit 3 and the amount of combustion in the heating cell unit 4 are constant, the temperature distribution inside the heating cell unit 4 is small, and It was also confirmed that the difference in rates was small.

[0007]

In a conventional multi-layer reformer, for example, the reforming cell unit 3 is controlled by the load of a fuel cell.
Immediately after the reforming amount in the reforming cell and the combustion amount in the heating cell unit 4 greatly change, a low-temperature portion 28 and a high-temperature portion 29 are generated in the surface of the reforming cell 5, and the low-temperature portion 28 of the reforming cell 5
That the overall reforming rate may be reduced even temporarily, resulting in fuel deficiency in the fuel cell, which may lead to fuel cell corrosion. There was a problem.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and it is an object of the present invention to provide a laminated type which can ensure a high reforming rate even when a remarkable temperature distribution occurs in a reforming cell. The purpose is to obtain a reformer.

[0009]

According to a first aspect of the present invention, there is provided a multi-layer reformer, wherein a reforming material gas supplied from a reforming material gas supply hole is supplied to a surface of a reforming cell. A partition plate is provided for discharging from the reformed gas discharge hole after turning back.

[0010] In the stacked reformer according to claim 2 of the present invention, the reforming cell unit includes a first reforming cell adjacent to the heating cell unit and a second reforming cell adjacent to the first reforming cell.
The reforming raw material gas is reformed into the reformed gas by heat from the heating cell unit after entering the surface of the first reforming cell from the reforming raw material gas supply hole. The reformed gas passes through the surface of the second reforming cell and is discharged from the reformed gas discharge hole.

According to a third aspect of the present invention, a partition plate is provided in the plane of the first reforming cell so as to fold the reforming raw material gas in the plane.

[0012] In the laminated reformer according to a fourth aspect of the present invention, the partition plate is configured to bend the reforming material gas a plurality of times in a plane.

According to a fifth aspect of the present invention, the reforming raw material gas is methyl alcohol, and the partition plate is made of aluminum.

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a laminated reformer according to the present invention will be described. The same or corresponding parts as those of the conventional laminated reformer are denoted by the same reference numerals.

Embodiment 1 FIG. 1 is a side view of a stacked reformer according to Embodiment 1 of the present invention, and FIG. 2 is a plan view of the reforming cell of FIG.
In the figure, reference numeral 100 denotes a reforming cell unit, which comprises a two-stage reforming cell 50 filled with a pellet reforming catalyst. Reference numeral 30 denotes a partition plate for dividing the surface of the reforming cell 50 into a first section 31, a second section 32, and a third section 33, and 34 is provided at one end of the first section 31 of the reforming cell 50 and has a communication path 21. Connected to the reforming material gas supply hole 11 through
, The other end of the first section 31 and the second
A second manifold provided at one end of the section 32;
Reference numeral 6 denotes a third manifold provided at the other end of the second section 32 and one end of the third section 33, and reference numeral 37 denotes a third manifold provided at the other end of the third section 33 and connected via the communication path 24. A fourth manifold connected to the raw gas discharge holes 12.

In the multi-layer reformer having the above-described structure, the reforming material gas supply hole 11, the communication path 21, and the first manifold 34 are provided.
The reforming raw material gas flows into the reforming cell 50 through. In the plane of the reforming cell 50, the gas is supplied to the first section 31, the second manifold 35, the second section 32, the third manifold 36, the third section 33, the fourth manifold 37, the communication path 24, and the Gas is discharged to the outside from the gas discharge hole 12, and in the middle of the meandering path that is folded twice,
The heat from the heating cell unit 4 is reformed into a reformed gas containing hydrogen as a main component. Note that the arrow B in the figure indicates the gas flow direction.

Therefore, immediately after the reforming amount in the reforming cell unit 50 and the combustion amount in the heating cell unit 4 are greatly changed by the load of the fuel cell, the heating cell unit 4
Even when a high-temperature portion and a low-temperature portion occur in the plane of the reforming cell 50 due to a transient change in the calorific value of the combustion gas due to the bias of the concentration distribution of the fuel gas in the inside, all reforming is performed. The raw material gas flows through the first section 31, the second section 32, and the third section 33, passes through the surface of the reforming cell 50, and passes through the reforming catalyst in the high-temperature portion with a high probability.

The inventor of the present application has constructed a partition plate 30 using lightweight and high thermal conductivity aluminum, using methanol as a reforming raw material gas, and using a copper-zinc pelletized reforming catalyst in each section. 31, 32, and 33, and an operation test was performed under the conditions of a steam carbon ratio of 1.5 and a reforming and fuel amount in a range of (3 to 1/3). As a result, in each case, a high reforming rate of 97% or more was obtained.

Embodiment 2 FIG. 3 is a plan view of a reforming cell of a stacked reformer according to Embodiment 2 of the present invention. In the figure, reference numeral 30 denotes an aluminum partition plate for partitioning the in-plane of the reforming cell 51 into a first section 31, a second section 32, a third section 33, a fourth section 38, and a fifth section 39.
4 is a first manifold provided at one end of the first section 31 of the reforming cell 51, 35 is a second manifold provided at the other end of the first section 31 and one end of the second section 32, 36 is a third manifold provided at the other end of the second section 32 and one end of the third section 33, and 40 is a third manifold provided at the other end of the third section 33 and one end of the fourth section 38. A fourth manifold 41, a fifth manifold provided at the other end of the fourth section 38 and one end of the fifth section 39;
Reference numeral 42 denotes a sixth manifold provided at the other end of the fifth section 39 and connected to the reformed gas discharge hole 12 via the communication path 24.

In the laminated type reformer having the above-described structure, the reforming material gas supply hole 11, the communication path 21, and the first manifold 34 are provided.
The reforming raw material gas flows into the surface of the reforming cell 51 through the flow passage. In the plane of the reforming cell 51, the gas flows into the first section 31,
The second manifold 35, the second section 32, the third manifold 36, the third section 33, the fourth manifold 40,
Fourth section 38, fifth manifold 41, fifth section 3
9. The sixth manifold 42, the communication path 24, and the reformed gas discharge hole 12 are configured to be discharged to the outside. It is reformed into a reformed gas as a main component. Note that the arrow C in the drawing indicates the gas flow direction.

In the second embodiment, as compared with the first embodiment, the number of times of folding is increased from two times to four times, and
Since the section is divided into five sections, the reforming raw material gas can more reliably pass through the high-temperature section having high reforming efficiency, and high reforming efficiency can be secured even when the high-temperature section is generated only locally. . However, increasing the number of sections complicates the structure,
Since the pressure loss of the gas also increases, the number of sections is changed according to the area of the reforming cell. If the area is small, the number of turns may be one, and if the area is large, the number of turns may be increased. It is desirable.

The inventor of the present application has constructed a partition plate 30 using lightweight and high thermal conductivity aluminum, using methanol as a reforming raw material gas, and using a copper-zinc pelletized reforming catalyst in each section. 31, 32, 33, 38, and 39, and an operation test was performed under the conditions of a steam carbon ratio of 1.5 and a reforming and fuel amount in a range of (3 to 1/3). As a result, in each case, a high reforming rate of 97% or more was obtained.

Embodiment 3 FIG. 4 is a side view of a stacked reformer according to Embodiment 3 of the present invention, FIG. 5 is a plan view of a first reforming cell in FIG. 4, and FIG. 6 is a plan view of a second reforming cell A. FIG. 7 is a plan view of the second reforming cell B. FIG.
In the figure, reference numeral 52 denotes a first cell adjacent to the heating cell unit 4.
Are the second reforming cell A and the second reforming cell B disposed between the first reforming cells 52,
The first reforming cell 52, the second reforming cell A53, and the second reforming cell B54 constitute a reforming cell unit 200. Reference numeral 30 designates a first section 31 and a second section 31 in the plane of the reforming cell 52.
An aluminum partition plate 34 divided into a section 32 and a third section 33 is provided at one end of the first section 31 of the reforming cell 51, and the reforming material gas supply hole 11 is provided through the communication path 21.
, The first manifold connected to the first section 31
A second manifold provided at the other end of the second section 32 and one end of the second section 32; a third manifold provided at the other end of the second section 32 and one end of the third section 33;
Are provided at the other end of the third section 33, the ends of the second reforming cell A53 and the second reforming cell B54, and are connected to the reformed gas discharge holes 12 through the passage 45. A fourth manifold 44 is a fifth manifold provided at an end of the second reforming cell A53 and the second reforming cell B54. The fourth manifold 43 is an outlet of the first reforming cell 52 and an inlet of the second reforming cell A53.
Are the outlet of the second reforming cell A53 and the inlet of the second reforming cell B54.

In the stacked reformer having the above-described structure, the reforming material gas supply hole 11, the communication path 21, and the first manifold 34 are provided.
The reforming raw material gas flows into the surface of the first reforming cell 52 through. In the plane of the first reforming cell 52, the gas
It flows through the section 31, the second manifold 35, the second section 32, the third manifold 36, and the third section 33. Thereafter, the gas flows in one direction in the plane of the second reforming cell A53 through the fourth manifold 43, and subsequently flows in one direction in the plane of the second reforming cell B54 from the fifth manifold 44, The gas is discharged from the passage 45 and the reformed gas discharge hole 12 to the outside. Note that, in the figure, the arrow D indicates the gas flow direction.

In this embodiment, the reforming raw material gas flows from the heating cell unit 4 adjacent to the first reforming cell 52 halfway along the meandering path in the plane of the first reforming cell 52 twice. Is reformed into a reformed gas containing hydrogen as a main component. In the plane of the first reforming cell 52, the reforming reaction is almost completed, and thereafter, the reformed gas flows in the planes of the second reforming cell A53 and the second reforming cell B54. Flows in the direction.

The inventor of the present application constructed the partition plate 30 using lightweight and high thermal conductivity aluminum, used methanol as a reforming raw material gas, and used a copper-zinc-based pellet-shaped reforming catalyst. An operation test was performed under the conditions of a steam carbon ratio of 1.5 and the reforming and fuel amounts in the range of (3 to 1/3 times). As a result, the reforming rate was 9 in each case.
A high reforming rate of 9% or more was obtained. Further, the concentration of carbon monoxide was 0.8%, which was lower than 1% in the first and second embodiments.

The reason why a higher reforming rate (97% → 99%) was obtained as compared with the first and second embodiments is that the second reforming cell A53 and the second reforming cell B54 also have a higher reforming rate. This is because the quality has advanced. In addition, the reason why the carbon monoxide concentration was lower than that in the first and second embodiments is that the second reforming cell A53 and the second reforming cell B54 are adjacent to the heating cell unit 4. The temperature is lower than that of the first reforming cell 52, and as the reforming temperature becomes lower, the reaction equilibrium (CO ₂ + H ₂ =
This is because CO + H ₂ O) shifts in a direction in which the concentration of carbon monoxide decreases. The lower the concentration of carbon monoxide after reforming,
Air is added to oxidize carbon monoxide (CO + (1/2) O ₂ ) in a CO selective oxidizer arranged in a post process of the reformer.
= CO ₂ ) to reduce the concentration of carbon monoxide.

In the third embodiment, the first reforming cell 5 is used to increase the reforming rate and reduce the concentration of carbon monoxide.
Although the partition plate 30 is used in 2, the partition plate may be deleted when the main purpose is only to reduce the concentration of carbon monoxide. Further, in each of the above embodiments, the case of methanol reforming has been described. However, the present invention can be applied to the case of reforming DME, natural gas, and butane. The present invention can also be applied to partial oxidation reforming in which reforming is performed while burning a part of the fuel in the cell unit, or a combined reforming method intermediate between steam reforming and partial oxidation reforming. Further, the present invention can be applied to a stacked reformer in which an evaporation unit and a selective oxidation unit of carbon monoxide are incorporated. When city gas is used as the reforming raw material gas, stainless steel is used as the material of the partition plate from the viewpoint of heat resistance.

[0029]

As described above, according to the multi-layer reformer according to the first aspect of the present invention, the reforming raw material gas supplied from the reforming material gas supply hole is supplied to the surface of the reforming cell. Since the partition plate is provided to be discharged from the reformed gas discharge hole after being turned back in the plane, even if a temperature distribution occurs in the heating cell unit, the reforming raw material gas is heated to a high temperature in the plane of the reforming cell. The probability of passing through the portion is increased, and a higher reforming rate can be secured accordingly. In addition, even if some of the reforming catalysts have deteriorated, the probability of passing through a reforming catalyst that has not deteriorated is increased as compared with the conventional catalyst, so that reforming is covered by the reforming catalyst that has not deteriorated, The service life of the laminated reformer can be kept long.

According to the stacked reformer of the second aspect of the present invention, the reforming cell unit includes the first reforming cell adjacent to the heating cell unit and the first reforming cell. An adjacent second reforming cell, wherein the reforming raw material gas enters the plane of the first reforming cell through the reforming raw material gas supply hole and is converted into the reformed gas by heat from the heating cell unit. Quality,
Since the reformed gas is discharged from the reformed gas discharge hole through the plane of the second reforming cell, the temperature of the second reforming gas is lower than that of the first reforming cell. When the reformed gas passes through the surface of the reforming cell, the reaction equilibrium (CO ₂ + H ₂ = C
O + H ₂ O) is shifted in a direction in which the concentration of carbon monoxide decreases, and a reformed gas having a low concentration of oxygen monoxide can be obtained.

According to the laminated reformer of the third aspect of the present invention, since the partition plate for turning the reforming material gas in the plane is provided in the plane of the first reforming cell. In addition, a reformed gas having a low concentration of oxygen monoxide can be obtained, and the probability that the reforming raw material gas passes through a high-temperature portion in the plane of the first reforming cell is increased. Obtainable. In addition, even if some of the reforming catalysts have deteriorated, the probability of passing through the reforming catalyst that has not deteriorated increases, so that reforming can be covered by the reforming catalyst that has not deteriorated, and Long life can be maintained.

Further, according to the laminated reformer according to the fourth aspect of the present invention, since the partition plate is configured to bend the reforming raw material gas a plurality of times in the plane, the reforming raw material gas is accordingly reduced. Thus, the probability of passing through a high temperature portion in the plane of the reforming cell becomes higher, and a higher reforming rate can be obtained.

Further, in the laminated reformer according to claim 5 of the present invention, when methyl alcohol is used as the reforming raw material gas, the partition plate is made of aluminum. A heat-resistant and low-cost partition plate can be obtained.

[Brief description of the drawings]

FIG. 1 is a side view of a stacked reformer according to a first embodiment.

FIG. 2 is a plan view of the reforming cell of FIG. 1;

FIG. 3 is a plan view of a stacked reformer according to a second embodiment.

FIG. 4 is a side view of a stacked reformer according to a third embodiment.

FIG. 5 is a plan view showing a configuration of a first reforming cell of FIG. 4;

FIG. 6 is a plan view showing a configuration of a second reforming cell A of FIG. 4;

FIG. 7 is a plan view showing a configuration of a second reforming cell B of FIG. 4;

FIG. 8 is a side view of a conventional multi-layer reformer.

FIG. 9 is a plan view of the reforming cell of FIG. 8;

[Description of Signs] 4 heating cell unit, 11 reforming material gas supply hole, 1
2 reformed gas discharge hole, 50, 51 reformed cell, 30 partition plate, 52 first reformed cell, 53 second reformed cell A, 54 second reformed cell B, 100, 200 reformed cell unit.

 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Kazunori Dono 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsui Electric Co., Ltd. (72) Yoshiaki Odai 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Electric Corporation F-term (reference) 4G040 EA02 EA06 EB23 EB44 EB46 EC08

Claims (5)

[Claims] 1. A reforming cell including a plate-shaped heating cell unit having an oxidation catalyst and a plate-shaped reforming cell having a reforming catalyst and having a reforming material gas supply hole and a reforming gas discharge hole formed therein. And a stacked reformer in which units are alternately stacked. In the plane of the reforming cell, the reforming raw material gas entering from the reforming raw material gas supply hole is folded back in the plane, and A stacked reformer provided with a partition plate to be discharged from a reformed gas discharge hole. 2. A plate-shaped heating cell unit having an oxidation catalyst and a plate-shaped reforming cell unit having a reforming catalyst and having a reforming material gas supply hole and a reforming gas discharge hole formed therein are alternately arranged. A stacked reformer, wherein the reforming cell unit includes a first reforming cell adjacent to the heating cell unit, and a second reforming cell adjacent to the first reforming cell. Wherein the reforming raw material gas enters the surface of the first reforming cell from the reforming gas supply hole and is reformed into a reformed gas by heat from the heating cell unit.
The stacked reformer, wherein the reformed gas passes through the plane of the second reforming cell and is discharged from the reformed gas discharge hole. 3. The stacked reformer according to claim 2, wherein a partition plate for turning the reforming raw material gas in the plane of the first reforming cell is provided. 4. The stacked reformer according to claim 1, wherein the partition plate is configured to bend the reforming raw material gas a plurality of times in a plane. 5. The reforming raw material gas is methyl alcohol, and the partition plate is made of aluminum.
The stacked reformer according to claim 3.