JP5016795B2 - High temperature and high pressure reactor and method for treating organic matter using the high temperature and pressure reactor - Google Patents

Description

  The present invention includes two hydrothermal reactions, which are to denature or decompose organic substances in high-temperature and high-pressure water by the action of hot water in the absence of oxygen, and wet oxidation reactions that oxidize organic substances after the hydrothermal reaction by supplying an oxidizing agent. The present invention relates to a high-temperature and high-pressure reactor used for carrying out a reaction, and a method for treating organic matter using the high-temperature and high-pressure reactor.

  There is already a method for treating organic waste using a supercritical water oxidation reaction in which an aqueous solution containing organic substances is maintained in a supercritical state under high temperature and high pressure conditions, and air is blown into the aqueous solution to perform supercritical oxidation decomposition. It has been proposed by the inventors (Patent Document 1).

  Furthermore, when decomposing or modifying organic substances in water, the wet oxidation reaction can be made more gentle by performing a two-stage reaction in which a wet oxidation reaction is performed after a hydrothermal reaction, and the target It has also been reported by the present inventors that the product can be efficiently recovered (Patent Document 2). According to this method, when an organic substance is hydrothermally decomposed (hydrothermal reaction) in hot water at 200 to 350 ° C. and 5 to 30 MPa, mainly hydroxymethylfurfural (5-HMF) and furfural (2-FA) are produced. It was elucidated to do. Furthermore, when an aqueous solution of 5-HMF and 2-FA is subjected to an oxidation reaction (hydrothermal oxidation reaction) while supplying oxygen in hot water at 200 to 350 ° C. and 5 to 30 MPa, acetic acid and formic acid may be generated. It was elucidated. 5-HMF and 2-FA are considered to be intermediate products that are easily converted into acetic acid and formic acid.

By such a method, the acetic acid yield obtained from cellulose is simply higher than the acetic acid yield obtained by hydrothermal oxidation of organic substances, and reaches 20% of the total carbon of cellulose.
JP 2001-129508 A JP 2003-145090 A

  When the organic substance is treated by performing the two-stage reaction of the hydrothermal reaction and the wet oxidation reaction as described above, a hydrothermal reactor for performing the hydrothermal reaction and a wet oxidation reactor for performing the wet oxidation reaction; These two reactors were prepared, and hydrothermal reaction and wet oxidation reaction were performed in separate reactors.

  Since it is necessary to use two reactors in this way, the equipment cost increases, and if one set of reactors is prepared, the reaction time is uniquely determined by the capacity of each reactor, and the kind of organic matter It was difficult to set the reaction time freely according to the above.

  The present invention has been made in view of the above circumstances, and it is possible to reduce the equipment cost by performing both the hydrothermal reaction and the wet oxidation reaction using a single reactor, and the reaction time can be freely set. It is an object of the present invention to provide a high-temperature and high-pressure reactor that can be set and a method for treating organic substances using the high-temperature and high-pressure reactor.

  When the present inventors use a single reactor and supply the oxidant to a predetermined position of the reactor by the oxidant supply means, the hydrothermal reaction and the wet oxidation reaction can be performed in a single reactor. The present inventors have found that the following two reactions can be performed, and have completed the present invention.

That is, the high-temperature and high-pressure reactor of the present invention has high-temperature and high-pressure water inlets and outlets at both ends so that high-temperature and high-pressure water containing organic matter flows continuously from the inlet side toward the outlet side. A single high-temperature high-pressure reactor, and at least one oxidant supply means for supplying an oxidant to a predetermined position inside the reactor, wherein the inside of the reactor is high-temperature high-pressure Hydrothermal reaction part that denatures or decomposes organic matter in high-temperature and high-pressure water by the action of hot water in the upstream region from the predetermined position of the water flow and hydrothermal heat from the predetermined position downstream of the high-temperature and high-pressure water flow It is comprised with the wet oxidation part which oxidizes the organic substance after reaction .

In the high-temperature and high-pressure reactor of the present invention, it is preferable that the inlet is provided at the lower end of the reactor and the carry-out port is provided at the upper end of the reactor.
It is preferable that the at least one oxidant supply means is arranged so that the ratio of the hydrothermal reaction part and the wet oxidation reaction part can be adjusted.

  In the high-temperature and high-pressure reactor of the present invention, the at least one oxidant supply means is a single oxidant supply nozzle inserted into the reactor from either the inlet side or the outlet side of the reactor. The insertion length of the oxidant supply nozzle into the reactor is preferably adjusted.

  In the high-temperature and high-pressure reactor of the present invention, the at least one oxidant supply means is a plurality of oxidant supply nozzles inserted into the reactor from either the inlet side or the outlet side of the reactor. In addition, it is preferable that each oxidant supply nozzle has a different insertion length into the reactor.

  In the high-temperature and high-pressure reactor of the present invention, the at least one oxidant supply means is a single oxidant supply nozzle inserted into the reactor from either the inlet side or the outlet side of the reactor. It is preferable that the oxidant supply nozzle has a plurality of oxidant outlets.

  The organic matter treatment method of the present invention is an organic matter treatment method using the high-temperature and high-pressure reactor described in any one of the above, wherein the high-temperature and high-pressure reactor is connected to the outlet from the inlet side of the reactor. A high-temperature and high-pressure water containing organic substances is continuously flowed toward the reactor, and an oxidant is supplied to a predetermined position inside the reactor by an oxidant supply means, so that a high-temperature and high-pressure from the inlet of the reactor to the predetermined position is supplied. In the upstream region of the water flow, hydrothermal reaction is performed to denature or decompose organic matter in the high temperature and high pressure water by the action of hot water in the absence of oxygen, and in the downstream region of the high temperature and high pressure water flow from the predetermined position to the discharge port It is characterized in that a wet oxidation reaction for oxidizing the organic substance after the hydrothermal reaction is performed.

  In the present invention, high-temperature and high-pressure water containing organic substances is continuously flowed from the inlet side to the outlet of the reactor of the high-temperature and high-pressure reactor, and the oxidizing agent is supplied to a predetermined position inside the reactor by the oxidizing agent supply means. Supplying, and causing a hydrothermal reaction to denature or decompose the organic matter in the high-temperature high-pressure water by the action of hot water in the oxygen-free state in the upstream region of the high-temperature high-pressure water flow from the inlet of the reactor to the predetermined position, Since the wet oxidation reaction for oxidizing the organic substance after the hydrothermal reaction is performed in the downstream region of the high-temperature high-pressure water flow from the predetermined position to the discharge port, both the hydrothermal reaction and the wet oxidation reaction are performed in a single manner. This can be carried out in a reactor, and the equipment cost can be reduced as compared with the conventional necessity of preparing two reactors.

  Further, since the insertion length inside the reactor of the oxidant supply means inserted into the reactor can be adjusted as appropriate, the ratio between the hydrothermal reaction section and the wet oxidation reaction section inside the reactor can be easily set. The time required for each reaction can be freely set.

  Hereinafter, with reference to the drawings, a high-temperature and high-pressure reactor of the present invention and a method for treating organic substances using the high-temperature and high-pressure reactor will be described in detail.

(Embodiment 1)
FIG. 1 is a schematic diagram showing a high-temperature and high-pressure reactor according to the first embodiment.

  The high-temperature and high-pressure reactor of Embodiment 1 has a reactor (1) that provides each reaction field for hydrothermal reaction and wet oxidation reaction. The reactor (1) must have heat resistance and pressure resistance so that a hydrothermal reaction and a wet oxidation reaction can be performed. For example, a reactor having a heat resistance temperature of 400 ° C. and a pressure resistance of 40 MPa is used. It is done. Moreover, although there is no limitation in particular also about the shape, a tubular thing is used, for example.

  At each end of the reactor (1), flanges (2a, 2b) are provided, which are sealed so that the internal pressure is maintained at a high pressure.

  Each flange (2a, 2b) has an inlet and an outlet for introducing and discharging high-temperature and high-pressure water into the reactor (1).

  In addition, a hole is formed in one of the flanges (2a, 2b), and the oxidant supply nozzle (3) is inserted through the hole. The tip of the oxidant supply nozzle (3) is formed in a cylindrical shape that ejects oxidant. The oxidizing agent supplied from the oxidizing agent supply nozzle (3) may be arbitrary, and examples thereof include liquid hydrogen peroxide solution, gaseous air, and oxygen.

  In the high-temperature high-pressure reactor shown in FIG. 1, a tubular reactor (1) is installed such that its longitudinal direction is along the vertical direction, and an inlet for high-temperature high-pressure water is formed in the flange (2b) at the lower end. A high-temperature and high-pressure water outlet was formed in the flange (2a) at the upper end. In this way, by allowing the high-temperature and high-pressure water to flow from the lower side to the upper side in the reactor (1), the gaseous or liquid oxidant ejected from the oxidant supply nozzle (3), particularly the gaseous state The direction of upward movement due to the buoyancy of the oxidant coincides with the flow direction of the high-temperature and high-pressure water, so that the backflow of the oxidant to the high-temperature and high-pressure water flow can be prevented. , The upstream side of the high-temperature and high-pressure water flow (region (A) in FIG. 1) from the predetermined position to the hydrothermal reaction section, and the downstream side of the high-temperature and high-pressure water flow from this predetermined position (region A). In FIG. 1, (B) region) can be defined as the wet oxidation reaction part.

  The oxidant supply nozzle (3) can appropriately adjust the insertion length into the reactor (1), thereby adjusting the ratio of the hydrothermal reaction section and the wet oxidation section in the reactor (1). The time required for each reaction can be easily adjusted according to the results of the basic test and the adjustment operation. Further, as shown in FIG. 1, the oxidant supply nozzle (3) is inserted from the upper end side, and the high-temperature high-pressure water generated before the oxidant reaches the jet port at the lower end of the oxidant supply nozzle (3). Since it passes through the flow, the effect of preheating can be expected by heat exchange with high-temperature and high-pressure water around the nozzle.

  In the high-temperature and high-pressure reactor shown in FIG. 1, the oxidant supply nozzle (3) is configured to be inserted from the upper end flange (2a), but the oxidant is supplied into the reactor (1). If it can, it may be inserted from any flange. FIG. 2 shows another high-temperature and high-pressure reactor of the first embodiment, which is configured by inserting an oxidant supply nozzle (3) from a flange (2b) at the lower end. 2 is exactly the same as that in FIG. 1 except for the insertion position of the oxidant supply nozzle (3), and therefore, the same reference numerals as those in FIG. Detailed description will be omitted.

  A heater (4) for heating the reactor (1) at each position is provided in a plurality of locations on the entire surface around the reactor (1). The heater (4) is provided in a plurality of locations, because the required amount of heat may be different at each position of the reactor (1), and the temperature state is controlled according to each location. The purpose is that.

  The water containing the raw material slurry, which is an organic substance, introduced into the introduction port of the high-temperature high-pressure water of the reactor (1) is brought into a high-pressure state by the high-pressure metering pump (5). Further, the oxidizing agent such as oxygen is pressurized by the high-pressure metering pump (6), and is thereby supplied at a predetermined pressure from the oxidizing agent supply nozzle (3).

  Using the high-temperature and high-pressure reactor of the above configuration, high-temperature and high-pressure water containing organic substances such as raw material slurry is continuously flowed from the inlet side to the outlet of the reactor (1) of this apparatus, and an oxidant supply nozzle If an oxidizing agent such as oxygen is supplied from (3), the region from the lower end side of the reactor (1) to the oxidizing agent outlet of the oxidizing agent supply nozzle (3) ((A) in FIG. 1) In this case, a hydrothermal reaction can be performed by the action of hot water in an oxygen-free state, and the organic matter in the high-temperature and high-pressure water is denatured or decomposed. In addition, the organic substance hydrothermally reacted in the region A reaches a region (shown by (B) in FIG. 1) from the oxidant outlet of the oxidant supply nozzle (3) to the upper end by the flow of high-temperature and high-pressure water. In this region B, the organic matter after the hydrothermal reaction is oxidized by the action of the oxidizing agent. The organic matter after the hydrothermal reaction and wet oxidation reaction, the unreacted oxidant and the generated gas are discharged from the outlet.

  By sequentially performing such a hydrothermal reaction and a wet oxidation reaction, for example, specifically, the temperature inside the reactor is set to 200 to 450 ° C., and an aqueous solution introduced from the inlet is used as an alkali such as sodium hydroxide. A lower monocarboxylic acid such as acetic acid and formic acid can be obtained in a high yield by using an aqueous solution containing an organic substance such as a catalyst and cellulose at a pressure of 5 to 40 MPa and introducing from an inlet.

(Embodiment 2)
FIG. 3 is a schematic diagram showing the high-temperature and high-pressure reactor according to the second embodiment, in which (a) shows an oxidant supply nozzle inserted from the upper end, and (b) shows an oxidant supply nozzle from the lower end. Indicates the inserted one.

  In this high-temperature and high-pressure reactor, an oxidant supply nozzle (11) for supplying an oxidant is detachable into several blocks by screwing or the like. The insertion length of the nozzle (11) can be adjusted. Thereby, it is possible to adjust the ratio of the hydrothermal reaction part and the wet oxidation part in the reactor (1), and easily adjust the time required for each reaction according to the results of the basic test and the adjustment operation. be able to. Since the other configuration is the same as that of the high-temperature and high-pressure reactor of the first embodiment, detailed description thereof will be omitted assuming that the same reference numerals as those in FIG. In FIG. 3, a heater for heating the periphery of the reactor is omitted in order to make the drawing easy to see.

(Embodiment 3)
4A and 4B are schematic views showing the high-temperature and high-pressure reactor according to the third embodiment. FIG. 4A is a diagram in which an oxidant supply nozzle is inserted from the upper end, and FIG. 4B is an oxidant supply nozzle from the lower end. Indicates the inserted one.

  This high-temperature and high-pressure reactor has a plurality of oxidant supply nozzles (21) for supplying an oxidant, and the oxidant supply nozzles (21) have different lengths. . Each oxidant supply nozzle (21) is connected to the switching valve (22) outside the reactor, and the supply of the oxidant is opened and closed separately by switching the switching valve (22). By switching selection of this oxidant supply nozzle (22), it is possible to adjust the ratio of the hydrothermal reaction part and the wet oxidation part inside the reactor (1), and depending on the results of the basic test and adjustment operation, The time required for each reaction can be easily adjusted. Further, by supplying oxidant simultaneously from the oxidant supply nozzles (21) having different insertion lengths, stepwise oxidation is performed in which the amount of oxidant supplied in stages increases toward the downstream of the flow. It is also possible. Since the other configuration is the same as that of the high-temperature and high-pressure reactor of the first embodiment, detailed description thereof will be omitted assuming that the same reference numerals as those in FIG. In FIG. 4, a heater for heating the periphery of the reactor is omitted to make the drawing easier to see.

(Embodiment 4)
FIG. 5 is a schematic diagram showing the high-temperature and high-pressure reactor according to the fourth embodiment. FIG. 5A is a diagram in which an oxidant supply nozzle is inserted from the upper end, and FIG. Shows what was inserted.

  In this high-temperature and high-pressure reactor, the oxidant supply nozzle (31) has a jet port (32) for supplying an oxidant to a plurality of locations. Thereby, it is possible to adjust the ratio of the hydrothermal reaction part and the wet oxidation part in the reactor (1), and easily adjust the time required for each reaction according to the results of the basic test and the adjustment operation. be able to. In addition, since the oxidant jets (32) are provided at a plurality of locations, a small amount of oxidant can be supplied to the hydrothermal reaction section as a dehydration polymerization inhibitor in the hydrothermal reaction. Moreover, a rapid oxidation reaction can be prevented by supplying an oxidizing agent in steps at a plurality of locations. Since the other configuration is the same as that of the high-temperature and high-pressure reactor of the first embodiment, detailed description thereof will be omitted assuming that the same reference numerals as those in FIG. In FIG. 5, a heater for heating the periphery of the reactor is omitted in order to make the drawing easy to see.

  The present invention includes two hydrothermal reactions, which are to denature or decompose organic substances in high-temperature and high-pressure water by the action of hot water in the absence of oxygen, and wet oxidation reactions that oxidize organic substances after the hydrothermal reaction by supplying an oxidizing agent. High temperature and high pressure reactor used for reaction and processing method of organic substance using the high temperature and high pressure reactor, equipment by performing both hydrothermal reaction and wet oxidation reaction using a single reactor It is possible to provide a high-temperature high-pressure reactor capable of reducing costs and freely setting the reaction time, and a method for treating organic substances using the high-temperature high-pressure reactor.

1 is a schematic diagram showing a high-temperature and high-pressure reactor according to Embodiment 1. FIG. FIG. 2 is a schematic view showing another high-temperature and high-pressure reactor according to Embodiment 1. It is the schematic which shows the high temperature / high pressure type reactor of Embodiment 2, (a) is what the oxidant supply nozzle was inserted from the upper end, (b) is what the oxidant supply nozzle was inserted from the lower end. Is shown. It is the schematic which shows the high temperature / high pressure type reactor of Embodiment 3, (a) is what the oxidant supply nozzle was inserted from the upper end, (b) is what the oxidant supply nozzle was inserted from the lower end. Is shown. It is the schematic which shows the high temperature / high pressure type reactor of Embodiment 4, (a) is what the oxidant supply nozzle was inserted from the upper end, (b) is what the oxidant supply nozzle was inserted from the lower end. Is shown.

Explanation of symbols

1 Reactor 2a Flange 2b Flange 3 Oxidant Supply Nozzle 4 Heater 5 High Pressure Metering Pump 6 High Pressure Metering Pump

Claims (7)

A single high-temperature high-pressure type that has high-temperature and high-pressure water inlets and outlets at both ends, and allows high-temperature and high-pressure water containing organic substances to flow continuously from the inlet side to the outlet side. A reactor,
At least one oxidant supply means for supplying an oxidant to a predetermined position inside the reactor ;
A hydrothermal reaction section in which the inside of the reactor denatures or decomposes organic matter in high-temperature high-pressure water by the action of hot water in an oxygen-free state upstream from the predetermined position of the high-temperature high-pressure water flow, and the predetermined high-temperature high-pressure water flow. A high-temperature and high-pressure reactor comprising a wet oxidation unit that oxidizes an organic substance after a hydrothermal reaction in a downstream region from a position . The lower end of the inlet is the reactor, the upper end of the outlet the reactor, are provided, high-temperature high-pressure reactor as claimed in claim 1. 3. The high-temperature and high-pressure reactor according to claim 1, wherein the at least one oxidant supply unit is arranged so that a ratio between the hydrothermal reaction unit and the wet oxidation reaction unit can be adjusted. The at least one oxidant supply means is a single oxidant supply nozzle inserted into the reactor from either the inlet side or the outlet side of the reactor, and the oxidant supply nozzle is The high-temperature and high-pressure reactor according to any one of claims 1 to 3 , wherein an insertion length into the reactor is adjustable. The at least one oxidant supply means is a plurality of oxidant supply nozzles inserted into the reactor from either the inlet side or the outlet side of the reactor, and each oxidant supply nozzle has the reaction The high-temperature and high-pressure reactor according to any one of claims 1 to 3 , wherein insertion lengths into the vessel are different from each other. The at least one oxidant supply means is a single oxidant supply nozzle inserted into the reactor from either the inlet side or the outlet side of the reactor, and the oxidant supply nozzle is an oxidant supply nozzle. The high-temperature and high-pressure reactor according to any one of claims 1 to 3 , wherein the agent has jet nozzles at a plurality of locations. It is a processing method of the organic substance using the high temperature / high pressure type reactor according to any one of claims 1 to 6 ,
High-temperature high-pressure water containing organic substances is continuously flowed from the inlet side to the outlet of the reactor of the high-temperature and high-pressure reactor, and the oxidizing agent is supplied to a predetermined position inside the reactor by the oxidizing agent supply means. A hydrothermal reaction in which the organic matter in the high-temperature and high-pressure water is denatured or decomposed by the action of hot water in the absence of oxygen in the upstream region of the high-temperature and high-pressure water flow from the inlet of the reactor to the predetermined position, A method for treating organic matter, characterized by causing a wet oxidation reaction to oxidize organic matter after hydrothermal reaction in a downstream region of a high-temperature and high-pressure water flow from a predetermined position to a discharge port.

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