JP4744271B2 - Method and apparatus for treating fluid organic compound - Google Patents

Description

The present invention relates to a method and apparatus for reforming an organic compound. Specifically, a fluid organic compound such as a hydrocarbon is removed in the presence of a reactive gas (eg, H ₂ O, CO ₂ , O _2, etc.). Thus, the present invention relates to a method and apparatus for treating a fluid organic compound suitable for performing a decomposition reaction and / or a reforming reaction.

  Here, the fluid organic compounds include not only gas or liquid hydrocarbons (including aliphatic, alicyclic and aromatic), but also thermal decomposition of plastics such as polyethylene and polypropylene (including waste plastics). Includes gas and liquid. Further, the fluid includes not only a normal temperature fluid compound but also all states that become a fluid upon reaction.

  In recent years, interest in fuel cells has increased from an environmental standpoint, and it is predicted that the demand for hydrogen as a raw material for fuel cells will increase in the future, and development of technology for producing hydrogen at low cost has been demanded.

  On the other hand, from the environmental point of view, recycling of waste plastics is desired. When the waste plastics are heat-treated, a large amount of hydrocarbons are generated by thermal decomposition. Therefore, hydrogen can be obtained by reforming hydrocarbons or the like with steam or oxygen.

  For example, Patent Document 1 discloses a reforming reaction apparatus in which a catalyst body that generates hydrogen by a catalytic reaction from a reaction fluid containing an organic compound (hydrocarbon or alcohol) or carbon monoxide is provided in a fluid flow path. In addition, a catalytic reaction apparatus is described in which at least a part of the catalyst body is configured to generate heat when energized. Then, using this apparatus, a reaction fluid containing an organic compound and water vapor (reforming gas) as a reactant is passed through to reform the organic compound to prepare a reformed gas such as hydrogen. (See paragraphs 0038 to 0040 of Patent Document 1 and FIG. 10).

  In this technique, the heating in the reforming process is premised on resistance heat generation, and the heating element that also serves as the catalyst body (catalyst carrier) is a honeycomb structure made of an alloy such as Fe-Cr-Al, Fe-Al, Fe-Cr, etc. It is formed by a body or the like (see paragraph 0041).

  In addition, as a further issue, harmful organic compounds that adversely affect the human body may be released into the atmosphere, and from the viewpoint of environmental protection, these organic compounds are made harmless before being released into the atmosphere. Decomposition and modification are desired.

  In order to cope with this, various technologies have been proposed in which harmful organic compounds are adsorbed and then reformed to harmless carbon dioxide, etc. by heating to a temperature required for decomposition using a catalyst or an oxidation aid. ing.

  For example, in Patent Document 2, an activated carbon adsorption layer provided with means capable of heating to the desorption temperature by resistance heating in the exhaust gas flow, and an oxidizer layer that oxidizes an organic compound on the downstream side thereof are installed. A method is disclosed in which the organic compound is adsorbed and heated and desorbed, and further, the organic compound is decomposed and modified after desorption in the oxidizer layer. In the case of this method, it is assumed that the adsorbent capable of resistance heating such as activated carbon is directly energized, and since activated carbon is used, it cannot be heated to a temperature range higher than the ignition point of activated carbon. Further, since direct energization is performed, if dust or the like in the exhaust gas accumulates in the resistance heating body, the resistance value fluctuates, making it difficult to control the entire temperature.

Similar to this method, Patent Document 3 discloses a method in which an organic compound is adsorbed on an adsorbent having an oxidizing function and then the inside of the adsorbed layer is decomposed by creeping discharge with low-temperature plasma. In the case of this method, since the decomposition temperature is not a method of heating the adsorbent itself at a high temperature, the object to be treated is limited to a low concentration volatile organic substance.
JP-A-11-130405 Japanese Patent Laid-Open No. 9-206557 (see claims) JP 2004-41884 A (refer to claims etc.)

  The present invention provides a fluid organic compound reforming method capable of easily decomposing and / or modifying a fluid organic compound and improving productivity with a novel configuration not described in the above-mentioned prior art documents. And it is set as a subject (object) to provide a processing apparatus.

  The fluid organic compound treatment method of the present invention solves the above object (problem) by the following constitution.

In the present invention, a fluid organic compound as a starting material is adsorbed in a reaction layer and decomposed in the presence of at least one reaction gas selected from the group consisting of H ₂ O, CO ₂ , CO, and O _2. In a method for treating a fluid organic compound that obtains a reformed gas by performing a reaction and / or a treatment by a reforming reaction (referred to as “decomposition reforming treatment”, hereinafter the same applies)
A fluid adsorption step in which at least part of the reaction layer is formed of a substance that generates heat by absorbing microwaves (hereinafter referred to as “microwave exothermic substance”), and adsorbs an organic compound to the reaction layer at room temperature;
While the supply of the fluid organic compound is stopped, the reaction layer is heated or maintained at a first set temperature at which the fluid organic compound can be decomposed and modified by microwave heating means, and the reaction gas is supplied. A cracking and reforming process for cracking and reforming;
And a reaction layer regeneration step for performing a regeneration treatment of the microwave exothermic material while heating or maintaining the reaction layer at a second preset temperature higher than the first preset temperature by a microwave heating means,
The three steps are sequentially repeated.

  As described above, the decomposition and reforming treatment is divided into three steps of the adsorption step, the decomposition and reforming step, and the reaction layer regeneration step, and the following effects are obtained by repeating the steps sequentially.

  Since the fluid organic compound is adsorbed to the reaction layer that has undergone the reaction layer regeneration process at room temperature, the adsorption efficiency of the fluid organic compound is better than when the fluid organic compound and the reaction gas are simultaneously introduced into the high-temperature reaction layer. Become. This is because the reaction layer is in an unused or regenerated (activated) state suitable for adsorption, and the adsorption property is generally better at a low temperature than at a high temperature. Further, since the fluid organic compound and the reaction gas are not simultaneously introduced into the reaction layer, the reaction control is facilitated.

  For the fluid organic compound stably adsorbed on the reaction layer, the reaction gas (reforming gas) can be selectively introduced into the reaction layer heated and maintained at a temperature suitable for the reaction (first set temperature). The reaction efficiency (reforming efficiency) can be maximized.

  By using the reaction layer as a microwave exothermic substance, direct heating (dielectric heating) is possible when microwave irradiation is performed. For this reason, uniform heating is possible by controlling the temperature to be suitable for the decomposition and reforming reaction of the fluid organic compound that is the object to be processed. In microwave heating, temperature control and uniform heating are easier than resistance heating. In addition, the fluid organic compound (dielectric) is also directly heated (dielectric heating) by the microwave, and thermal decomposition is easily promoted. Furthermore, since direct current is not applied like the resistance heating elements of Patent Documents 1 and 2, dust or the like in the exhaust gas is accumulated, and there is no problem that the resistance value fluctuates and temperature control becomes difficult. Furthermore, even in steam reforming, measures for electric leakage are not required. Moreover, the thermal decomposition component (hydrocarbon etc.) of waste plastic can be used as a raw material, and hydrogen etc. can be manufactured at low cost.

  The reforming reaction of fluid organic compounds (including those generated with the decomposition reaction) in the reaction layer in the presence of the reaction gas is as follows in the case of aliphatic hydrocarbons or aliphatic alcohols. In each of the following reaction formulas, “+ Q” indicates a calorific value, and “−Q” indicates an endothermic amount.

1) Direct reforming of aliphatic hydrocarbons by catalytic oxidation ...
2C _n H _{2n + 2} + (3n + 1) O ₂ → 2nCO ₂ +2 (n + 1) H ₂ O + Q1
2) Reforming of aliphatic hydrocarbons with steam
_{C n H 2n + 2 + nH} 2 O → nCO + (2n + 1) H 2 -Q2
3) Modification of aliphatic hydrocarbons with carbon dioxide
_{C n H 2n + 2 + nCO} 2 → 2nCO + 2 (n + 1) H 2 -Q3
4) Reforming of aliphatic hydrocarbons with carbon monoxide
CH ₄ + CO → C ₂ H ₂ + H ₂ O-Q4
C ₂ H ₆ + CO + H ₂ O → 2CH ₃ COOH-Q4 ′
5) Modification of aliphatic alcohol by steam ...
_{C n H 2n + 1 (OH} ) + nH 2 O → nCO 2 + (2n + 1) H 2 -Q5
These reactions are all endothermic except for 1), and the reaction to the right side is promoted by heating.

  In the above 2) and 3), in the case of the fuel gas, this may be left as it is. However, when the reformed gas is used as a fuel cell in the fuel cell, the CO of the product gas is changed by the following CO shift reaction or CO selective oxidation reaction. Further reforming treatment is necessary to reduce it. This is because CO may poison the fuel cell electrode. (See Patent Document 1, paragraph 0018).

6) CO shift reaction: CO + H ₂ O → CO ₂ + H ₂ + Q6
7) CO selective oxidation reaction: CO + 1 / 2O ₂ → CO ₂ + Q7
In the above configuration, the first set temperature is 100 to 600 ° C., and the second set temperature is appropriately selected from the range of 200 to 900 ° C. according to the type of fluid organic compound and reaction gas and the type of reformed gas. .

  Moreover, although the processing method of this invention can also be set as the structure with a single reaction layer, it can be set as each following structure provided with two or more of the following reaction layers.

  One aspect thereof is a configuration in which a plurality of the reaction layers are provided in parallel, the adsorption step is sequentially performed in another reaction layer, and a time difference is provided. That is, before the adsorption step is performed again in each reaction layer, a time difference is set so as to end the reaction layer regeneration step in each reaction layer, and the fluid organic compound is continuously supplied and processed. In addition, it is not necessary to stop the supply of the fluid organic compound as a raw material to the reaction layer during the reaction step or the reaction layer regeneration step. In addition, because the reaction layer that has undergone the reaction layer regeneration step is used in the adsorption step, the adsorption efficiency is good, and the catalytic ability of the cracking catalyst is recovered and used in the cracking and reforming step. Can be maintained.

In another aspect, a plurality of the reaction layers are provided in series, the reaction layers are formed of packed particles, and the packed particles are moved continuously or intermittently in the order of arrangement of the reaction layers, In each reaction layer, all the processes of the adsorption process, the decomposition reforming process, and the reaction layer regeneration process are sequentially performed , or the adsorption process is performed in the first reaction layer, and in the remaining reaction layers, In this configuration, the decomposition and reforming step and the reaction layer regeneration step are continuously performed in an inclined manner , and the discharged packed particles are reintroduced into the front reaction layer. Before the reaction layer is degraded by the catalyst poison (for example, CO) and the catalytic action of the decomposition catalyst is lowered, the packed particles forming the reaction layer are moved to the regeneration treatment container and further used for circulation. The closed system can be operated continuously.

  It is preferable that at least a part of the reaction layer is a decomposition catalyst component of the fluid organic compound. This is because the decomposition reaction of the fluid organic compound at a low temperature can be promoted, and the temperature can be easily controlled.

  The microwave exothermic substance is usually composed of one or two or more selected from metal oxides, metal carbides or carbons, or composites thereof, or mainly composed thereof.

  Here, the metal oxide as the microwave exothermic material is selected from one or more of a group of transition metal oxides and a group of typical metal oxides composed of aluminum, lead, indium and tin. Many of these have selectivity for the decomposition reaction of fluid organic compounds and have high catalytic activity, and can also serve as decomposition catalyst components.

  Among the metal oxides, β-alumina, γ-alumina, titanium oxide, iron oxide, zirconium oxide and cerium oxide (hereinafter referred to as “specific metal oxide”) have particularly high catalytic activity and microwave heat generation characteristics. Is desirable and desirable.

  The composite as the microwave exothermic material is red mud, inorganic sludge, clinker (coal bottom ash), calcium ferrite, iron oxide-containing sludge, flue / boiler scale treated blast material, aluminum dross, incinerated ash, zeolite, One or more are selected from the group of sodium aluminate and coal fly ash. These have the same advantages as the specific metal oxides and are contained in a large amount in industrial waste, so that waste can be recycled.

  And the processing apparatus of the fluid organic compound suitable for the processing method of the said fluid organic compound becomes the following structure.

A process having a function of decomposing and reforming a raw material fluid organic compound in the presence of a reaction gas in the presence of the reaction gas to obtain a reformed gas, and further regenerating the reaction layer. In the device
A processing vessel provided with the reaction layer, a fluid supply means, and a microwave heating means,
The processing container includes therein a reaction layer containing a microwave exothermic material having at least a function of adsorbing the fluid organic compound, a fluid inlet for supplying the fluid organic compound or the reaction gas, and the reforming A gas outlet for discharging gas,
The fluid supply means is connected to the fluid inlet so that the fluid organic compound and the reaction gas can be independently fed,
The microwave heating means is characterized in that the reaction layer is provided so as to be able to be heated and maintained at each set temperature of the decomposition reforming process and the regeneration process of the reaction layer.

  In the apparatus, the reaction layer may be single, but the following configurations are suitable for continuous processing.

  In one aspect thereof, a plurality of the processing containers each having the reaction layer are arranged in parallel, and the fluid supply unit separately supplies the fluid organic compound and the reaction gas to the reaction layers in the processing containers. It is the structure which has the control mechanism which can be supplied simultaneously.

According to another aspect, a plurality of the processing containers provided with the reaction layer formed by the packed particles are arranged in series, and the packed particles are continuously or intermittently arranged in the order of arrangement between the processing containers. With moving means to move automatically,
The plurality of processing vessels include a raw material adsorption vessel having a raw material fluid inlet portion in order of arrangement, a reaction gas fluid inlet portion and a decomposition and reforming vessel having the microwave heating means, and the microwave heating means. Recycled containers
The cracking and reforming container and / or the regeneration processing container includes a reformed gas discharge port, and the outlet of the packed granule of the regeneration processing container is an inlet of the packed granule of the raw material adsorption container; It is the structure connected so that the said filling granular material after reproduction | regeneration can be returned.

  In the processing apparatus having the above configuration, the decomposition and reforming container and the regeneration processing container may be the same container.

  The mode of the microwave exothermic material forming the reaction layer in each of the above processing apparatuses is the same as in the above processing method.

  The fluid organic compound treatment method and treatment apparatus of the present invention can perform decomposition and / or modification of a fluid organic compound easily and with good productivity by the configuration and action as described above. That is, there is no problem in resistance heating such as non-uniform temperature distribution, difficult temperature control, and time-consuming heating as in Patent Documents 1 and 2, and There is no need to control the temperature below a predetermined temperature, and furthermore, as in Patent Document 3, the object to be treated is not limited to a low concentration volatile organic substance.

  The present invention will be described in further detail below. In the following description, “%” indicating the composition means “% by mass” unless otherwise specified.

A. First embodiment:
FIG. 1 shows a conceptual diagram of a single processing container (single reaction layer) type in the fluid organic compound processing apparatus used in the present invention.

  In this apparatus, basically, a fluid organic compound (raw material) that is an object to be processed is adsorbed to a fixed reaction layer 11 and decomposed and reformed in the presence of a reaction gas to provide a reformed gas. And a processing apparatus having a function of regenerating the reaction layer.

  A single processing vessel 13 including the reaction layer 11, a fluid supply unit, and a microwave heating unit 17 are provided.

  The processing vessel 13 includes a reaction layer 11 containing a microwave exothermic material having at least a part of a raw material adsorption function, a fluid inlet 19 for supplying the raw material or the reactive gas, and a gas outlet for discharging the reformed gas. Part 21. In addition, the process container 13 is normally enclosed with the heat insulating material. The gas outlet 21 is provided with an on-off valve 22 in order to prevent a short path of the fluid organic compound and reaction gas supplied to the reaction layer and to control the flow rate, but may be omitted. Is possible.

  The fluid supply means is connected to the fluid inlet 19 so that the fluid organic compound (raw material) and the reaction gas can be independently fed. For example, the fluid supply means is formed by raw material / reactant gas supply pipes 23 and 25 each having a tank for each fluid (not shown), a fluid generation device, and a feeding device such as a pump, and is connected to the fluid inlet via the switching valve 15. The unit 19 is connected. Note that the fluid organic compound or the reaction gas may be introduced by suction means. Further, in the illustrated example, the fluid organic compound and the reaction gas have a single fluid inlet portion 19 and the mounting direction is horizontal, but the position thereof is arbitrary as long as the decomposition and reforming reaction can be performed. The organic compound and the reaction gas inlet may be separated. For example, a fluid inlet for a fluid organic compound is provided above the reaction layer 11, and a fluid inlet 19 for a reaction gas is provided below the reaction layer 11.

  The microwave heating means 17 is provided so that the reaction layer 11 can be heated and maintained at the first and second set temperatures of the decomposition reforming process and the reaction layer regeneration process. The processing container 13 may be provided with a plurality of measurement ports (not shown) such as temperature / humidity for control, and a stirring fan may be attached in order to equalize the temperature in the processing container 13. Further, although not shown, the microwave heating means 17 is provided with a power monitor attached to the waveguide so that the microwave output signal can be taken out and the microwave output can be controlled.

  The reaction layer 11 is formed of a filled granule or a porous molded body. The form of the formed particles of the filled granule is arbitrary, such as spherical, pellet, cylindrical, etc., and the form of the porous molded body is also arbitrary, such as a honeycomb, a porous plate laminate, and an open cell molded body. From the viewpoint of improving the adsorption performance, it is desirable that the form of these filled granules or porous molded body is increased in specific surface area.

  In the above, the reaction layer 11 includes at least a microwave exothermic substance, and further includes a decomposition catalyst component.

  Here, the microwave exothermic material can be formed of a filler (compound) different from the cracking catalyst component, but usually forms part or all of the cracking catalyst component.

  The microwave exothermic substance is a substance made of a substance (compound) having a large dielectric loss (dielectric constant (ε) × dielectric power factor (tan δ)). In general, those having a high dielectric constant have a large dielectric loss and are easily heated by dielectric heating. As a microwave heating material, one having at least one selected from metal oxides (including double oxides), metal carbides, carbons, or composites thereof having a relatively high dielectric constant, or Those based on them can be used. The numbers in parentheses after the chemical formulas exemplified below are relative dielectric constants. The relative permittivity is mainly quoted from the Chemical Society of Japan, “Chemical Handbook Revision 3rd Edition, Basic Volume II” (Akira-5) Maruzen, p505.

  Examples of the metal oxide include transition metal oxides and typical metal oxides of aluminum (Al), lead (Pb), indium (In), and tin (Sn) among typical elements.

Transition metal oxide: FeO (14.2), Fe ₂ O ₃ , Fe ₃ O ₄ , TiO ₂ (85.8), Cr ₂ O ₃ (12.0), ZrO ₂ (12.5), etc. .

Typical metal oxide: Al ₂ O ₃ (especially β-form and γ-form have good heat generation efficiency and desirable) (11.5), PbO (14.3), In ₂ O ₃ , SnO, SnO ₂ , etc.

Metal carbide: SiC (10.2), Fe ₃ C, etc.

As the composite, red mud (main component: Fe ₂ O ₃ —Fe ₃ O ₄ ), inorganic sludge (main component: FeO—Fe ₂ O ₃ —Fe ₃ O ₄ ), clinker (main component: SiO ₂ ) _2- Al ₂ O ₃ —CaO—Fe ₂ O ₃ ), calcium ferrite (main component: CaO—Fe ₂ O ₃ ), iron oxide-containing sludge, flue / boiler scale-treated blast material (main component: SiO ₂ — Fe ₂ O ₃ —Fe ₃ O ₄ ), aluminum dross residual ash (main components: Al ₂ O ₃ —Fe ₂ O ₃ , Fe ₃ O ₄ ), incineration ash (main component: Al ₂ O ₃ —SiO ₂ ), Zeolite (main component: Al ₂ O ₃ —SiO ₂ —Fe ₂ O ₃ ), coal fly ash (main component: Al ₂ O ₃ —SiO ₂ —Fe ₂ O ₃ ), sodium aluminate (Na ₃ AlO ₃ , NaAlO) ₂₎ industrial wastes such as (those which contains a large amount of the unused resources) are discarded Desirable to be able to achieve the recycling.

  The fluid organic compound treatment method using this apparatus is performed by sequentially repeating the following three steps (see FIG. 2).

  1) Fluid adsorption step: A fluid organic compound is supplied to the reaction layer, and the fluid organic compound is adsorbed at room temperature.

  2) Decomposition and reforming step: With the supply of the fluid organic compound stopped, the reaction layer is heated to or maintained at the first set temperature by the microwave heating means, and the reaction gas is supplied to decompose and reform the fluid organic compound. To do. Here, the first set temperature varies depending on the kind of the fluid organic compound, the composition of the reaction layer, and the productivity (economic efficiency), but it is, for example, 100 to 600 ° C., preferably 160 to 300 ° C. Select as appropriate.

  3) Reaction layer regeneration treatment step: The reaction layer (microwave exothermic substance) is regenerated while the reaction layer is heated or maintained at a second preset temperature higher than the first preset temperature by microwave heating means. Here, the second set temperature varies depending on the composition of the reaction layer and the productivity (economic efficiency), but is appropriately selected from the range of 200 to 900 ° C, preferably 250 to 450 ° C.

B. Second embodiment:
FIG. 3 also shows a conceptual diagram of the reaction vessel non-moving type (fixed type) with a plurality of processing containers. In the figure, the same parts as those in FIG. 1 are denoted by the same reference numerals, and the corresponding parts are denoted by a suffix (upper case alphabet), and the description thereof is omitted in whole or in part.

  A plurality (three in the illustrated example) of processing containers 13A, 13B, and 13C provided with non-moving reaction layers 11A, 11B, and 11C are provided in parallel, and fluid supply means are provided in the processing containers 13A, 13B, and 13C. The reaction layers 11A, 11B, and 11C have a control mechanism that can supply the fluid organic compound and the reaction gas separately or simultaneously.

  In the illustrated example, a raw material supply pipe 23 and a reaction gas supply pipe 25 for a fluid organic compound (raw material) and a reaction gas are respectively connected to the processing containers 13A, 13B, and 13C. It can be switched and supplied to each via the reactive gas first and second switching valves 16A and 16B. Each reformed gas outlet 21A, 21B, 21C is extended and connected to one reformed gas recovery pipe 20, and a switching (open / close) valve connected to the reformed gas recovery pipe 20 at the connection. 22A is arranged.

  Configurations relating to other processing containers, reaction layers, and microwave heating means are basically the same as those in the first embodiment.

  The processing method of the fluid organic compound using this apparatus basically sends the adsorption step sequentially to another reaction layer and repeats the adsorption step in each reaction layer. In this reaction layer regeneration step, the fluid organic compound is continuously supplied and continuously processed (see FIG. 4).

(1) First step:
The raw material supply pipe 23 is electrically connected only to the first processing vessel 13A by the raw material first switching valve 15A. At this time, the first switching valve 16A for the reaction gas is in the fully closed position, and the microwave heating means 17A is not activated (is off).

  Then, the fluid organic compound is supplied to the first reaction layer 11A and is adsorbed until the fluid organic compound reaches a set saturation level equal to or lower than the adsorption saturation state. The determination of the degree of saturation is a conventional method, for example, a method based on time such as a timer setting based on pre-stored data, a method based on measurement of a set concentration with a gas alarm, a set value of the microwave input / output ratio It can be performed by the method by.

(2) Second step:
The raw material supply pipe 23 is connected to only the second processing vessel 13B by the raw material first and second switching valves 15A and 15B, and the reactive gas is supplied by the first and second switching valves 16A and 16B for the reactive gas. The piping 25 is electrically connected only to the first processing container 13A, and the microwave heating means 17A of the first processing container 13A is turned on (energized state).

  Then, the reaction gas is supplied to the first reaction layer 11A in the microwave heating state, and the fluid organic compound is decomposed and reformed (decomposition and reforming step).

  At the same time, a fluid organic compound is supplied to the second reaction layer 11B and adsorbed until it reaches a saturated state (fluid adsorption step).

(3) Third step:
The raw material supply pipe 23 is electrically connected only to the third processing vessel 13C by the raw material first and second switching valves 15A and 15B, and the reactive gas is supplied by the reactive gas first and second switching valves 16A and 16B. The pipe 25 is electrically connected to only the first and second processing containers 13A and 13B, and the microwave heating means 17B of the second processing container 13B is turned on together with the microwave heating means 17A of the first processing container 13A.

  Then, since the first reaction layer 11A is almost completely decomposed and reformed, the regeneration process is performed by continuing the microwave heating state (reaction layer regeneration process). At this time, since the reaction gas is also supplied, the regeneration processing efficiency is increased and promoted.

  In addition, the reaction gas is supplied to the second reaction layer 11B in the microwave heating state, and the second reaction layer 11B is heated to decompose and reform the fluid organic compound (decomposition and reforming step).

(4) Fourth step:
Again, as in the first step, the raw material supply pipe 23 is brought into conduction only with the first processing vessel 13A. At this time, the reaction gas supply pipe 25 switches to the conduction of only the second and third processing vessels 13B and 13C and turns off the first microwave heating means 17A (second and third microwave heating means 17B, 17C remains on). By this time, the first reaction layer 11A is set so that the reaction layer regeneration step is completed.

  Then, the fluid organic compound is again supplied to the first reaction layer 11A and adsorbed until the fluid organic compound is saturated (fluid adsorption step). Thereafter, the process returns to the second process described above, and the second to fourth processes are repeated.

  Thus, the fluid adsorption step is sequentially performed in the order of the first, second, and third reaction layers, and the fluid adsorption step, the decomposition reforming step, and the reaction layer regeneration step are sequentially performed in each reaction layer. The fluid organic compound can be continuously supplied, and the continuous treatment of the fluid organic compound can be performed efficiently.

  In addition, when the total time of the decomposition reforming process and the reaction layer regeneration process in each reaction layer is longer than the time required to go around each reaction layer in the fluid adsorption process, the number of processing containers (reaction layers) is reduced. It is necessary to increase appropriately from three of the embodiments. Conversely, if the total time of the cracking and reforming step and the reaction layer regeneration step is the same as or shorter than the time of the fluid adsorption step, the cracking and reforming step and the reaction layer regeneration step are performed in the same processing vessel. The total number of containers may be two.

C. Third embodiment:
FIG. 5 shows an example in which a plurality of the reaction layers, which are formed of packed particles and are movable type capable of introducing and discharging the packed particles, are provided in series.

  In the illustrated example, a plurality of processing vessels 113A, 113B, and 113C including reaction layers 111A, 111B, and 111C are arranged in series, and the reaction layers 111A, 111B, and 111C are formed of packed granules F. The processing vessels 113A, 113B, and 113C are connected to each other through sealed ducts 26A and 26B that include moving means for moving the filled particles continuously or intermittently. The moving means may be a dead weight dropping method, but a forced moving method such as a screw. This is because the residence time in each reaction layer can be easily controlled.

  Each processing vessel has a raw material adsorbing vessel 113A provided with a raw material fluid inlet portion (referred to as “raw material inlet portion”, hereinafter the same) 119A in the order of arrangement, and the reaction gas fluid inlet portion (hereinafter referred to as “reactive gas inlet portion”). The same is applied to the cracking / reforming vessel 113B provided with 119B and the first microwave heating means 117A, and the regeneration processing vessel 113C provided with the reaction gas inlet 119C and the second microwave heating means 117B.

  The decomposition reforming vessel 113B and the regeneration processing vessel 113C are provided with reformed gas outlets 121A and 121B, and the inlet 27 for the charged particles of the raw material adsorption vessel 113A is provided at the outlet 27 of the charged particles of the regeneration processing vessel 113C. 29 and the regenerated filled particles F are connected so as to be able to be returned.

  Configurations relating to other processing containers, reaction layers, and microwave heating means are basically the same as in the above embodiment.

The fluid organic compound treatment method using this apparatus basically moves the packed particles continuously or intermittently in the order of arrangement of the reaction layers provided in series, and in each reaction layer, the adsorption step, All the processes of the decomposition reforming process and the reaction layer regeneration process are sequentially performed (see FIG. 6).

  While the microwave heating means 117A and 117B are turned on, the raw material and the reaction gas are introduced into the raw material adsorption vessel 113A with the first, second, and third on-off valves 115A, 115B, and 115C opened, and the reaction The gas is introduced into the decomposition reforming vessel 113B and the regeneration processing vessel 113C. At the same time, a moving means (not shown) such as a screw conveyor for the packed granules F is activated.

  Then, the fluid organic compound supplied to the raw material adsorption container 113A is adsorbed to the reaction layer 111A formed in the adsorption container. Then, the reaction layer 111A on which the fluid organic compound is adsorbed is moved into the decomposition reforming vessel 113B continuously or intermittently by the moving means to become the reaction layer 111B. Initially, in order to cause the reaction layer 111A to sufficiently adsorb (until substantially saturated), the movement of the packed granules F to the decomposition and reforming vessel 113B can be started after a predetermined time has elapsed. desirable.

  Here, the reaction gas is supplied into the decomposition reforming vessel 113B and heated by the first microwave heating means 117A in the on state, and in the reaction layer 111B in the decomposition reforming vessel 113B, the fluid organic compound Is decomposed and modified. The reformed gas generated by the cracking and reforming is recovered in the gas tank or the like as the reformed gas from the reformed gas outlet 121A.

  Furthermore, since the reaction gas is supplied also in the regeneration processing vessel 113C and heated by the second microwave heating means 117B in the on state, the reaction layer 111C is regenerated in the regeneration processing vessel 113C. Note that when the cracking and reforming is not complete in the cracking and reforming vessel 113B, the cracking and reforming is also performed in the reaction layer 111C in the regeneration processing vessel 113C. In this case, the generated reformed gas is recovered from the gas discharge port 121B. 122A and 122B are flow rate control on-off valves.

<Test example>
Tests conducted to confirm that the metal oxides and their composites used in the present invention exhibit good microwave characteristics will be described.

  200 g of each of the following 6 commercially available raw material powders were filled in φ90 × 65 mm alumina felt and irradiated with 1 kW microwave (2.45 GHz), and a temperature rise test was performed.

Commercial raw material powder: α-alumina, β-alumina, sodium aluminate, calcium ferrite, zeolite and coal fly ash From FIG. 7 showing the results, excluding α-alumina, each raw material powder such as β-alumina and calcium ferrite is It was confirmed that good microwave characteristics were exhibited.

It is a conceptual diagram of one processing container type in the processing apparatus provided with the fixed reaction layer of the fluid organic compound. It is a flowchart which shows the processing method (1st embodiment) of the fluid organic compound using the apparatus of FIG. It is a conceptual diagram of several types of processing containers in the processing apparatus provided with the fixed reaction layer of the fluid organic compound. It is a flowchart which shows the processing method (2nd embodiment) of the fluid organic compound using the apparatus of FIG. It is a conceptual diagram of several types of processing containers in the processing apparatus provided with the movement reaction layer of the fluid organic compound. It is a flowchart which shows the processing method (3rd embodiment) of the fluid organic compound using the apparatus of FIG. It is a graph which shows the test result of the microwave heat_generation | fever characteristic about the powder raw material which is a commercially available microwave heat generating body.

Explanation of symbols

11, 111A, 111B, 111C ... Reaction layer 11A ... First reaction layer 11B ... Second reaction layer 11C ... Third reaction layer 13 ... Processing vessel 13A ... First processing vessel 13B ... second processing vessel 13C ... third processing vessel 17 ... microwave heating means 17A, 117A ... first microwave heating means 17B, 117B ... second microwave heating means 17C ..Third microwave heating means 19, 119A ... Fluid inlet portion 21, 21A, 21B, 21C, 121A, 121B ... Reformed gas outlet portion 113A ... Raw material adsorption vessel (processing vessel)
113B ... Decomposition and reforming vessel (processing vessel)
113C ... Regeneration processing container (processing container)

Claims (19)

A fluid organic compound as a raw material is adsorbed on a reaction layer, and a decomposition reaction and / or a reforming reaction is performed in the presence of at least one kind of reaction gas selected from the group of H ₂ O, CO ₂ , CO, and O _2. In the method for treating a fluid organic compound to obtain a reformed gas by performing the treatment by the following (hereinafter referred to as "decomposition reforming treatment")
At least a part of the reaction layer is formed of a substance that absorbs microwaves and generates heat (hereinafter referred to as “microwave exothermic substance”), the fluid organic compound is supplied to the reaction layer, and the reaction layer is heated at room temperature. A fluid adsorption process for adsorbing fluid organic compounds;
In a state where supply of the fluid organic compound is stopped, the reaction gas is supplied while heating or maintaining the reaction layer at a first set temperature at which the fluid organic compound can be decomposed and modified by microwave heating means, A decomposition and reforming process for performing a decomposition and reforming treatment of the fluid organic compound;
And a reaction layer regeneration step of performing the regeneration treatment of the reaction layer while heating or maintaining the reaction layer at a second preset temperature higher than the first preset temperature by microwave heating means,
A method for treating a fluid organic compound, comprising sequentially repeating three steps.   The method for treating a fluid organic compound according to claim 1, wherein the first preset temperature is 100 to 600 ° C, and the second preset temperature is 200 to 900 ° C.   3. The method for treating a fluid organic compound according to claim 1, wherein the reaction layer is single.   The method for treating a fluid organic compound according to claim 1 or 2, wherein a plurality of the reaction layers are provided in parallel, the adsorption step is sequentially performed in another reaction layer, and a time difference is provided. A plurality of the reaction layers are provided in series, each reaction layer is formed of packed particles, the packed particles are moved continuously or intermittently in the order of arrangement of the reaction layers, and the reaction layers The entire process of the adsorption process, the decomposition reforming process and the reaction layer regeneration process is sequentially performed , or the adsorption process is performed by the front reaction layer, and the decomposition reaction reforming process and the remaining reaction layer are performed. 3. The fluid organic according to claim 1, wherein the reaction layer regeneration step is continuously performed in an inclined manner , and the discharged packed particles are reintroduced into the reaction layer in the foremost stage. Compound processing method.   The method for treating a fluid organic compound according to claim 1, wherein at least a part of the reaction layer is used as a decomposition catalyst component of the fluid organic compound.   2. The microwave exothermic material is one or two or more selected from metal oxides, metal carbides or carbons, or a composite thereof, or a substance mainly composed of them. The processing method of the fluid organic compound in any one of -6.   The metal oxide as the microwave heating substance is one or more selected from a group of transition metal oxides and a group of typical metal oxides composed of aluminum, lead, indium and tin. A method for treating a fluid organic compound according to claim 7.   9. The method for treating a fluid organic compound according to claim 8, wherein the metal oxide is β-alumina, γ-alumina, titanium oxide, iron oxide, zirconium oxide, or cerium oxide.   The composite as the microwave exothermic material is red mud, inorganic sludge, clinker (coal bottom ash), calcium ferrite, iron oxide containing sludge, flue / boiler scale treated blast material, aluminum dross, incinerated ash, zeolite, 8. The method for treating a fluid organic compound according to claim 7, wherein one or more kinds are selected from the group consisting of sodium aluminate and coal fly ash. A process having a function of decomposing and reforming a raw material fluid organic compound in the presence of a reaction gas in the presence of the reaction gas to obtain a reformed gas, and further regenerating the reaction layer. In the device
A processing vessel provided with the reaction layer, a fluid supply means, and a microwave heating means,
The processing container includes therein a reaction layer containing a microwave exothermic material having at least a function of adsorbing the fluid organic compound, a fluid inlet for supplying the fluid organic compound or the reaction gas, and the reforming A gas outlet for discharging gas,
The fluid supply means is connected to the fluid inlet so that the fluid organic compound and the reaction gas can be independently fed,
The microwave heating means is provided so that the reaction layer can be heated and maintained at each set processing temperature of the decomposition reforming process and the regeneration process of the reaction layer,
An apparatus for treating a fluid organic compound.   12. The fluid organic compound processing apparatus according to claim 11, wherein the reaction layer is single. Arranging a plurality of the processing vessels provided with the reaction layer in parallel,
12. The fluid organic compound according to claim 11, wherein the fluid supply means has a control mechanism capable of supplying the fluid organic compound and the reaction gas separately or simultaneously to the reaction layer in each processing container. Processing equipment. A plurality of the processing vessels provided with reaction layers formed by packed particles are arranged in series, and the moving particles move the packed particles continuously or intermittently between the processing vessels in the order of arrangement. connection,
The plurality of processing vessels include a raw material adsorption vessel provided with a raw material fluid inlet portion in order of arrangement, a reaction gas fluid inlet portion and a decomposition and reforming vessel provided with the microwave heating means, and the microwave heating means. A recycling container equipped with
The cracking and reforming container and / or the regeneration processing container includes a reformed gas discharge port, and the outlet of the packed granule of the regeneration processing container is an inlet of the packed granule of the raw material adsorption container; 12. The fluid organic compound treatment device according to claim 11, wherein the regenerated filled particles are connected so that they can be returned.   15. The fluid organic compound treatment apparatus according to claim 14, wherein the decomposition reforming vessel and the regeneration treatment vessel are the same vessel.   12. The microwave exothermic material is one or more selected from metal oxides, metal carbides or carbons, or a composite thereof, or is mainly composed of them. The processing apparatus of the fluid organic compound in any one of -15. The metal oxide as the microwave exothermic material is selected from one or more of the group of transition metal oxides and typical metal oxides of aluminum, lead, indium and tin. The processing apparatus of the fluid organic compound of Claim 16.   The fluid organic compound treatment apparatus according to claim 17, wherein the metal oxide is β-alumina, γ-alumina, titanium oxide, iron oxide, zirconium oxide, or cerium oxide.   The composite as the microwave exothermic material is red mud, inorganic sludge, clinker (coal bottom ash), calcium ferrite, iron oxide containing sludge, flue / boiler scale treated blast material, aluminum dross, incinerated ash, zeolite, 17. The apparatus for treating a fluid organic compound according to claim 16, wherein one or more kinds are selected from the group consisting of sodium aluminate and coal fly ash.

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