JP5706294B2 - Catalytic reactor - Google Patents

Description

The present invention is a catalytic reaction in which a hydrocarbon-containing compound as a raw material is stirred and mixed in a reaction tube with a powder catalyst, and the hydrocarbon-containing compound is thermally decomposed by catalytic reaction to produce ultrafine carbon together with hydrogen (H ₂ ). Relates to the device.

  Here, methane, which is a lower hydrocarbon, will be mainly described as an example of the hydrocarbon-containing compound.

  The meanings of the technical terms “hydrocarbon compound” and “ultrafine carbon” in the present specification and claims are as follows.

  “Hydrocarbon-containing compounds”: not only saturated / unsaturated aliphatic / alicyclic and aromatic hydrocarbons, but also hydrocarbon derivatives frequently used as organic solvents, such as alcohols, acids, esters, ethers, etc. Including. In addition, the “hydrocarbon compound as a raw material” includes those mainly containing the “hydrocarbon compound” including impurities (other components).

  “Ultra fine carbon”: Fine carbon of 200 mesh (DIN) or less, including nano carbon (nanofibers, nanotubes) of less than 1 μm.

Various CO ₂ reduction measures have been implemented in order to achieve the numerical targets for the regulation of greenhouse gas emissions including CO ₂ under the Kyoto Protocol.

Methane is a major component of natural gas (LNG), methane hydrate, coal seam methane, biogas, etc., and is a hydrocarbon with abundant resources and the smallest amount of CO ₂ generated per unit calorific value. They tend to be used as alternative fuels for conventional coal and oil.

Further, since hydrogen (H ₂ ) does not generate CO ₂ when burned, development of hydrogen fuel cell vehicles and hydrogen fuel power generation is also being promoted.

However, when hydrogen is produced by the methane steam reforming method (CH ₄ + 2H ₂ O = CO ₂ + 4H ₂ ), CO ₂ is by-produced. For this reason, the treatment of CO ₂ generated in the methane steam reforming method becomes a problem.

For this reason, a methane direct reforming method (CH ₄ = C + 2H ₂ ) in which methane is directly reformed with hydrogen (H ₂ ) and carbon (C) using a catalyst can be considered.

However, as shown in the above reaction formulas, in the methane direct reforming method, hydrogen (H ₂ ) is ½ that of the methane steam reforming method, and the combustion heat of carbon (the methane steam reforming method generates heat). (Reaction) cannot be used, so the current situation is deceived from the viewpoint of manufacturing cost.

  On the other hand, if the carbon material obtained together with hydrogen in the methane direct reforming method becomes a high added value product (high value product) such as nanocarbon, the total profit is considered to be the same as the steam reforming method.

Furthermore, direct reforming of biomass-derived methane (hereinafter referred to as “biomethane”) can reduce CO ₂ in the atmosphere by going through the route of atmospheric CO ₂ → biomass → biomethane → carbon (+ hydrogen). The realization of carbon minus can also be expected.

  From the above viewpoints, Patent Documents 1 and 2 propose nanocarbon or hydrogen production methods and catalytic reaction apparatuses for producing nanocarbon having the following contents.

  That is, Patent Document 1 states that “a lower hydrocarbon and a catalyst are continuously supplied by a screw feeder so as to be in contact with each other in a countercurrent or countercurrent state, and the lower hydrocarbon and the catalyst are placed on the catalyst in the screw feeder. While thermally decomposing hydrocarbons, the nanocarbon-catalyst composite material produced on the catalyst by the pyrolysis is continuously transferred to the downstream side of the screw feeder by a screw and screwed at the downstream end side of the screw feeder. There has been proposed a nanocarbon production method and a reaction apparatus for producing nanocarbon characterized by being sent out of a feeder (see claim 1).

  Further, Patent Document 2 states that “in the reaction of directly decomposing lower hydrocarbons using a catalyst to obtain functional nanocarbon and hydrogen, the lower hydrocarbons contain low-concentration oxidizing gas or reducing gas or those gases. A method for producing functional nanocarbon and hydrogen from lower hydrocarbons, which is provided for the above reaction in the presence of a mixture gas of “

JP 2006-290682 A JP 2006-315891 A

According to the present invention described in Patent Document 1, “hydrocarbon as a raw material is stirred and mixed in a reaction tube with a powder catalyst, the hydrocarbon is thermally decomposed by catalytic reaction, and ultrafine carbon together with hydrogen in the reaction tube” "Catalytic reactor" that is improved based on the "catalytic reactor" that has a novel configuration that enables more efficient and continuous mass production of ultra-fine carbon containing nanocarbon (nanocarbon) The purpose is to provide.

  Another object of the present invention is to provide a catalytic reactor that can be applied not only to gas-containing hydrocarbon compounds such as methane as a raw material but also to thermal decomposition by catalytic reaction of liquid or solid hydrocarbon compounds. Objective.

  As a result of diligent development, the present inventors have conceived a “catalytic reaction apparatus” having the following configuration. For reference, a figure symbol is attached in parentheses.

In the reaction tube (3) provided with the external heating means (2), the hydrocarbon-containing compound as a raw material is stirred and mixed with the powder catalyst, and the hydrocarbon-containing compound is thermally decomposed by a catalytic reaction, whereby the reaction tube (3) A catalytic reactor for generating ultrafine carbon together with hydrogen in the interior ,
The reaction tube (3) has a built-in rotary conveyance stirring means (7), and
A raw material supply means (11) for airtightly supplying the raw material at one or a plurality of locations in the reaction tube (3);
Catalyst supply means (17), (19) for airtightly supplying the catalyst in one or a plurality of locations in the reaction tube (3);
A powder discharge means (25) connected to the front end side in the transport direction of the reaction tube (3) and discharging the powder product together with the catalyst in an airtight manner;
Gas discharge means (30), (34) and (35) connected to one or a plurality of locations on the upper side of the reaction tube (3) to suck and discharge gas components;
Is attached to the reaction tube (3) under reduced pressure to enable the catalytic reaction.

  In the catalytic reaction apparatus according to the present invention, the inside of all communicating apparatuses is depressurized by the suction action by the gas discharge means at the time of raw material supply and catalyst supply, and at the time of discharge of the powder product and the powder product, Since it is thermally decomposed under reduced pressure, the catalytic reaction is promoted, backflow and backfire are prevented, and continuous treatment can be safely performed.

If a gaseous component (exhaust gas) containing hydrogen separated from the reaction tube or separated from hydrogen is introduced into a hot air heating furnace, it can be completely pyrolyzed. In other words, the inside of the hot air heating furnace is maintained at a combustion temperature of 800 ° C. or higher and a high temperature residence time of 2 seconds or longer, which are required for suppressing the generation of diocins by the “waste sweeping method”, etc. It is.

  In addition, the catalytic reaction apparatus according to the present invention can be mass-produced safely and inexpensively with a simple apparatus from the viewpoints of both hydrogen production and ultrafine carbon (nanocarbon) production.

Nanocarbons that can be mass-produced at low cost in this way are expected to have various uses in the future, and can be expected to be expanded. As a use, for example, in the case of powder, the polymer material can be provided with conductivity or can be made of a carbon fiber material. In addition, it can be used for reinforcing the strength of rubber materials (tires, etc.), metal materials, asphalt materials, cement materials, etc. by utilizing the wear resistance and light weight properties that are the material characteristics of nanocarbon. Furthermore, it can be expected to be used for CO ₂ fixation, hydrogen storage, nanofilters, fuel cells, etc. by utilizing the characteristics of high specific surface area and ultra-light weight.

  From the viewpoint of producing nanocarbon, there are an arc discharge method, a laser evaporation method, and a CVD method. However, these methods are not suitable for continuous mass production and are expensive.

  Further, from the viewpoint of raw materials, not only gases but also liquids and solids having any properties can be applied as long as they are hydrocarbon-containing compounds.

Moreover, when biomethane obtained by methane fermentation of garbage and sludge is used as a raw material, hydrogen and nanocarbon can be obtained from organic waste, which contributes to CO ₂ reduction.

It is a flowchart which shows an example in case the hydrocarbon-containing compound as a raw material is a gas in the production apparatus of ultra fine carbon and hydrogen incorporating the catalytic reaction apparatus of the present invention. In FIG. 1, it is the change partial figure at the time of making the hydrocarbon-containing compound as a raw material into a liquid. (A)-(E) are sectional drawings which show each example of a reaction tube.

  An embodiment of a production facility for ultrafine carbon and hydrogen, which is applied when the raw material is a lower hydrocarbon (gaseous material), will be mainly described with reference to FIG.

  The catalyst reaction apparatus used in this embodiment basically includes a reaction tube 3 including a hot air heating furnace (external heating means) 2, a raw material supply means (A), a catalyst supply means (B), and a powder discharge. It comprises means (C) and suction / discharge means (D).

  In the illustrated example, the external heating means is a hot-air heating furnace 2 provided with an ejector (reduced pressure suction machine) 35 having a blower 36 as a drive source on a side wall. By introducing all of the exhaust gas from the reaction tube 3 or the exhaust gas after hydrogen separation into the ejector 35, it is possible to perform both thermal decomposition and purification of the exhaust gas and decompression operation in the reaction tube 3. The external heating means may be resistance heating, induction heating, high-frequency heating or the like, or a direct fire burner.

  In addition to the ejector 35, a burner 4 for generating hot air is provided below the reaction tube 3 on the side wall of the hot air heating furnace 2. The ceiling wall is provided with an exhaust cylinder 43 provided with an automatic exhaust bumper 42. The peripheral wall 2a of the hot air heating furnace 2 is made of a refractory material, and a temperature sensor 41 is attached to the bottom wall. The temperature sensor 41 transmits the temperature signal to the operation valve 67 of the burner 4 and the drive unit of the automatic exhaust bumper 42 to control the temperature in the hot air heating furnace 2.

  The fuel to the burner 4 can be supplied via a fuel supply pipe 5A branched from a raw material supply main pipe 5, which will be described later, and can also be used as a gas raw material (hydrocarbon compound). Of course, other general-purpose fuels may be supplied to the burner 4 by another route without using a gaseous raw material.

  The reaction tube 3 incorporates a rotary conveying stirrer 7.

  Here, the conveying agitator 7 has a stirring blade 7a formed on the peripheral surface of the rotating shaft 8 which is hollow (FIG. 3). The stirring blade 7a is a screw blade in the illustrated example, but may be a ribbon screw blade, a paddle blade (FIG. 3D), or the like. Further, as shown in FIG. 3C, the transport agitator 7 may be a biaxial type.

  The rotary shaft 8 is connected to the output shaft of the reduction motor 45 and is driven to rotate forward and backward. Both ends of the rotating shaft 8 are rotatably supported by bearings 47, 47 attached to both ends of the reaction tube 3, and are sealed with a heat-resistant gland packing 48 inside the both ends of the reaction tube 3. A rotary joint 9 is connected to the distal end side (non-driving side) of the rotating shaft 8.

  A plurality of (two in the illustrated example) injection nozzles 10 each having a diffusion cap attached thereto are formed on the rotating shaft 8.

  In addition, a discharge passage 27 is provided along the upper side of the stirring blade 7a so as to communicate with the exhaust inside the upper portion of the reaction tube 3. This is to facilitate specific separation of the product gas (low specific gravity gas) from the raw material (gas). 3A to 3E show cross-sectional views of the exhaust passage 27. FIG.

  In the reaction tube 3, a raw material supply port 6 and an exhaust gas outlet 28 are formed at positions on the transport direction base portion side and the transport direction front end side of the transport stirrer 7. In the illustrated example, the exhaust gas outlet 28 is one place, but may be a plurality of places. In the case of multiple places, they are usually gathered via a manifold hold.

  Here, the reaction tube 3 is horizontal in the illustrated example, but may be inclined upward in the transport direction (inclination angle: 30 to 60 °). When the reaction tube 3 is inclined, it can be expected that the contact mixing of the powder catalyst and the raw material is promoted due to partial falling of the powder catalyst by its own weight.

  (A) The raw material supply means supplies the raw material in an airtight manner to the reaction tube 3 at one or a plurality of locations, and is configured as follows.

  The outlet of the raw material cylinder 11 filled with the gaseous raw material (gaseous hydrocarbon compound) is connected to the first raw material supply port 6 and the first raw material supply port 6 through the first and second raw material supply pipes 5 a and 5 b branched from the raw material supply main pipe 5. It is connected to a rotary joint 9 which is a two raw material supply port. The first and second raw material supply pipes 5a and 5b are provided with flow control valves 70 and 68, respectively, to which flow meters 71 and 69 are attached.

  (B) The catalyst supply means supplies the catalyst in an airtight manner at one place or a plurality of places (one place in the illustrated example) of the reaction tube 3 and is configured as follows.

  The funnel-shaped catalyst receiving tank 17 and the catalyst supply tank 19 are connected in upper and lower stages via a connecting pipe 20 provided with a rotary valve 21 in the middle, and the outlet side of the catalyst supply tank 19 is the catalyst of the reaction tube 3. It is connected to the supply port 23. Thus, the powder catalyst can be supplied to the reaction tube 3 in an airtight manner. The tanks 17 and 19 are provided with extrusion screws 18 and 22, respectively. The extrusion screws 18 and 22 are hermetically held by gland packings 77 and 78 disposed inside the ceiling walls of the tanks 17 and 19, and are connected to output shafts of the speed reduction motors 76 and 79, thereby supplying a fixed amount of powder catalyst. Is possible.

  (C) The powder discharge means is connected to the powder discharge port 49 of the reaction tube 3 and discharges the powder product together with the catalyst in an airtight manner, and the configuration thereof is as follows.

  A powder discharge connecting pipe 50 is connected to a powder inlet 49 a of the cooling transport pipe 51 at the powder discharge port 49 of the reaction tube 3, and a rotary valve 53 is provided in the middle of the powder discharge connecting pipe 50. . This is because the gas is shut off between the reaction tube 3 and the cooling conveyance tube 51 to discharge the powder in an airtight manner.

  The outside of the cooling transport pipe 51 is covered with a cooling jacket 52 using cold air or water as a cooling medium.

  A screw-type transport machine 57 is further provided inside the cooling transport pipe 51. One end of the rotation shaft 61 of the transport device 57 is connected to the output shaft of the reduction motor 59 and is driven to rotate. As with the reaction tube 3, the rotating shaft 61 is held by bearings 58 and 58 attached to both ends of the cooling transport pipe 51, and ground packings 62 and 62 are arranged on both inner sides of the cooling transport pipe 51 to rotate. Sealed as possible.

  The cooling conveyance pipe 51 is arranged horizontally in the illustrated example, but it is desirable that the cooling conveyance pipe 51 be inclined upward in the conveyance direction. The powder can be expected to fall due to its own weight, and the mixing of the powder can be promoted to improve the cooling efficiency. As with the reaction tube 3, the inclination angle is desirably 30 to 60 °.

  A powder recovery pipe 64 having a rotary valve 65 is connected to the outlet 51b of the cooling transfer pipe 51 in the middle, and the powder product (ultrafine carbon / catalyst) is airtight to the recovered powder storage can 66. It is discharged and can be collected.

  (D) The gas suction / discharge means sucks and discharges gas components at one or a plurality of locations on the upper side of the reaction tube 3 and is configured as follows.

  In the illustrated example, the exhaust gas outlet 28 is one place on the carry-out direction side, but it may be further provided at one place or a plurality of places in the intermediate portion. This is because the produced exhaust gas having a low specific gravity containing hydrogen rises and separates from the raw material gas even at an intermediate position in the conveying direction.

  The exhaust gas outlet 28 formed in the upper part of the reaction tube 3 in communication with the exhaust passage 27 of the reaction tube 3 is connected to a pressure pump 31 on the inlet side through an exhaust gas pipe 29 provided with a dust filter 30 in the middle. It is connected to an attached hydrogen separator 32. As the hydrogen separation device 32, a “hydrogen separation membrane device” (for example, “UBE hydrogen separation membrane” manufactured by Ube Industries, Ltd.) is used, but is not particularly limited as long as hydrogen can be separated. The hydrogen discharge side of the hydrogen separator 32 is connected to a hydrogen gas holder 33. Further, the separation gas discharge side of the hydrogen separation device 32 is connected to an ejector 35 via a suction pipe 34.

  Further, a bypass pipe 37 directly connected to the ejector 35 is connected to the exhaust gas pipe 29 on the outlet side from the dust filter 30. A bypass switching valve 38 is provided in the bypass pipe 37, and an inlet valve 39 and an outlet valve 40 are provided in the pipes 29 and 34 on the inlet side and outlet side of the hydrogen separator 32, respectively.

  In addition, when more processing capacity is required in the above manufacturing equipment, a plurality of reaction tubes 3 are installed in a stacked manner, and a multi-stage system in which one upper and lower sides are connected to each other, a plurality of reaction tubes connected side by side are connected. With the connected pipe system, etc., it can be handled with a larger capacity.

  Next, a method for producing ultrafine carbon and hydrogen using the production equipment will be described.

  Here, the hydrocarbon-containing compound as the raw material is preferably only a lower hydrocarbon (gas raw material) because the thermal decomposition by the catalyst is promoted.

  Examples of the lower hydrocarbon filled in the raw material cylinder 11 include natural gas, city gas, biomethane, and the like mainly composed of methane, ethane, propane, butane, and the like.

  While starting the air blower 36 of the ejector 35, simultaneously, the burner 4 is ignited and the inside of the hot air heating furnace 2 is heated to a predetermined temperature (800 ° C. or higher).

  Further, a powder catalyst is supplied to the catalyst receiving tank 17, extruded to the catalyst supply tank 19, supplied in an airtight manner into the reaction tube 3, filled to the vicinity of the powder discharge port 49 of the reaction tube 3, and continuously quantified. It can be supplied. Although not shown in the drawing, the powder catalyst may be supplied between the two valves instead of the rotary valve 21 and the supply and discharge may be repeatedly supplied by alternately opening and closing the valves. The powder catalyst can be supplied in an airtight manner.

  Here, iron powder, white metal, and rare earth, which are transition metals, are effective as the powder catalyst. In particular, iron, cobalt, and nickel, which are iron groups, are desirable because of their versatility.

  The burner 4 attached to the heating furnace (hot air generating furnace) 2 can be controlled at a furnace temperature of 800 to 1100 ° C., and heats the reaction tube 3 with hot air generated by the burner 4. At this time, the temperature in the reaction tube and the degree of vacuum vary depending on the properties of the gas raw material and the type of catalyst, but the temperature is 800 to 1100 ° C. (further 800 to 900 ° C.), and the degree of vacuum is −10 to −110 mmHg ( Further, -50 to -90 mmHg) is desirable.

  In such a state, the gaseous material is supplied from the material cylinder 11 to the burner 4, the first material supply port 6, and the inlet (second material supply port) of the rotary joint 9. Specifically, the flow rate is confirmed and controlled by the control valves 68 and 70 and the flow meters 69 and 71, and supplied to the reaction tube 3. At this time, although not shown, the gas pressure of the gas source is reduced by a fine pressure adjusting pressure reducing valve until it reaches a set value (for example, 0.1 PaG). This is to facilitate control of the degree of vacuum in the reaction tube 3.

  Thus, the gaseous raw material is ejected from the plurality of injection nozzles 10 into the reaction tube 3 through the first raw material supply port 6 and the rotary joint (second raw material supply port) 9.

  By the forward rotation / reverse rotation of the stirrer 7 (for example, forward rotation 3 times and reverse rotation 2 times), the residence time in the reaction tube 3 is maintained, and the powder catalyst and the gas raw material are mixed and stirred. In this way, the gaseous raw material (hydrocarbon compound) is decomposed into carbon and hydrogen by thermal decomposition, and the powder catalyst surrounds the carbon, and ultrafine carbon is grown.

  Then, the ultrafine carbon (nanocarbon) grown on the powder catalyst is gradually conveyed to the powder discharge port 49 of the reaction tube 3, and the cooling conveyance tube 51 provided with the rotary valves 53 and 65 at the inlet and outlet. After that, it is discharged and collected in a collected powder container 66 while being cooled.

  If the powder catalyst is removed from the recovered ultrafine carbon, nanocarbon can be produced with very high accuracy. For removing the powder catalyst, a conventional hydrothermal method, centrifugal separation method, ultrafiltration method, or oxidation method can be used.

On the other hand, hydrogen is lighter than the hydrocarbon-containing compound that is the raw material (hydrogen has a specific gravity of 1/4 that of methane ), so the low specific gravity gas such as generated hydrogen and off-gas is preferentially separated from the gas raw material (methane, etc.) by specific gravity. Rise.

  The product gas and undecomposed gas (partially decomposed gas, trace nitrogen gas, odorous gas contained in city gas, etc.) pass through the exhaust passage 27 that is the upper space of the reaction tube 3 and the upper part on the outlet side of the reaction tube 3. The exhaust gas is discharged from the exhaust gas outlet 28.

  Nanocarbon flowing out from the exhaust gas outlet 28 through the pipe 29 together with hydrogen and exhaust gas is captured by the dust filter 30. The hydrogen and exhaust gas that have passed through the filter 30 are pressurized (for example, 1 MPa) by a compression / pressure pump 31 and sent to the hydrogen separator 32, where they are separated into exhaust gas (after separation) and hydrogen. Stored in the holder 33.

  The exhaust gas (after separation) passes through a suction pipe 34 and is sucked into a suction chamber of an ejector (reduced pressure suction machine) 35, mixed with the atmosphere in the ejector 35, sent to the hot air heating furnace 2, and pyrolyzed. Purified.

  Thus, the inside of the reaction tube 3 is depressurized to −10 to −100 mmHg by the ejector 35 using the blower 36 as a drive source.

  When hydrogen pyrolyzed in the reaction tube 3 is used as a heat source for pyrolysis, the exhaust gas on the inlet side to the hydrogen separator 32 is operated by operating the switching valves 38, 39, 40 of the exhaust gas pipe 29. The piping 29 and the outlet suction piping 34 are closed (non-conducting), and the bypass piping 37 is opened (conducting). Thus, the exhaust gas containing hydrogen gas (unseparated) can be sucked under reduced pressure by the suction pipe 34 to the ejector 35 without passing through the hydrogen separator 32 and introduced into the hot air heating furnace 2 to be burned. .

  In this case, the burner 4 is also burning, but if the temperature becomes too high, the operation valve 67 is operated by a signal from the temperature sensor 41 to reduce the fuel supply to the burner 4 and the temperature in the hot air heating furnace 2 is increased. Take control.

  The properties of the raw materials of the catalytic reaction apparatus of the present invention are not limited as in Patent Document 1 (hereinafter referred to as “prior art”). The reason is considered as follows.

The chemical reaction formula of methane by pyrolysis is
_{CH 4 = C + 2H 2 -74.8kJ} / mol
The decomposition reaction is an endothermic reaction while the volume is doubled.

  That is, in the present invention, the reaction is carried out while reducing the pressure, not under the pressure of 10 atm (1.013 MPa) or less as in the prior art described in Patent Document 1, and the reaction tube temperature can be set higher than in the prior art. .

  For example, at the example level, the conventional technology has 650 ° C. × 0.2 MPG (3 atmospheres) (paragraph 0035 of Patent Document 1), while the present invention has 800-830 ° C. (proportional control) × −1.5 kPaG. Therefore, the catalytic reaction is further improved in efficiency. Moreover, even if the raw material is a liquid, it is easily vaporized, and the catalytic reaction is promoted as in the case of lower hydrocarbons. Even if the raw material is powdery, the gas (hydrocarbon) generated through carbonization (pyrolysis) reaction by dry distillation is further pyrolyzed by catalytic reaction because it is at high temperature under reduced pressure. Produces.

  FIG. 2 is a modified partial view when the gas raw material is a liquid raw material in the ultrafine carbon and hydrogen production facility of FIG. 1.

  The main change is that the raw material cylinder 11 is changed to a raw material oil tank 12 provided with an oil supply pump 13. The same parts as those in FIG. 1 are denoted by the same reference numerals, and description thereof is omitted.

As the feedstock oil, petroleum-based fuels (gasoline, light oil, kerosene, heavy oil) mainly composed of hydrocarbons having 6 to 10 carbon atoms, liquefied coal, etc., recycled oil obtained from waste tires and waste plastics, Mention may be made of terpenes ((C ₅ H ₈ ) _n ) derived from plant fungi.

  Then, the feedstock is supplied to the reaction tube 3 as follows.

  The fuel oil is supplied as fuel to the burner 4 through the fuel supply pipe 5A branched from the raw material supply main pipe 5 by the oil supply pump 13 connected to the raw material tank 12, and the first and second raw material supply pipes 5a, The raw material oil is supplied into the reaction tube from the raw material supply port 6 through 5b. A perforated plate or net 11 for attaching liquid hydrocarbons to fine oil droplets is attached to the lower part of the raw material supply port 6. Although not shown, the raw material supply port may be an injection nozzle.

  In addition, when the raw material is a solid hydrocarbon compound, fine coal can be used in addition to paraffin which is a higher hydrocarbon. Although the solid hydrocarbon compound is powdered, illustration is omitted, but the raw material can be supplied into the reaction tube in an airtight manner by a supply method using two upper and lower tanks in the same manner as the powder catalyst. The supply location may include a plurality of raw material supply ports on the transport direction base side.

  When the powder raw material is finely powdered coal, the higher hydrocarbon can be used as a raw material for a burner (combustion heating means) together with the coal fine powder and the like.

  Using an experimental apparatus with the following specifications, production experiments of ultrafine carbon and hydrogen were conducted under the following operating conditions.

<Pyrolysis reaction tube equipment specifications>
1) Installation area of main unit: width 1,200 mm x length 4,000 mm x height 1,500 mm
2) Reaction tube (3) dimensions: Φ220mm x length 3,100mm
3) Transport stirrer (7) Dimensions: Φ200mm x Length 3,000mm
4) Deceleration motor (45) ... 0.2kw
5) Reaction tube stirrer rotation speed: 0.1 to 1 rpm
6) Hot air heating furnace (2) Dimensions: 1,200mm wide x 2,800mm long x 1,300mm high
7） Burner (4) ・ ・ ・ Gas burner 0.25kw × 300,000kcal / H
8) Catalyst receiving tank (17) ... 8L
9) Catalyst first supply tank (19) ... 10L
10) Dust filter (30) Dimensions: Φ50mm × 250L 40μ mesh
11） Compression and pressure pump (31) ・ ・ ・ 0.75kw × 1Mpa
12) Hydrogen separator (32) ・ ・ ・ Φ100mm × 2,000Lmm
13) Cooling transport pipe (51) ... Φ160mm × 1,500Lmm
14） Conveyer (57) ・ ・ ・ Φ100mm × 1,000Lmm
15) Deceleration motor (59) ... 0.1kw
16) Blower (36) ... 0.75kw

<Operating conditions>
1) Raw gas: City gas (13A)
2) Gas burner: Supply pressure 2.0kPa
3) Source gas supply amount: 30 Nm ³ / H
4) Hot air heating furnace temperature: 800-850 ° C (proportional control)
5) Temperature in the reaction tube: 800-830 ° C
6) Metal powder catalyst: Iron catalyst
7) Catalyst supply amount: 1kg / H

<Experimental result>
1) Hydrogen production: 60m ³ / H
2) Generated carbide: 16.9kg / H

<Example results>
The obtained hydrogen had a purity of 99% or more. In addition, the obtained ultrafine carbon was nanocarbon (nanofiber or nanotube) grown starting from entanglement with the iron catalyst.

  The nanofiber was in the form of a fiber having a size of several nanometers to several hundred nanometers.

2 Hot air heating furnace (external heating means)
3 Reaction tube 4 Burner 7 Transport stirrer (transport stirrer)
DESCRIPTION OF SYMBOLS 8 Hollow rotating shaft 10 Raw material cylinder 12 Raw material oil tank 17 Catalyst receiving tank 19 Catalyst supply tank 21 Rotary valve 27 Exhaust passage 28 Exhaust gas outlet 30 Dust filter 32 Hydrogen separator 33 Hydrogen holder 35 Ejector (vacuum suction machine)
51 Cooling transfer pipe 66 Collected powder storage can

Claims (6)

In a reaction tube equipped with an external heating means, the hydrocarbon compound as a raw material is stirred and mixed with a powder catalyst, and the hydrocarbon compound is thermally decomposed by a catalytic reaction to produce ultrafine carbon together with hydrogen in the reaction tube. A catalytic reactor,
The reaction tube has a built-in rotary conveying stirring means, and
A raw material supply means for airtightly supplying the raw material at one or a plurality of locations in the reaction tube;
Catalyst supply means for airtightly supplying the catalyst at one or a plurality of locations in the reaction tube;
A powder discharging means connected to the front end side of the reaction tube in the conveying direction and discharging the powder product together with the catalyst in an airtight manner;
A suction / discharge means connected at one or a plurality of locations on the upper side of the reaction tube and sucking and discharging a gas component with a vacuum suction machine;
The catalytic reaction is made possible by reducing the inside of the reaction tube under reduced pressure ,
The external heating means is a hot air heating furnace equipped with a burner and an ejector, and the vacuum suction machine is the ejector.
A catalytic reactor characterized by the above.   2. The catalytic reaction apparatus according to claim 1, further comprising a discharge passage communicating with the gas discharge means inside an upper portion of the reaction tube along an upper side of the stirring blade of the transport stirring means.   3. The catalytic reaction apparatus according to claim 1, wherein the raw material supply means is connected to one end of the rotary shaft so that the raw material can be ejected from a peripheral wall of the rotary shaft made hollow of the conveying and stirring means. . The catalytic reaction apparatus according to any one of claims 1 to 3 , wherein the hydrocarbon-containing compound is gas fuel, petroleum-based fuel (liquid), liquefied coal, or pulverized coal. Using the hydrocarbon-containing compound as a gas fuel, the heating temperature in the reaction tube is set to a range of 800 to 1100 ° C., and the degree of vacuum is set to a range of −1.33 to −13.3 kPa (−10 to −100 mmHg) to cause the catalytic reaction. The method for operating a catalytic reaction device according to any one of claims 1 to 3 . A facility for producing ultrafine carbon and hydrogen using the catalytic reactor according to claim 1 ,
The suction / discharge unit further includes a hydrogen separator, and an outlet side of the separation exhaust gas of the hydrogen separator is connected to the ejector so that hydrogen can be separated and recovered from the gas component. Production facility for ultrafine carbon and hydrogen.

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