JPS60246201A - Reforming device for methanol - Google Patents

Abstract

PURPOSE:To make operation easy, and to raise energy efficiency, by making a mixed gas of methanol and steam flow through a catalytic layer of reaction tubes, circulating a combustion gas between an inner column and a group of reaction tubes. CONSTITUTION:The inner column 3 is set in the cylindrical container 1, tube sheets are laid at the upper and the lower parts of the container 1 and the inner column 3, and the tube sheets are provided with the sheath pipes 22. The reaction tubes 6 containing the catalytic layer 24 are inserted into the sheath pipes 22, and supported on the top of the sheath pipes 22. The heights at the tops of the reaction tubes 6 are stepwise varied by taking header attachment into account. The circulating fan 5 is set at the top of the inner column 3. Another cylindrical column 9 is laid in the inner column 3, and a combustion gas from a burner is introduced into the cylindrical column. The inlet regulator 11 for secondary air is set before an inlet of the combustion gas, and the heater 10 for a mixed gas of methanol and steam is set at the rear part of the flow. By this reforming device, methanol is efficiently decomposed to give hydrogen.

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention This invention relates to an improvement in an apparatus for producing hydrogen from methanol by a steam refluxing reaction.

Although the process of obtaining hydrogen from methanol by steam refluxing and reaction has been known since H., it has not been carried out much in practice. In terms of price, it is not as cheap as using methanol as a fuel.

However, due to the rise in the price of general energy and the decline in the price of -IJ methanol, this method is being reconsidered. In other words, it has come to be seen as a desirable medium-sized hydrogen supply tank that does not require large quantities.

Advantages of methanol other than price include firstly that it is easy to transport and secondly that reforming is easier than with other hydrocarbons. Therefore (installation in hydrogen demand areas)
Ming Vj. It becomes possible to easily install a station and supply 1C and hydrogen.

In this way, the IO required for purchasing a 4J equipment is that it should not only be reasonably priced and have a low impact, but also be easy to operate (if possible, it should be possible to operate unmanned; 1
High energy efficiency.

The riffing device provided here by the projectors is intended to meet this requirement.

Conventional technology The steam refrigeration A-forming reaction of methanol involves the following methanol decomposition reaction (1) - oxidative conversion reaction (rl)
A combination of these is possible.

ClhOII→CO-)2N2-21.7Kcaf/I
llol・・・・・・(1) GO +- IL O+Co2+H2-l- 9.8K
caf/11101...N) CLI3 011+112 0+CO2 (-3112
- 11.9K cal/mol --- ・-(
m) The reaction in (1) is an endothermic reaction, and therefore (from the standpoint of equilibrium, a higher temperature is desirable; Ij) is a heat-mediated reaction, and a lower temperature is desirable.

If this reaction is carried out in a heat insulating layer, the reaction temperature will drop too much since the whole is endothermic, and the reaction oil 1a will be lowered (IL) and the reaction will proceed sufficiently. In order to achieve this, there are J: and X in terms of temperature, power, methanol/steam ratio, catalyst activity, etc., but it is necessary to use a catalyst with strong low-temperature activity, to first raise the lq, then to gradually lower it. It is best to carry out the reaction at a temperature of about 100 mL.For this purpose, the catalyst layer should be a heat insulating layer -c'.'; stomach.

The amount of heat given to the catalyst layer is determined by the amount of heat given to the catalyst layer (medium volume of catalyst, medium yield per hour) and bll! It is desirable to be able to control the temperature of the catalyst layer (by allowing the temperature of the catalyst layer to vary freely).

A liquid heat carrier is generally used to transfer heat to the catalyst layer. This is because the heat transfer coefficient is large (1), which makes it easier to control the temperature.
There was a lot of screaming and yelling in the middle of the equipment.

If gas (combustion scum) is used as a heat transfer medium, the amount of nitrogen will be extremely high in the cylinder. If you have any questions, please use combustion scum 'l' k
It is possible to incorporate the b''1 and the IA! layers into an integrated device, i.e., there is no intermediate liquid heat transfer medium (because it is simpler).

However, when heating a gas body, heat transfer is poor, so a large amount of hot parts are heated. It is difficult for me to understand, and it is difficult for me to
(Limiting heat 113 by reducing the amount of reaction in the catalyst layer)
Even one stage such as 4j is necessary, because the 1.1 culm is faster than the 1-41 amputation equipment.

Structure of the Invention The refrigeration system provided by successive inventions allows this large amount of heat to be generated by combustion gas with a sufficient margin.

FIG. 1 shows the principle of this invention.

An inner cylinder 3 is installed inside the cylindrical container 1 coaxially with the container. A reaction tube 6 is installed in a 1% portion between this cylindrical container and the inner tube.A catalyst is filled inside this cylindrical container, and a reaction tube 6 is placed in the P row on the central axis of the cylindrical container. , are arranged approximately evenly in the annular part.

A mixed gas of methanol and steam heated to a predetermined temperature flows from -+ and 6 of this reaction tube, passes through the catalyst layer,
It flows out from the other end.

In addition, in the claims in this specification, the combustion gas circulating in LJ and the container is referred to as "combustion gas", and the newly replenished combustion gas is referred to as "new combustion gas", but since it is complicated, In the explanation section, all symbols are ``combustion gas°°''.

Inside the inner cylinder, a combustion gas generating device, that is, a burnout or combustion gas introduction port 14, and a combustion gas circulation nozzle 5 are installed. When a suitable combustion gas is obtained externally, it is advisable to introduce the combustion gas, and when a suitable combustion gas is obtained, fuel and air are fed into the burner, The combustion gas circulation unit mixes the combustion gas in the device U with the new high-temperature combustion gas in the inner cylinder C, and transfers the gas at an appropriate temperature to the reaction tube 8Y.
1) Avoid circulating between 1) and 4) heat the reaction tube.

Home country (gooi (combustion) Jsu (, 1 inner cylinder 1. to 11\
, warp, the tube RY flows from 1 to 10, and the mixed residue flows through the reaction tube from 1 to 1).
1'L.

It's good in the street of Otsui, b < , 10'l - On the other hand, Otsufl'l Hide problem is good. , In 1, the flow direction of the combustion gas and the mixed residue is cocurrent, but depending on the temperature condition (depending on 1), there may be countercurrent flow. Therefore, cocurrent flow is preferable, but in cases where the negative heat transfer part is small as a whole, the temperature of catalyst II is too high, or because of the heat resistance of the catalyst, very strong heating is not desirable. There may be cases where self-streaming is appropriate.

The reaction tubes disposed in the annular part need only be arranged approximately evenly in this part. If they are not evenly arranged, the gas flow will be uneven, and there is a risk that the amount of heat raised will be uneven.

The most six ways to arrange them is to arrange them at equal intervals on a circumference concentric with the central axis of the cylindrical container.

From the point of uniformity of gas flow and bamboo, these concentric circles are the same
〇 − It is desirable that the goals are equally spaced. However, the connection LJ between the reaction amount and the header) +111 il+ , \・l, 1
．． lJ・Rerawoto 1AT L, (Nnime/, 1 Tsuno/
p l (The height when holding 1° is l\rack 5-2 (I1
．． 1, '1'71/Masari (□・ノ.

Kiru J, Uni, As shown in the picture, Hatakesa 4th floor r'no (5.1
(If you install it, it is recommended.

If the heat transfer direction measures described later are not applied to this reaction tube, two kinds of donut-shaped balanor plates with different sizes of inner and outer diameters are placed in the annular part at equal intervals. , heat transfer can be improved.

If the baffle spacing is too small, the resistance will be too large and the temperature will be unbalanced, so it is better to install them sparsely.

Means of Composition of the Invention As mentioned earlier, the personnel of the present invention adopted the combustion gas heating method which simplifies the whole process and was able to achieve sufficient heat transfer. As a countermeasure for this heat transfer direction, we took the following measures.

See Figure 2.3.4 (1) Use an ordinary tube as a reaction tube.

10- (if) Install axial heat transfer fins 26 on the outside of the fSL reaction tube. Vertical fins are used to reduce gas flow resistance.

(m> Outside this reaction tube, a sheath tube 22 with an inner diameter of approximately the same size as the reaction tube is installed ()), and the combustion gas is passed between this reaction tube and the tube. L cannot pass through.Specifically, the tube plate 21 is installed in the annular part,
Add a sheath tube to this tube plate, b shell and -f-3-,
Type 7 heat exchanger J is installed. Insert the reaction tube into this sheath tube.

This state is shown in FIG.

Since this tube sheet supports the reaction tube and serves as a weir for combustion gas, a heat exchanger that is as durable is not necessary. In addition, the reaction tube is suspended on this tube sheet, and the lower tube sheet is simply used for swinging the reaction tube (J is sufficient.
be. Combustion gas passes through the narrowed section at a high flow rate, improving heat transfer.

When installing this sheath tube, the heat transfer fins described in the previous section may or may not be present. Coupled with the twin effect, the heat transfer coefficient is dramatically reduced.

Note that if the flow velocity in this part is not increased too much, the head of the combustion gas circulation unit will become crowded and the head will become large, so the design should be designed to take into account the heat transfer coefficient and take into account the vernonce. is desirable.

Heat transfer is most difficult with scales forming on the heat transfer surface, so the combustion gas will not emit at all, so the gas must be as clean as possible. However, it may be difficult to completely prevent scale.

In that case, remove one cover and react with the header? If you connect 1 to the outside, you can easily center the reaction tube t.

In this way, the heat transfer surface is completely ffi? I can do IJ. It is important to make it easy to remove the cover, disconnect the reaction tube connections, etc. Also, as mentioned before installing the reaction tube, it is desirable to set the height of the IJl and connect it to the header.

(iv) The inner tube 25 is coaxially inserted into the reaction tube, the catalyst is filled in the annular part between both tubes, and the raw material mixed gas flows from one end of the inner tube and reaches the other end. Then, it turns over, flows into the catalyst layer, and flows out from the other end of the outer tube.

This is shown in Figure 3.

When heat can be transferred to a catalyst tube, for example, when comparing a 1f tube and a 3J tube, the surface area per catalyst cross-sectional area in the case of a 3f tube is 1. /3.

Therefore, even if sufficient heat is supplied to the catalyst layer packed in one tube, in the case of three tubes, sufficient heat cannot be supplied as is. In this case, if a 2J tube is inserted inside and heat can be supplied from inside, even a 31-inch platform can supply the same amount of heat to the W layer as an 11-inch platform. .

Hit and touch v! 1. This is because the ratio of the layer cross-sectional area to the tube surface area is exactly the same as in the case of 1 zun. In this case, it can be considered that the cross-sectional area of the catalyst layer is t, and it has 5 times the capacity of 11 n as a reaction tube.

In such a reactor, it is necessary to install many small reaction tubes, and the cost of the apparatus is 2$1.
7J is preferable because it requires as few large reaction tubes as possible. This inner tube therefore helps greatly to simplify the device.

-13-IJ On the other hand, since heat is given from the inside, the amount of heat given to the combustion gas from the outside is reduced, making the overall design easier.

From the viewpoint of the heat resistance of the low-temperature active catalyst 1 itself, it is desirable to suppress the temperature noise of the catalyst layer below a certain limit.
By using a Φ pipe, the inlet temperature of the mixed gas is increased to a certain degree, and the temperature is 100%. iH 4 people: “-4 is below a certain limit”
It can be held down to

The outer diameter of the inner tube is preferably about 80 to 30% of the inner diameter of the outer tube.

(v) A sparrow with heat transfer fins 27 is used inside the above-mentioned inner tube. Internal heat transfer is enhanced and becomes more effective.

Heat transfer improves with at least one of the above methods.
If you do all of the above, the heat transfer coefficient will improve dramatically, and of course it will be the best, but depending on the situation. ! , you may not need to do all of them.

The combinations of these various cases are shown in Figure 4.

When carrying out the above (iv> or (V)), 14
- The heating stone of the mixed horn should be made considerably higher than the catalyst body [1. In this case, heat the mixed scum with a warm stone 1) Use a hot stone:
J,') 'j 7J There are 7 people, but N b I+! + tit As an economical method, one method is to introduce combustion gas [-1 or Pernod 1-1 combustion gas, or dilute this combustion gas with secondary air, so that the hot stone becomes low and IJ gas J is the one that heats up. 6th
See diagram.

Because gas hot stones are quite expensive? It is the heat transfer surface G of the heating device! J
Therefore, it can be made smaller, and the temperature is less than 1 inch.The roll absorbs the primary air more easily.

For this purpose, another circular ring 9 is installed coaxially inside the inner cylinder.
1, this cylinder's inlet [-1 is the secondary air inlet [1 and 1゛v
The heater 10 described above can be placed 1QIJ in the downstream cylinder.

There is a combustion gas circulation tube (,1, axial flow tube or 07 suitable), but there is no need to do it unless it is a usable tube. But-
15 ~ By combining this fan with combustion gas or burnout, the device can be extremely simplified, so I will introduce it next. As shown in FIG.
The combustion gas inlet or burnout passes through this shirt,
Combustion gases, fuel aj and air are introduced from this center. The starter and the bearing are attached to this tubular seat. The motor is thermally insulated or cooled with air to prevent overheating.

The circulation fan, its drive motor and burner are integrated, making it extremely compact and easy to maintain.

Embodiments FIG. 6 shows 15 embodiments of the apparatus of the present invention described above. This includes most of the items 11 already explained.

16- The whole is housed in a cylindrical container 1, and an inner tube 3 is installed inside it.The cylindrical container and 10 parts of the inner tube have roots attached, A sheath tube is installed on this information board as if it were a heat exchanger.
It is fixed to the tube plate and freely supported by the tube machine at the bottom. The first part tube sheet is designed so that gas cannot pass through it except through the sheath tube, but the first part tube sheet allows gas to pass through it freely. The L section of the tube plate serves as a barrier to gas passage through the reaction tube, and is extremely simple compared to the tube plate of the Caotong heat exchanger.

The reaction tube is inserted into this sheath and supported at one end of the sheath. The height of the upper end of the reaction tube is stepped in order to accommodate the installation of the ladder.

It is desirable that both ends of this sheath tube widen into the trumpet paddle 1 from the viewpoint of reducing the flow resistance of the combustion gas.

This reaction tube is a one-way tube type as shown in the above-mentioned h/) or (v), and the raw material mixed gas is introduced into the inner tube from the upper end, turns around at the lower end, enters the catalyst layer, and the outside = 17- The header for the mixed gas and cracked gas flows out to the outside at the lower end of the side.The header for the mixed gas and cracked gas becomes a ring pipe. It is only removable, so it is easy to install headers and reaction tubes, fill and replace catalysts, circulate fans, burner maintenance, etc.

A circulation fan 5 is provided in one part of the inner cylinder.Another cylinder 9 is provided within this inner cylinder, and the combustion gas from the burnout is made to flow into this cylinder. In front of the combustion gas input [-], there is a primary and quaternary air input role regulator 11, and in the wake (J mixed gas heater 10 gQ tl).

Of course, it is also possible to use an IJ circulation fan combined with the barb described in FIG.

In the two-Φ tube type reaction tube mentioned above, it has become possible to raise the temperature of the mixed gas, and this heater allows the high-temperature raw material mixed gas to be heated to 1! ? It will be done. With this device, methanol is decomposed with an efficiency of 18- and hydrogen is converted into 11-.

Next, I will talk about these four dangerous driving points.
゜The important temperatures in this device are the temperature of the combustion gas entering the reaction tube heating section, the catalyst temperature of the mixed gas, and the output [
1. It's wet pox.

The temperature of the combustion gas depends on the combustion of the fuel gas or the temperature of the combustion gas introduced from the outside.
The hot stone at the outlet of the layer is heated by the circulation of combustion gas.
It is better to do so. The flow rate of each gas can be satisfactorily controlled by simultaneous control of the main valve, regulator 1 and circulation fan. These three pleasures are synonymous! Since the eyes are related to each other, it can be controlled comprehensively by 21 people. It is also possible to do so.

Next, methanol was decomposed using the apparatus shown in FIG. 6, and the Iζ results will be described.

Water vapor, methanol molar ratio 1.5 combustion gas knitting
380°C Mixed gust F capacity 5kg/cwl (1 liter of catalyst layer) Temperature 250°C There are various types of C catalysts, including catalysts for use, but catalysts with strong low-temperature adsorption are desirable.However, catalysts with strong low-temperature adsorption usually have the disadvantage of poor heat resistance. degree is desirable.

The 4A paddy used in this device is warm and does not lose its culm, so it is possible to use carbon steel material made by Totsu. In particular, stainless steel is partially used for the snow in the bar 9- where the temperature is particularly high.

The cylindrical container, J, and cover that house the entire device are pressureless containers, making it a low-cost device.

[Brief explanation of drawings]

Figure 1: Riff A-ming of the present invention] Tori map Figure 2
Longitudinal cross-sectional view of the reaction tube (double tube type) (Figure 3) Longitudinal cross-sectional view of the reaction tube (double tube type) Figure 4 Cross-sectional view of various combinations of reaction tubes (Figure 5) Combustion gas light/I♂♂゛1° combined circulation fan concept Fig. 6 One part view of the rifting device according to the present invention 1 Cylindrical container 2 Cover 3 Inner cylinder 4 Barb or combustion gas introduction I] 5 Combustion gas circulation fan 6 Reaction tube 7ff2 combined gas header 8 Cracking gas header 9 cylinder 10 heater 11 secondary air inlet regulator 211 tube plate 22 sheath tube 23 reaction tube (outer tube) 24 catalyst 25 inner tube 26 outer tube heat transfer fin 27 inner tube heat transfer fin applicant
Toyo Njinino Ring Co., Ltd.21

Claims (7)

[Claims] (1) Suboumuri 7A- which decomposes a mixed gas of methanol and water vapor by passing it through a catalyst layer.
In Mining HE, an inner cylinder is provided inside the cylindrical container coaxially with the cylindrical container, and a reaction tube filled with a catalyst is placed in the annular part formed between the cylindrical container and the inner cylinder, and the reaction tube is connected to the central axis of the cylindrical container. Arranged in parallel and approximately uniformly, the mixed gas is prevented from flowing through the catalyst layer of this reaction tube from one end to the other, while four generators U or (J) of fresh combustion gas are placed inside the inner tube. [Introduction 1], d3 and a combustion gas circulation fan are provided, and the combustion gas obtained here is circulated between the inner cylinder and the reaction tube to heat the reaction tube. Riff 4-ming set. (2) The claim that the reaction groups are arranged at equal intervals on one or more circles having the same center as the central axis of the reaction container! ′! I Ij'+, the rhino-ohming device Fi of methanol. (3) Into the annular portion, attach donut-shaped batonol plays 1 of two sizes, large and small, with inner and outer diameters, respectively, at right angles to the central axis of the cylindrical container and at equal intervals across the cylindrical container. Q ++ /, -. The method of rinsing methanol according to either claim 1 or the second claim. (4) (i) Using a regular tube as a reaction tube
Attach an axial heat transfer twin 4 to the outside of this reaction tube. (lfl) Install this reaction tube coaxially with this reaction tube.
, the inner diameter is larger than the reaction tube jh! S. Installed inside a sheath tube of approximately the same length as the reaction tube, allowing the combustion gas to pass only between the reaction tube and the sheath tube.J. Unizuro, (tv) An inner tube is installed inside this reaction tube. Insert coaxially and touch v1. The annular portion between both tubes is filled with the mixed gas, which flows in from one end of this inner tube, turns around when it reaches the other end, flows into the catalyst layer, and flows out from the other end of the outer tube. (ν) With axial heat transfer fins on the inner surface (i1' + J/
, Reno A performed in the same manner as above (tv) using x inner tube.
- Mink equipment. (5)) Let the combustion power station tI'i ring horn drive electric motor drive seat 71~ be the tubular shape Pno1~ (]shi,
ノ、・ん（、1 Penetrating the center of this dot, a new combustion gas generator t1 stomach or μ capacitor 11 is attached.Claims 1 to 4 11'l The methanol renoiming device according to any one of the above. (6) Inside the inner cylinder, another cylinder is installed coaxially with the inner cylinder, and the new combustion gas is first poured into this cylinder,
At the entrance of this cylinder, a primary air ``Lugi'' re-u is installed, and in the wake of the new combustion gas, a heater made by Eizawa Goka is installed (J, 1) Revised scope No. 111 'i<c 5th
The methanol Reno A arming neck attachment according to any one of In. (7) The temperature of the reaction tube heating part of the combustion scum is 1', the mixed gas catalyst is sick'-1 1α, and the catalyst notification temperature 1a, the amount of new combustion scum introduced, the new combustion gas enters' next,
Methanol paste 74-min'17 B! i.