JP5382679B2 - Phosphate recovery method - Google Patents

Description

  The present invention relates to a method of treating phosphorus-containing biomass with a high-temperature and high-pressure gas and recovering phosphate from a treated product.

  Conventionally, livestock excrement has been treated by recycling, such as composting and returning to farmland. However, since the compost is in an excessive supply state, a new method for treating livestock excreta different from the above method has been desired.

Under such circumstances, in recent years, energy conversion technology using biomass such as livestock manure, garbage, food waste, sewage sludge and the like as a raw material has been developed. As an energy conversion technology using biomass as a raw material, for example, a method of fermenting biomass with microorganisms to generate fuel gas, a method of generating pressurized fuel water using water contained in biomass, and generating fuel gas As the improved method of the latter, a method of gasifying wet biomass with supercritical water using a catalyst to generate fuel gas is known (for example, see Patent Documents 1 to 3). .
Japanese National Patent Publication No. 11-502891 JP 2002-105466 A JP 2002-105467 A

However, the by-products obtained from the energy conversion technology using biomass as a raw material have not been effectively used.
Then, this invention aims at providing the method of processing the biomass containing phosphorus with high temperature high pressure gas, and collect | recovering phosphates from the reaction material after a process.

  As shown in the following examples, the present inventors apply an impact from the outside of the piping of the second heat exchanger provided in the biomass gasification system, thereby removing the biomass slurry attached to the piping. It was clarified that the clogging in the piping caused by the biomass slurry body peeled off and adhered in the piping could be prevented. At the same time, as shown in the examples below, the present inventors recovered chicken phosphate containing hydroxyapatite from the reaction product (supercritical water gasification byproduct) obtained by treating chicken manure with high-temperature and high-pressure gas. It has been clarified that this can be done, and the present invention has been completed.

  That is, the phosphate recovery method according to the present invention is a method in which phosphorus-containing biomass is treated with a high-temperature and high-pressure gas, and phosphate is recovered from the treated product, in the presence of a nonmetallic catalyst. In the above, the non-metallic catalyst obtained by hydrothermally treating biomass under conditions of a temperature in the range of 100 to 250 ° C. and a pressure in the range of 0.1 to 4 MPa, The biomass slurry containing is introduced into a heater and heated, the heated biomass slurry is introduced into a preheater and preheated, and the preheated biomass slurry is introduced into a reactor. Hydrothermally treated under conditions of a temperature of 374 ° C. or higher and a pressure of 22.1 MPa or higher, the ash generated in the hydrothermal treatment is reacted with hydrochloric acid, and the hydrochloric acid after the reaction with the ash is filtered, Filter hydrochloric acid Reacting the filtrate with an aqueous sodium hydroxide solution, collecting the precipitate formed after reacting the filtrate with the aqueous sodium hydroxide solution, the heater with the biomass slurry attached thereto, the preheating The adhering biomass slurry body is peeled off from the inner surface by giving an impact to at least one inner surface of the piping connecting the reactor and the reactor or the inner surface of the reactor. .

  The step of applying an impact to the inner surface preferably includes the step of applying vibration to the inner surface or the step of spraying a gas on the inner surface. In the phosphate recovery method, it is preferable that an impact is applied to the inner surface when the pressure in the heater becomes 26.0 MPa or more.

  In the phosphate recovery method, the product gas, ash, nonmetallic catalyst, and water produced by hydrothermal treatment are mixed with the product gas, the ash, the nonmetallic catalyst, and water. The ash may be reacted with hydrochloric acid by reacting the mixed solution with hydrochloric acid.

  Here, it is preferable to make it react with sodium hydroxide aqueous solution so that the pH of the said filtrate may be 6.0-9.0. Examples of the precipitate include monetite (dicalcium phosphate) and / or hydroxyapatite.

Further, in the phosphate recovery method, the phosphorus is obtained by using exhaust heat of a power generation device that generates power using the generated gas or heat of exhaust gas obtained by burning the generated gas with the heater. The contained biomass may be heated.

Furthermore, in the phosphate recovery method, in the step of introducing and heating the slurry body into a heater, the slurry body is heated by burning a part of the generated gas in a gas containing oxygen,
The oxygen-containing gas may be preheated using exhaust heat of a power generation device that generates power using the generated gas or heat of exhaust gas obtained by burning the generated gas with the heater.

Moreover, the phosphate collection | recovery system concerning this invention is the temperature in the range of 100-250 degreeC, and the pressure in the range of 0.1-4 MPa of biomass containing phosphorus in presence of a nonmetallic catalyst. A pretreatment device for hydrothermal treatment under conditions, a biomass slurry obtained by hydrothermal treatment in the pretreatment device and containing the non-metallic catalyst at a temperature of 374 ° C. or higher, and 22. A reactor that performs hydrothermal treatment under conditions of a pressure of 1 MPa or more, a power generation device that generates electric power using a product gas generated by hydrothermal treatment in the reactor, and a gas containing oxygen as part of the product gas A heater that burns in the reactor and heats the slurry body in the reactor, a preheater that preheats the oxygen-containing gas used in the heater using exhaust heat of the power generator, and the water A hydrochloric acid reactor for reacting the ash produced in the treatment with hydrochloric acid, a filtration device for filtering the hydrochloric acid after reacting with the ash, and sodium hydroxide for reacting the filtrate obtained by filtering the hydrochloric acid with an aqueous sodium hydroxide solution A reaction device, and a recovery device for recovering a precipitate generated by reacting the filtrate with the sodium hydroxide aqueous solution, and the reactor, the heater, or the preheater and the reactor, The reactor, the heater, or the pipe is provided with at least one peeling device that peels off the biomass slurry adhering to the inner surface of the pipe connecting the pipes.

  Here, the peeling device is preferably a vibration device or a gas injection device.

  The phosphate recovery system is a mixed liquid containing the product gas, the ash, the non-metallic catalyst, and water discharged from the reactor, the product gas, the ash, the non-metallic catalyst, and water. A gas-liquid separator that separates the gas and liquid may be provided.

  In addition, the phosphate recovery system may include a power generation device that generates electric power using a generated gas generated by hydrothermal treatment in the reactor.

  Further, the phosphate recovery system may include a heater that heats the slurry body in the reactor by burning a part of the generated gas discharged from the reactor in a gas containing oxygen. Good. Moreover, you may further provide the preheater which preheats the gas containing the oxygen used with the said heater.

  Here, it is preferable to make it react with sodium hydroxide aqueous solution so that the pH of the said filtrate may be 6.0-9.0. Examples of the precipitate include monetite (dicalcium phosphate) and / or hydroxyapatite.

  The pretreatment device may include means for heating the biomass containing phosphorus using exhaust heat of the power generation device or heat of exhaust gas obtained by burning the product gas with the heater. . The preheater may include means for preheating the oxygen-containing gas using exhaust heat of the power generation apparatus or heat of exhaust gas obtained by burning the generated gas with the heater. .

  The phosphate recovery system may include a heat exchanger that preheats the slurry body hydrothermally treated in the reactor using heat of the product gas discharged from the reactor, A heat exchanger that preheats the biomass containing phosphorus that is hydrothermally treated in the pretreatment device using heat of the slurry body hydrothermally treated in the reactor may be provided, or the reaction A heat exchanger that preheats the biomass containing phosphorus that is hydrothermally treated by the pretreatment device using heat of the product gas discharged from the vessel may be provided.

  The phosphate recovery system is disposed between a slurry supply device that receives the slurry body from the pretreatment device and supplies the slurry body to the reactor, and the pretreatment device and the slurry supply device, A first pressure accumulator for accumulating the slurry body received in the slurry supply apparatus; and a first accumulator disposed between the slurry supply apparatus and the reactor for accumulating the slurry body supplied from the slurry supply apparatus. The pressure supply device further includes an inlet for injecting water, an outlet for discharging the injected water, and an inlet for receiving the slurry body from the pretreatment device. A supply port for supplying the slurry body to the reactor, and the water in each cylinder and the slurry body are separated from each other. A piston provided at each end, a stirrer for stirring the slurry body in each cylinder, and receiving the slurry body from the pretreatment device into the first cylinder, and the pretreatment device A first step of injecting the water into the second cylinder such that the slurry body received in the second cylinder is supplied to the reactor; and the slurry body received in the first cylinder And a second step of injecting the water into the first cylinder so that the slurry is received from the pretreatment device into the second cylinder. You may provide the water injection apparatus to perform.

  The shaft may further include contact preventing means for preventing contact between the piston and the stirrer. Further, the water injection device may inject water at a constant flow rate for each cylinder.

  In the phosphate recovery system, the reactor includes an inlet for introducing the slurry body into the reactor from below, a product gas and ash generated by hydrothermal treatment in the reactor, and the A discharge port for discharging the nonmetallic catalyst and water from the top to the outside of the reactor, a fluid medium for forming a fluidized bed in the reactor by introduction of the slurry body, and the slurry body introduced from the introduction port. And a dispersion part for dispersion under the fluidized bed, and the fluidized medium may be configured in a shape that is not discharged at the introduction speed of the slurry body. The fluid medium is, for example, an alumina ball. The dispersion part may be formed by stacking alumina balls. The phosphate recovery system may further include means for recovering the nonmetallic catalyst in the mixed solution.

  In addition, the phosphate recovery system may further include a crusher that crushes in advance the biomass containing the phosphorus to be hydrothermally treated by the pretreatment device.

  According to the present invention, energy is efficiently used from biomass containing phosphorus, biomass is gasified with supercritical water to efficiently generate fuel gas such as methane and hydrogen, and hydroxy is obtained from the reaction product after treatment. A method for recovering a phosphate containing apatite can be provided.

  Hereinafter, preferred embodiments of a phosphate recovery system (hereinafter referred to as a phosphate recovery system) according to the present invention will be described in detail with reference to the accompanying drawings. This phosphate recovery system gasifies biomass and efficiently generates fuel gas such as methane and hydrogen, and generates biomass gas with biomass adhesion prevention function to generate electricity with the obtained fuel gas and supply electric power. It consists of a power generation system and a recovery system for generating and recovering phosphate from by-products obtained from this biomass gasification power generation system. Since these systems can be designed independently, the configuration of each system will be described separately below. In the following system, biomass containing phosphorus is used.

== Configuration of biomass gasification system with biomass adhesion prevention function ==
FIG. 1 is a diagram showing an overall configuration of a biomass gasification system with a biomass adhesion preventing function described as an embodiment of the present invention. As shown in FIG. 1, a biomass gasification system 200 with a biomass adhesion preventing function according to the present invention includes a regulating tank 100, a crusher 110, a supply pump 120, a first heat exchanger 130, a second heat exchanger 131, a front Processing unit 140, slurry supply unit 150, reactor 160, heater 161, preheater 162, heater 163, preheater 164, cooler 170, decompressor 171, gas-liquid separator 180, gas tank 181, catalyst recovery unit 182, A power generator 190 and the like are provided.

  The pretreatment device 140 is a device that forms a biomass slurry. Formation of a biomass slurry is performed by hydrothermal treatment of biomass in the presence of a non-metallic catalyst at a temperature in the range of 100 to 250 ° C. and a pressure in the range of 0.1 to 4 MPa. Done.

The adjustment tank 100 is a tank that mixes biomass, water, a nonmetallic catalyst, and the like while adjusting the mixing amount of water and a nonmetallic catalyst according to the type, amount, moisture content, and the like of the biomass.
The crusher 110 crushes the mixture mixed in the adjustment tank 100 so that the biomass in the mixture has a uniform size in advance (preferably an average particle size of 500 μm or less, more preferably an average particle size of 300 μm or less). It is a device.
The supply pump 120 is a device that transfers the mixture crushed by the crusher 110 to the pretreatment device 140.

  The reactor 160 is a device that gasifies biomass with supercritical water. Biomass gasification with supercritical water is carried out by using a biomass slurry containing a nonmetallic catalyst that has been hydrothermally treated in the pretreatment device 140 at a temperature of 374 ° C. or higher, using the nonmetallic catalyst. It is performed by hydrothermal treatment under conditions of a pressure of 22.1 MPa or more. By treating the slurry body with supercritical water in this way, biomass can be decomposed and fuel gas such as hydrogen gas, methane, ethane, or ethylene can be generated.

  The reactor 160 is not particularly limited as long as it is a device capable of hydrothermally treating a biomass slurry in the presence of a nonmetallic catalyst under the above-described conditions. A tubular reactor, a fluidized bed reactor or the like can be used.

  Here, when the biomass slurry body is hydrothermally treated in the reactor 160, if the biomass slurry body adheres to the inner surface of the reactor 160, the efficiency of the hydrothermal treatment is reduced, and the fuel gas decomposed from the biomass The production amount of is reduced. In order to solve this problem, a peeling device 250 that peels off the biomass slurry attached to the inner surface of the reactor 160 is provided, and an impact is applied to the inner surface to which the biomass slurry is attached using the peeling device 250. By giving, the biomass slurry adhered to the inner surface of the reactor 160 is peeled off from the inner surface. The stripping device 250 may be anything as long as the biomass slurry adhered to the inner surface of the reactor 160 can be stripped from the inner surface, for example, a vibration device capable of applying vibration to the surface to which the biomass slurry has adhered, An injection device that blows gas onto the surface to which the biomass slurry is attached may be used. Examples of the vibration device include an air knocker (seishin corporation, product number: SK air knocker, SK-LP type), but a vibration motor (for example, EXEN Corporation, product number: KM202 PA) may also be used. Absent.

  Although the mounting position of the peeling device 250 is not particularly limited, when the peeling device 250 is a vibration device, the peeling device 250 may be directly attached to the inner surface of the reactor 160 or directly on the outer surface of the reactor 160. It may be provided attached or indirectly attached to the material encapsulating the reactor 160. On the other hand, when the peeling device 250 is an injection device, the peeling device 250 is provided on the inner surface of the reactor 160. Here, the gas that can be used in the injection device typically includes a compressed gas (for example, nitrogen or carbon dioxide having a pressure of 0.3 MPa or more), but is not limited thereto. Note that when the biomass slurry adheres to the inner surface of the reactor 160, the pressure in the reactor 160 increases. Therefore, various sensors such as a sensor for measuring the pressure in the reactor 160 may be provided in the reactor 160 in order to check whether or not the biomass slurry is attached in the reactor 160. The output value of each sensor may be controlled by a measuring instrument or a computer, and is controlled so that the peeling device 250 is activated when the pressure in the reactor 160 rises above a certain level (for example, 26.0 MPa or more). May be.

  By adopting the above configuration, even if the inside of the reactor 160 is blocked due to the biomass slurry attached to the inner surface of the reactor 160, the biomass slurry is attached using the peeling device 250. If the biomass slurry adhering to the inner surface of the reactor 160 is peeled off from the inner surface by applying an appropriate impact to the inner surface, blockage in the reactor 160 can be prevented. Thus, the reactor 160 can be operated continuously without clogging the biomass slurry. In addition, when the slurry body of the biomass adhering to the inside of the reactor 160 was analyzed, it became clear that the cause of the blockage was mainly hydroxyapatite as shown in the Examples.

  Hereinafter, an example of a schematic configuration of the tubular reactor 160 in one embodiment of the present invention is shown, but the present invention is not limited to this configuration.

  The tubular reactor 160 is a reactor having a coiled tube as shown in FIG. 2, and an inlet 210 for introducing a slurry body of biomass containing a nonmetallic catalyst into the tubular reactor 160 from below, Product gas and ash content including fuel gas generated by hydrothermal treatment of the slurry body in a tubular reactor 160 under conditions of a temperature of 374 ° C. or higher and a pressure of 22.1 MPa or higher, and nonmetal An inner pipe having a discharge port 220 for discharging the system catalyst and water (supercritical water) from above to the tubular reactor 160, and an introduction port 211 for introducing heat of the discharge discharged from the heater 163, A discharge port 221 for discharging the heat of the discharge discharged from the tubular reactor 160 and a peeling device 250 for peeling the biomass slurry attached to the inner surface of the tubular reactor 160 are provided.

  The tube used for the tubular reactor 160 can be produced, for example, by turning a tube such as a copper tube (with fins) in a coil shape with a length of 10 to 200 m.

  The stripping device 250 may be anything as long as it can strip the biomass slurry adhered to the inner surface of the tubular reactor 160, that is, in this embodiment, from the inner surface of the tube. Examples thereof include a vibration device capable of applying vibration to the surface to which the slurry body is adhered, and an injection device for blowing gas onto the surface to which the biomass slurry body is adhered. When the peeling device 250 is a vibration device, the peeling device 250 may be directly attached to the outer surface of the tubular reactor 160 as shown in FIG. 2, or may be directly attached to the inner surface of the tube. Good. On the other hand, when the peeling device 250 is an injection device, the peeling device 250 is preferably provided inside the pipe. Specific examples of the vibration device and the injection device are as described above.

  FIG. 3 shows a schematic configuration of a fluidized bed reactor 160 capable of continuous operation in an embodiment of the present invention. A fluidized bed reactor 160 as shown in FIG. 3 includes an inlet 210 for introducing a biomass slurry containing a nonmetallic catalyst into the fluidized bed reactor 160 from below, and the slurry in the fluidized bed reactor 160. Produced gas and ash containing a fuel gas produced by hydrothermal treatment under conditions of a temperature of 374 ° C. or higher and a pressure of 22.1 MPa or higher, and a nonmetallic catalyst and water (supercritical water) A discharge port 220 for discharging the fluidized bed reactor 160 from above, a fluidized medium 230 for forming a fluidized bed in the fluidized bed reactor 160 by introducing the slurry body, and a slurry body introduced from the inlet 210 into the fluidized bed. Dispersing section 240 for dispersing below, and stripping device 250 for stripping the biomass slurry adhering to the inner surface of fluidized bed reactor 160 are provided.

  The fluid medium 230 has a shape that is not discharged at the introduction speed of the slurry body. That is, the fluidized bed is formed at a speed at which the slurry body is introduced from the introduction port 210, but has a weight that cannot be discharged from the discharge port 220. In addition, when the mesh-shaped plate is installed in the discharge port 220, the fluid medium 230 may be configured with a size larger than the mesh of the plate. The fluid medium 230 is not particularly limited as long as it does not change the particle size even in a supercritical state, that is, the fluid medium is not easily broken. For example, alumina balls, zirconia balls, silica balls, etc. Can be mentioned.

  The dispersion unit 240 may be, for example, a known dispersion plate (for example, a mesh plate) used in a fluidized bed reactor or the like, but in order to prevent an increase in pressure due to clogging of the slurry body, It is a layer formed by stacking spherical media (for example, spherical media such as alumina balls) configured in a shape that does not flow at the speed at which the slurry body is introduced (for example, a weight that cannot flow at the speed at which the slurry body is introduced). Is preferred.

  The stripping device 250 may be anything as long as it can strip the biomass slurry adhering to the inner surface of the fluidized bed reactor 160, that is, the inner wall surface of the fluidized bed reactor 160 in this embodiment, Examples thereof include a vibration device capable of applying vibration to the surface to which the biomass slurry body is adhered, and an injection device for blowing gas onto the surface to which the biomass slurry body is adhered. When the peeling device 250 is a vibration device, the peeling device 250 may be directly attached to the outer wall surface of the fluidized bed reactor 160 as shown in FIG. 3 or directly on the inner wall surface of the fluidized bed reactor 160. You may attach and provide. On the other hand, when the peeling device 250 is an injection device, the peeling device 250 is preferably provided inside the fluidized bed reactor 160. Specific examples of the vibration device and the injection device are as described above.

  By using the tubular reactor 160 to which the peeling device 250 as described above is attached, even if the reactor 160 is clogged due to a biomass slurry adhering to the inner surface of the tubular reactor 160, the peeling is performed. If an impact is appropriately applied to the inner surface to which the biomass slurry is adhered using the apparatus 250 and the biomass slurry adhered to the inner surface of the tubular reactor 160 is peeled off from the inner surface, the reactor 160 is blocked. Can be prevented. Thus, the tubular reactor 160 can be operated continuously without clogging the biomass slurry. Therefore, the product gas (including fuel gas) and ash produced by the reaction in the reactor and the lighter and smaller substance than the fluid medium such as non-metallic catalyst and water are efficiently discharged from the discharge port 220. Will be able to. In addition, it is possible to continuously introduce a biomass slurry containing a nonmetallic catalyst and continuously perform a gasification reaction with supercritical water.

  The slurry supply device 150 is a device that supplies a biomass slurry containing a nonmetallic catalyst obtained by performing the hydrothermal treatment in the pretreatment device 140 to the reactor 160. The slurry supply device 150 is not particularly limited as long as it is a device that can supply a slurry body of biomass containing a nonmetallic catalyst. For example, a high-pressure pump or a mono pump can be used as shown in FIG. It is preferable to use an apparatus that can continuously supply the above slurry body, which is easily separated into a solid component and a liquid component, to the reactor 160 at a constant concentration.

  FIG. 4 is a diagram showing a schematic configuration of a slurry supply apparatus 150 described as an embodiment of the present invention. A slurry supply apparatus 150 as shown in FIG. 4 receives a biomass slurry body containing a nonmetallic catalyst obtained by performing hydrothermal treatment in the pretreatment apparatus 140 from the pretreatment apparatus 140, and enters the reactor 160. It is a device to supply. The slurry supply device 150 includes two cylinders 310 and 320, a shaft 330, two pistons 331 and 332, two agitators 340 and 350, a water injection device 360, valves 361, 362, 363, 364, 373, 374, and 375. , 376, three-way valves 371, 372 and the like.

  The water injection device 360 is a device for injecting water into the cylinders 310 and 320 by alternately switching the cylinders 310 and 320 for injecting water. The water injection device 360 is, for example, a pump, a high pressure pump, a back pressure pump, or the like.

The cylinders 310 and 320 are provided with injection / discharge ports for injecting water from the water injection device 360 and discharging the injected water. Further, the cylinders 310 and 320 are provided with receiving / supplying ports that receive the slurry body from the pretreatment device 140 and supply the received slurry body to the reactor 160.
Pistons 331 and 332 are disposed in the cylinders 310 and 320 so as to partition water injected from the water injection device 360 and a slurry body received from the pretreatment device 140.

  Pistons 331 and 332 are provided at both ends of the shaft 330. The pistons 331 and 332 move in the cylinders 310 and 320 when water is injected into the cylinders 310 and 320 from the water injection device 360, and the slurry bodies in the cylinders 310 and 320 are pressed to make the slurry into the reactor 160. Supply the body. As the one piston 331, 332 moves, the other piston 332, 331 moves in the same direction as the one piston 331, 332, receives the slurry body from the pretreatment device 140, and in the cylinders 320, 310 Drain the water.

  In order to prevent the water in the cylinders 310 and 320 and the slurry from being mixed, a piston ring may be provided on the pistons 331 and 332 to improve the airtightness between the pistons 331 and 332 and the cylinders 310 and 320.

  In the present embodiment, a stopper 333 is provided at the center of the shaft 330. The stopper 333 is a device that prevents contact between the pistons 331 and 332 and the stirrers 340 and 350. When the stopper 333 comes into contact with the cylinders 310 and 320, the pistons 331 and 332 cannot move toward the stirrers 340 and 350.

  The valves 361, 362, 363, and 364 are devices that switch the water to flow from the water injection device 360 to the cylinders 310 and 320 and switch the water in the cylinders 310 and 320 to discharge. The valves 361, 362, 363, 364 are, for example, electromagnetic valves.

  In the present embodiment, the valves 361, 362, 363, and 364 are switched so that water flows into the cylinders 310 and 320 by the water injection of the water injection device 360. Further, the valves 361, 362, 363, and 364 are switched so that water is discharged by drainage from the cylinders 310 and 320. Such switching can be performed electrically with water injection from the water injection device 360 or drainage from the cylinders 310 and 320, for example. Specifically, when it is detected that the stopper 333 provided on the shaft 330 has come into contact with one of the cylinders 310 and 320, the water injection device 360 changes the water injection destination from the cylinders 310 and 320 to the other cylinders 320 and 310. The valves 363 and 361 are opened so that water flows from the water injection device 360 to the cylinders 320 and 310, and the valves 364 and 362 are not discharged so that water injected from the water injection device 360 to the cylinders 320 and 310 is not discharged. The valves 362 and 364 are opened so that water is discharged from the cylinders 310 and 320, and the valves 361 and 363 are closed so that water discharged from the cylinders 310 and 320 does not flow to the water injection device 360. May be performed respectively.

  In the present embodiment, the slurry supply device 150 is provided with valves 361, 362, 363, 364, but instead of these valves 361, 362, 363, 364, two three-way valves are provided, It may be switched so that water flows into the cylinders 310 and 320 by water injection from the injection device 360, or may be switched so that water is discharged by drainage from the cylinders 320 and 310. Such switching can be mechanically performed, for example, by a valve or the like for preventing backflow, but can also be electrically performed in accordance with water injection from the water injection device 360 or drainage from the cylinders 310 and 320. Specifically, when it is detected that the stopper 333 provided on the shaft 330 has come into contact with one of the cylinders 310 and 320, the water injection device 360 changes the water injection destination from the cylinders 310 and 320 to the other cylinders 320 and 310. One of the three-way valves may be switched so that water flows from the water injection device 360 to the cylinders 320 and 310, and the other three-way valve may be switched so that water is discharged from the cylinders 310 and 320.

  The three-way valves 371 and 372 are switched so that the slurry body flows from the pretreatment device 140 to the cylinders 310 and 320 by the reciprocating motion of the pistons 331 and 332, and the slurry bodies received in the cylinders 310 and 320 are cylinders 310 and 320. To switch to flow into the reactor 160.

  In the present embodiment, when receiving the slurry body from the pretreatment device 140, the three-way valves 371 and 372 are switched so that the slurry body flows from the pretreatment device 140 to the cylinders 310 and 320. The three-way valves 371 and 372 are switched so that the slurry body flows from the cylinders 310 and 320 to the reactor 160 when the slurry body is supplied from the cylinders 310 and 320. Such switching can be mechanically performed by, for example, a valve that prevents backflow, but is electrically performed in accordance with the slurry body supply from the cylinders 310 and 320 and the slurry body supply from the pretreatment device 140. You can also. Specifically, when it is detected that the stopper 333 provided on the shaft 330 contacts one of the cylinders 310 and 320, the three-way valves 371 and 372 cause the slurry body to flow from the pretreatment device 140 to the cylinders 310 and 320. The other three-way valves 372 and 371 may be controlled so that the slurry body flows from the other cylinders 320 and 310 to the reactor 160, respectively.

  Note that the detection of the contact between the stopper 333 and the cylinders 310 and 320 is performed, for example, by providing a switch in a part of the region where the stopper 333 and the cylinder 310 and 320 are in contact and pressing the switch. Also good.

  The valves 373 and 374 are used when the cylinder that supplies the slurry body to the reactor 160 is switched from one cylinder 310 or 320 to the other cylinder 320 or 310, that is, the cylinder 310 or 320 into which the water injection device 360 injects water. Is a device that temporarily shuts off the flow (supply) of the slurry body from the cylinders 310, 320 to the reactor 160 when switching from one cylinder 310, 320 to the other cylinder 320, 310. The valves 375 and 376 are slurries from the pretreatment device 140 to the cylinders 310 and 320 when the water injection device 360 switches the cylinders 310 and 320 into which water is injected from the one cylinder 310 and 320 to the other cylinder 320 and 310. It is a device that temporarily blocks the body from flowing. The valves 373, 374, 375, and 376 are, for example, electromagnetic valves.

  The above-described blocking by the valves 373, 374, 375, and 376 may be performed electrically, for example, with water injection from the water injection device 360 or drainage from the cylinders 310 and 320. Specifically, when it is detected that the stopper 333 provided on the shaft 330 is in contact with one of the cylinders 310 and 320, the valves 373 and 374 flow (supply) the slurry body from the cylinders 310 and 320 to the reactor 160. The valves 376 and 375 are closed so as to block the flow (acceptance) of the slurry body from the pretreatment device 140 to the cylinders 320 and 310, and the water injection device 360 controls the water injection destination. After switching from the cylinder 310, 320 to the other cylinder 320, 310, one of the valves 373, 374, one valve 374, 373 flows the slurry body from the cylinder 320, 310 to the reactor 160 via the three-way valve 372, 371. Of the valves 375 and 376, one of the valves 375 and 376 Control of opening from the processing unit 140 to flow into the cylinder 310 the may be performed, respectively.

  The agitators 340 and 350 are devices that agitate the slurry body received in the cylinders 310 and 320 from the pretreatment device 140 via the valves 375 and 376 and the three-way valves 371 and 372. Thus, by stirring the slurry body with the stirrers 340 and 350 in the cylinders 310 and 320, it is possible to prevent the precipitation of solid matter such as non-metallic catalyst and biomass particles contained in the slurry body. The slurry body having a constant concentration can be supplied to the reactor 160.

  In the present embodiment, between the slurry supply device 150 and the reactor 160, the pressure accumulator 380 that accumulates the slurry body supplied from the slurry supply device 150, and between the pretreatment device 140 and the slurry supply device 150. And a pressure accumulator 381 for accumulating a slurry body received by the slurry supply device 150. By providing these, the pressure in the piping connecting the slurry supply device 150 and the reactor 160 and the pressure in the piping connecting the pretreatment device 140 and the slurry supply device 150 can be kept constant, and pulsation It is possible to prevent the occurrence of water hammer or water hammer.

  It should be noted that the switching of the water injection destination performed by the water injection device 360 described above may be performed electrically at the timing when the stopper 333 provided on the shaft 330 contacts the cylinders 310 and 320, or in each cylinder 310 or 320. It may be performed by detecting that the pressure has increased. The water injected by the water injection device 360 into the cylinders 310 and 320 is preferably water having the same temperature as the temperature of the slurry body received in the cylinders 310 and 320. Thereby, the cylinders 310 and 320 are cooled by the water injected into the cylinders 310 and 320, and the temperature of the slurry body received in the cylinders 310 and 320 can be suppressed from decreasing. The water injection into the cylinders 310 and 320 by the water injection device 360 is preferably performed at a constant flow rate so that the slurry body is supplied to the reactor 160 at a constant flow rate.

  In the above description, the stopper 333 is provided on the shaft 330 of the slurry supply device 150 to prevent contact between the pistons 331 and 332 and the stirrers 340 and 350. It is possible to prevent the pistons 331 and 332 from coming into contact with the stirrers 340 and 350 by adjusting the length of the water, or to add water in an amount that does not contact the pistons 331 and 332 and the stirrers 340 and 350. 360 may be alternately injected into each of the cylinders 310 and 320 to prevent the pistons 331 and 332 from coming into contact with the stirrers 340 and 350. Moreover, you may provide the stopper (for example, unevenness | corrugation etc.) which controls the movement of piston 331,332 in cylinder 310,320 so that piston 331,332 and stirrer 340,350 may not contact.

  Further, in the above description, one port (injection / discharge port) for injecting water from the water injection device 360 and discharging the injected water is provided in the cylinders 310 and 320, but water is injected from the water injection device 360. The cylinders 310 and 320 may be provided with two ports, an injection port for discharging and a discharge port for discharging the injected water.

  In the above description, the cylinders 310 and 320 are provided with one port (acceptance / supply port) for receiving the slurry body from the pretreatment device 140 and supplying the received slurry body to the reactor 160. The cylinders 310 and 320 may be provided with two ports, an inlet for receiving the slurry body from 140 and a supply port for supplying the received slurry body to the reactor 160.

  The preheater 162 is an apparatus that preheats a biomass slurry body containing a nonmetallic catalyst, which is supplied from the slurry supply apparatus 150 to the reactor 160. By providing the biomass gasification system 200 with the biomass adhesion preventing function 200 with the preheater 162, it becomes possible to supply a slurry body having a predetermined temperature to the reactor 160.

  The biomass slurry heated in the preheater 162 may adhere to the inner surface of the pipe connecting the preheater 162 and the reactor 160. As described above, when the biomass slurry body adheres to the inner surface of the pipe, the supply amount of the biomass slurry body to the reactor 160 is reduced, and as a result, the fuel gas decomposed from the biomass in the reactor 160 is reduced. Reduced production. In order to solve this problem, a peeling device 250 that peels off the biomass slurry attached to the inner surface of the pipe connecting the preheater 162 and the reactor 160 is provided. By giving an impact to the adhered inner surface, the biomass slurry adhered to the inner surface of the pipe is peeled off from the inner surface. The peeling device 250 may be anything as long as it can peel the biomass slurry attached to the pipe from the inner surface, for example, a vibration device capable of applying vibration to the surface to which the biomass slurry is attached, An injection device that blows gas onto the surface to which the biomass slurry is attached may be used. Examples of the vibration device include an air knocker (seishin corporation, product number: SK air knocker, SK-LP type), but a vibration motor (for example, EXEN Corporation, product number: KM202 PA) may also be used. Absent. The mounting position of the peeling device 250 is not particularly limited, but when the peeling device 250 is a vibration device, the peeling device 250 may be directly attached to the inner surface of the pipe connecting the preheater 162 and the reactor 160. Alternatively, it may be provided directly attached to the outer surface of the pipe connecting the preheater 162 and the reactor 160, or provided indirectly attached to the material encapsulating the pipe connecting the preheater 162 and the reactor 160. Also good. On the other hand, when the peeling device 250 is an injection device, the peeling device 250 is provided on the inner surface of a pipe connecting the preheater 162 and the reactor 160. Here, the gas that can be used in the injection device typically includes a compressed gas (for example, nitrogen or carbon dioxide having a pressure of 0.3 MPa or more), but is not limited thereto. A sensor for measuring the pressure in the pipe connecting the preheater 162 and the reactor 160 in order to check whether or not the biomass slurry is attached to the inner surface of the pipe connecting the preheater 162 and the reactor 160. These sensors may be provided in the pipe. The output value of each sensor may be controlled by a measuring device or a computer, and is controlled so that the peeling device 250 is activated when the pressure in the pipe rises above a certain level (for example, 26.0 MPa or more). Also good.

  As described above, even if the inside of the piping is blocked due to the biomass slurry adhering to the inner surface of the pipe connecting the preheater 162 and the reactor 160, the biomass slurry body is adhered using the peeling device 250. If the biomass slurry adhered to the inner surface of the pipe is peeled off from the inner surface by applying an appropriate impact to the inner surface, blockage in the pipe can be prevented. Thus, the biomass slurry body can be continuously supplied from the preheater 162 to the reactor 160 without clogging the biomass slurry body.

  The cooler 170 is a device that cools the discharge discharged from the reactor 160. The exhaust discharged from the reactor 160 contains a product gas such as highly explosive fuel gas (for example, hydrogen, methane, ethane, ethylene, etc.) or water vapor (supercritical water). The cooler 170 is provided in the biomass gasification system 200 with a biomass adhesion preventing function of the present invention for the purpose of reducing water vapor or converting water vapor into water. In the present embodiment, the cooler 170 is described as an example of a device for cooling the discharge discharged from the reactor 160, but the device that can cool the discharge discharged from the reactor 160. Any device may be used as long as it is.

  The decompressor 171 is a device that reduces the pressure of the effluent discharged from the reactor 160. As a result, the danger caused by the high-pressure fuel gas can be prevented beforehand. Note that a pressure adjusting pump may be provided between the cooler 170 and the decompressor 171 in order to adjust the pressure of the discharge discharged from the reactor 160 to be constant.

The gas-liquid separator 180 converts the exhaust discharged from the reactor 160 into a gas mixture (for example, a product gas such as fuel gas) and a liquid component (water, or a mixture containing water, ash, a nonmetallic catalyst, etc.). ). As the gas-liquid separator 180, for example, an existing gas-liquid separator such as a separator can be used.
The gas tank 181 is a container (preferably a pressure resistant container) that stores the gas component (product gas) separated by the gas-liquid separator 180.

  The heater 161 combusts a part of the generated gas (fuel gas) stored in the gas tank 181 in a gas containing oxygen (for example, oxygen gas, air, etc.) to heat the reactor 160, and the slurry body is predetermined. It is the apparatus which heats to the temperature. In addition, the heater 163 burns a part of the generated gas (fuel gas) stored in the gas tank 181 in a gas containing oxygen (for example, oxygen gas, air, etc.) to heat the preheater 162, and the slurry body Is a device that heats to a predetermined temperature. The heaters 161 and 163 are existing devices that burn and heat fuel gas, such as a burner, for example.

  The catalyst recovery unit 182 recovers the nonmetallic catalyst from the liquid component when the liquid component separated by the gas-liquid separator 180 contains a nonmetallic catalyst other than water, ash, or the like. An apparatus for separating a metal catalyst from a liquid component. In FIG. 5, the schematic block diagram of the catalyst collection | recovery device 182 which isolate | separates ash in a liquid component, a nonmetallic catalyst, and water each demonstrated as one Embodiment of this invention is shown. In the present embodiment, the case where the nonmetallic catalyst is activated carbon having a lower sedimentation rate (termination rate) than ash will be described.

  As shown in FIG. 5, the catalyst recovery unit 182 includes a mixed liquid injection unit 410, a water tank 420, a circulation pump 430, a supply pipe 440, an ash receiving unit 450, valves 460, 461, and 470.

  The liquid mixture injection unit 410 is a pipe for injecting the liquid component (mixed liquid containing ash, activated carbon, water, etc.) separated by the gas-liquid separator 180. The water tank 420 is a cylindrical container in which water for slowly sinking ash and activated carbon in the mixed liquid injected from the mixed liquid injection unit 410 is placed. The water tank 420 has a discharge port 421 for allowing ash in the liquid mixture injected from the liquid mixture injection unit 410 to settle and discharge the water from the water tank 420, an activated carbon receiving part 422 423 for receiving activated carbon in the liquid mixture, and an ash floating in the water tank 420. And a drain outlet 424 for discharging suspended matter such as activated carbon and water together with water.

  The ash receiving unit 450 is a container that receives the ash that has settled from the discharge port 421. The circulation pump 430 is a pump that circulates the water in the water tank 420. The supply pipe 440 is a pipe that introduces water circulated by the circulation pump 430 into the water tank 420 through the discharge port 421. The water circulated by the circulation pump 430 is supplied from the discharge port 421 to the water tank 420 at a flow rate that is faster than the sedimentation rate of the activated carbon and slower than the sedimentation rate of the ash. Thereby, the ash in the mixed liquid injected from the mixed liquid injection unit 410 settles in the ash receiving unit 450 through the discharge port 421, but the activated carbon in the mixed liquid injected from the mixed liquid injection unit 410 is It moves to the activated carbon receiving part 422,423 without passing through the discharge port 421.

  In the present embodiment, the activated carbon receivers 422 and 423 are provided with ridges 425 and 426 made of finer mesh than the activated carbon particles so that the activated carbon collected in the receivers 422 and 423 can be collected. The ash receiving unit 450 is provided with a ridge 451 made of a mesh finer than ash particles so that the ash collected in the receiving unit 450 can be collected.

  The valves 460 and 461 are valves that discharge water from the water tank 420. After separating the ash and activated carbon in the mixed solution injected from the gas-liquid separator 180, the activated carbon accumulated in the tanks 425 and 426 is recovered by draining the water in the water tank 420 through the valves 460 and 461. Can do. Further, the valve 470 is a valve for draining water from the ash receiving unit 450. After separating the ash and activated carbon in the mixed solution injected from the gas-liquid separator 180, the ash collected in the tub 451 can be recovered by draining the water of the ash receiving portion 450 by the valve 470. .

  By providing the catalyst recovery unit 182 as described above in the biomass gasification system 200 with a biomass adhesion preventing function of the present invention, the mixed solution can be separated into a nonmetallic catalyst, ash, and water. It becomes possible to collect. This makes it possible to reuse the recovered nonmetallic catalyst.

  Further, the liquid component (including ash) separated by the gas-liquid separator 180 or the ash separated by the catalyst recovery unit 182 is used in the following “recovery system”, and a phosphate containing hydroxyapatite is used. It can also be collected.

  The catalyst recovery unit 182 includes an existing solid-liquid separator that separates the mixed liquid containing the ash, the nonmetallic catalyst, and water separated by the gas-liquid separator 180 into a solid component and a liquid component; It may be a combination with an existing sieve device that separates the ash in the separated solid component and the nonmetallic catalyst by sieving.

  The first heat exchanger 130 is obtained by hydrothermal treatment in the pretreatment device 140, and uses the heat of the biomass slurry containing the nonmetallic catalyst to be hydrothermally treated in the reactor 160. 140 is an apparatus for preheating biomass or the like to be subjected to hot water treatment.

  The second heat exchanger 131 is hydrothermally treated in the reactor 160 using the heat of the effluent discharged from the reactor 160 including the product gas generated by hydrothermal treatment in the reactor 160. An apparatus for preheating a biomass slurry containing a non-metallic catalyst. As the second heat exchanger 131, for example, a double tube heat exchanger as shown in FIG. 6 is preferably used. As a method of using the double-pipe heat exchanger, for example, a biomass slurry containing a nonmetallic catalyst hydrothermally treated in the reactor 160 is introduced inside the double-pipe heat exchanger. The product produced by hydrothermal treatment in the reactor 160 is introduced outside the double-pipe heat exchanger. Here, the biomass slurry body preheated in the second heat exchanger 131 may adhere to the inner surface of the second heat exchanger 131 when the biomass slurry body is heated in the second heat exchanger 131. is there. Thus, when the biomass slurry body adheres to the inner surface of the second heat exchanger 131, the supply amount of the biomass slurry body to the reactor 160 decreases, and as a result, the reactor 160 decomposes from the biomass. The amount of generated fuel gas is reduced. In order to solve this problem, as shown in FIG. 6, a peeling device 250 that peels off the biomass slurry adhered to the inner surface of the second heat exchanger 131 is provided. By applying an impact to the inner surface to which the body is attached, the biomass slurry attached to the inner surface of the second heat exchanger 131 is peeled off from the inner surface. The peeling device 250 may be anything as long as it can peel the biomass slurry attached to the inner surface of the second heat exchanger 131 from the inner surface. For example, it gives vibration to the surface to which the biomass slurry adheres. And a jetting device that blows gas onto the surface to which the biomass slurry is attached. Examples of the vibration device include an air knocker (seishin corporation, product number: SK air knocker, SK-LP type), but a vibration motor (for example, EXEN Corporation, product number: KM202 PA) may also be used. Absent. The mounting position of the peeling device 250 is not particularly limited, but when the peeling device 250 is a vibration device, the peeling device 250 may be directly attached to the inner surface of the second heat exchanger 131 or may be provided with the second heat exchange. It may be provided directly attached to the outer surface of the vessel 131 or may be provided indirectly attached to the material encapsulating the second heat exchanger 131. On the other hand, when the peeling device 250 is an injection device, the peeling device 250 is provided on the inner surface of the second heat exchanger 131. Here, the gas that can be used in the injection device typically includes a compressed gas (for example, nitrogen or carbon dioxide having a pressure of 0.3 MPa or more), but is not limited thereto. In order to check whether the biomass slurry is attached to the inner surface of the second heat exchanger 131, various sensors such as a sensor for measuring the pressure in the second heat exchanger 131 may be provided in the pipe. Good. The output value of each sensor may be controlled by a measuring device or a computer, and is controlled so that the peeling device 250 is activated when the pressure in the pipe rises above a certain level (for example, 26.0 MPa or more). Also good.

  As described above, by providing the heat exchangers 130 and 131 in the biomass gasification system 200 with a biomass adhesion preventing function of the present invention, energy can be used effectively, so that fuel from biomass can be obtained at low energy and low cost. Gas can be generated. Moreover, since the heating time in each apparatus 140,160 is shortened, fuel gas can be efficiently generated from biomass. Therefore, it can be said that the biomass gasification system 200 with the biomass adhesion preventing function including the heat exchangers 130 and 131 is excellent in economic efficiency. Further, even if the inside of the second heat exchanger 131 is blocked due to the biomass slurry adhering to the inner surface of the second heat exchanger 131, the biomass slurry body adheres using the peeling device 250. If the biomass slurry adhered to the inner surface of the second heat exchanger 131 is peeled off from the inner surface by applying an appropriate impact to the inner surface, blockage in the second heat exchanger 131 can be prevented. Thus, the biomass slurry body can be continuously supplied from the second heat exchanger 131 to the preheater 162 without clogging the biomass slurry body. In addition, when the slurry body of the biomass adhering to the inner surface of the soot of the reactor 160 was analyzed, it became clear that the cause of the blockage was mainly hydroxyapatite as shown in the Examples. Here, the exhaust discharged from the outlet 220 of the reactor 160 is introduced into the second heat exchanger 131. Therefore, the cause of the blockage of the second heat exchanger 131 is mainly hydroxyapatite.

  Furthermore, the biomass gasification system 200 with a biomass adhesion preventing function of the present invention may include a power generator 190.

  Here, the power generation device 190 is a device that generates power using the generated gas (fuel gas) stored in the gas tank 181 as fuel. The power generation device 190 is an existing device such as a gas engine (reciprocating engine, rotary engine), gas turbine, Stirling engine, fuel cell, or the like.

  In the present embodiment, as shown in FIG. 1, biomass is generated using heat (exhaust heat) of exhaust gas discharged from the power generation device 190 when the power generation device 190 generates power using the generated gas as fuel. The pretreatment device 140 includes a heat exchanger for heating, and the biomass gasification system 200 with a biomass adhesion preventing function includes a preheater 164 having a heat exchanger for preheating a gas containing oxygen used in the heaters 161 and 163. It is. As described above, since the biomass gasification system 200 with the biomass adhesion preventing function of the present invention includes the pretreatment device 140 having a heat exchanger and / or the preheater 164, energy can be efficiently used, so that low energy・ It is possible not only to generate fuel gas such as methane and hydrogen from biomass at low cost, but also to generate power and supply power with low energy and low cost. Accordingly, it is possible to reduce the amount of heated fuel used, reduce the amount of exhaust gas generated, and the like.

  As described above, the exhaust heat of the power generation device 190 may be used by the pretreatment device 140 and the preheater 164 regardless of the temperature of the exhaust heat of the power generation device 190, but the exhaust heat depends on the exhaust gas temperature of the power generation device 190. You may change how to use heat suitably. Specifically, when the exhaust gas temperature of the power generator 190 is higher than the reaction temperature in the reactor 160, the exhaust heat may be used only by the preheater 164 as shown in FIG. Only the exhaust heat may be used. Further, when the exhaust gas temperature of the power generator 190 is lower than the reaction temperature in the reactor 160 and higher than the treatment temperature in the pretreatment device 140, the exhaust heat is used only by the pretreatment device 140 as shown in FIG. May be. As described above, by appropriately changing the method of using the exhaust heat according to the exhaust gas temperature of the power generation device 190, the exhaust heat of the power generation device 190 can be used more effectively.

  Further, in the present embodiment, as shown in FIGS. 1, 7, and 8, the heat of exhaust gas obtained by burning the product gas in a gas containing oxygen by the heater 163 is used. The reactor 160 is provided with a heat exchanger for heating the biomass slurry containing the nonmetallic catalyst. Further, the heat of the exhaust gas used to heat the slurry body in the reactor 160 and / or the heat of the exhaust gas obtained by burning the product gas in a gas containing oxygen by the heater 161 are used. In addition, the pretreatment device 140 includes a heat exchanger that heats the biomass, or the preheater 164 having a heat exchanger that preheats the gas containing oxygen used in the heaters 161 and 163 is converted into biomass gasification with a biomass adhesion preventing function. The system 200 is prepared. As described above, the heat of the exhaust gas obtained by combusting the produced gas in a gas containing oxygen by the heater 163 provided with a heat exchanger in the reactor 160, the pretreatment device 140, the preheater 164, and the like. By utilizing the heat of the exhaust gas used to heat the slurry body in the vessel 160, the heat of the exhaust gas obtained by burning the produced gas in a gas containing oxygen by the heater 161, etc. It can be used effectively.

  In the above description, the heat of the exhaust gas obtained by the heater 163 is used in the pretreatment device 140 or the preheater 164 after being used in the reactor 160, but in the pretreatment device 140 or the preheater 164. You may use it directly. Further, in the present embodiment, as shown in FIG. 1, the introduction material (specifically, gas containing biomass, oxygen, or the like) introduced into the pretreatment device 140 or the preheater 164 is discharged from the power generation device 190. After heating with a heat exchanger that uses heat, the heat of the exhaust gas used to heat the slurry body in the reactor 160 and / or combustion of the product gas in a gas containing oxygen by the heater 161 However, these positions may be appropriately changed according to the temperature of each exhaust gas.

  Furthermore, in the above description, the biomass gasification system 200 with the biomass adhesion preventing function of the present invention includes the second heat exchanger 131 that preheats the slurry body using the heat of the exhaust discharged from the reactor 160. However, using the heat of the exhaust discharged from the reactor 160, including the product gas generated by the hydrothermal treatment in the reactor 160, the biomass that is hydrothermally treated in the pretreatment device 140 is preheated. You may provide the biomass gasification system 200 with a biomass adhesion prevention function of this invention with the heat exchanger to perform.

  In addition, since the biomass gasification system 200 with the biomass adhesion preventing function according to the present invention is provided with the pretreatment device 140 that performs the hydrothermal treatment of the biomass in advance, the biomass can be decomposed from a polymer to a low molecule, so It is possible to increase the contact efficiency between the biomass to be treated in 160 and water or a non-metallic catalyst, prevent the generation of char and tar, and efficiently generate fuel gas from the biomass.

  Furthermore, since the biomass slurry body having excellent fluidity can be formed by hydrothermally treating the biomass in the pretreatment device 140, the slurry body can be smoothly supplied to the reactor 160 by the slurry supply device 150. It becomes possible to prevent clogging of equipment and piping due to the biomass slurry in the supply to the reactor 160.

  Moreover, the non-metallic catalyst used in the hydrothermal treatment in the pretreatment device 140 can be used in the hydrothermal reaction in the reactor 160 by the biomass gasification system 200 with a biomass adhesion preventing function according to the present invention. Therefore, it is possible to reduce the consumption of the catalyst.

  Furthermore, by providing the biomass gasification system 200 with a biomass adhesion preventing function 200 according to the present invention with the reactor 160, ash (residue) obtained by gasifying biomass with supercritical water is accumulated in the reactor 160. The gasification process of biomass with supercritical water can be performed continuously, and fuel gas can be generated more efficiently from biomass.

  In addition, by providing the biomass gasification system 200 with a biomass adhesion preventing function according to the present invention with a slurry supply device 150 as shown in FIG. 4, the above-mentioned slurry body that is easily separated into a solid component and a liquid component can be obtained at a constant concentration. Since it can be continuously supplied to the reactor 160, a slurry body containing a nonmetallic catalyst, biomass, or the like can be continuously supplied to the reactor 160 under a concentration condition with the highest gasification efficiency of supercritical water, and fuel gas can be supplied from the biomass. It becomes possible to generate more efficiently.

  Furthermore, the biomass gasification system 200 with the biomass adhesion preventing function according to the present invention includes a cooler 170, a decompressor 171, a gas-liquid separator 180, and the like, so that fuel gas is contained in the exhaust discharged from the reactor 160. The product gas can be recovered safely.

  Moreover, since the biomass can be crushed beforehand by providing the biomass gasification system 200 with a biomass adhesion preventing function according to the present invention with the crusher 110 that crushes biomass, the efficiency of biomass slurrying and gasification can be increased. Will be able to.

  In the present embodiment, the mixture obtained by mixing the nonmetallic catalyst, biomass and water in the adjustment tank 100 is processed by the crusher 110 and supplied to the pretreatment device 140 by the supply pump 120. The system catalyst may be supplied directly to the pretreatment device 140, or after the mixture of biomass and water is processed by the crusher 110, the nonmetallic catalyst may be mixed and supplied to the pretreatment device 140.

== Operating method of biomass gasification system and biomass adhesion prevention method in the biomass gasification system ==
Next, as one embodiment of the present invention, a method for operating a biomass gasification system that generates fuel gas from biomass by a gasification reaction with supercritical water and generates power using the fuel gas, and the biomass gasification system, The biomass adhesion preventing method will be described.

  First, a mixture in which biomass, a nonmetallic catalyst, and water are mixed in the adjustment tank 100 is prepared. The mass ratio between the nonmetallic catalyst and the biomass (the dried biomass) is preferably in the range of 1: 5 to 20: 1, and the biomass gasification efficiency is high of 1: 2 to 20: 1. It is particularly preferable that it is within the range. Moreover, it is preferable to adjust the quantity of the water to mix so that the moisture content of biomass may be 70-95 wt%. Thereby, the gasification efficiency by the supercritical water of biomass can be improved.

  As described above, the amount of the non-metallic catalyst mixed with the biomass and the amount of water is adjusted, and the mixture obtained by mixing these is crushed by the crusher 110 and is fed by the supply pump 120 via the first heat exchanger 130. It is transferred to the processing device 140. The biomass supplied to the pretreatment device 140 is hydrothermally treated under conditions of a predetermined pressure and a predetermined temperature in the presence of a nonmetallic catalyst supplied together with the biomass.

  The conditions for the hydrothermal treatment are not particularly limited as long as the temperature is in the range of 100 to 250 ° C. and the pressure is in the range of 0.1 to 4 MPa. From the viewpoint of the efficiency of the treatment of decomposing into low molecules, it is preferably the saturation temperature of water under a pressure within these ranges, and from the viewpoint of energy saving, a temperature of 179.8 ° C. and a pressure of 1.0 MPa It is particularly preferred that Here, the reason why the hydrothermal treatment is performed at a temperature within the range of 100 ° C. to 250 ° C. is that the decomposition reaction rate of biomass is low below 100 ° C., and if it exceeds 250 ° C., generation of tar and char is concerned. is there. In addition, the hydrothermal treatment is performed at a pressure within the range of 0.1 to 4 MPa because the biomass decomposition reaction rate is low below 0.1 MPa, and the influence on the decomposition reaction rate is much higher even when a pressure higher than 4 MPa is applied. This is because I thought that it might not be.

  Thus, biomass can be efficiently decomposed from a polymer to a low molecule by hydrothermal treatment of the biomass in the presence of a nonmetallic catalyst.

  The biomass slurry containing the nonmetallic catalyst obtained as described above provides heat to the mixture supplied from the supply pump 120 to the pretreatment device 140 by the first heat exchanger 130, and the slurry supply device 150 is transferred to the reactor 160 via the second heat exchanger 131 and the preheater 162. The slurry body that has passed through the preheater 162 is heated to a predetermined temperature.

  Here, when transferring the biomass slurry body, the biomass slurry body is appropriately operated by appropriately operating the peeling apparatus 250 provided in the pipe connecting the second heat exchanger 131 or the preheater 162 and the reactor 160. It is preferable to prevent adhesion to the second heat exchanger 131 or the pipe. Specifically, when the pressure in the second heat exchanger 131 or the pipe is measured and rises above the pressure before operating the second heat exchanger 131 or the preheater 162 (for example, the second heat exchanger 131 When the pressure in 131 becomes 26.0 MPa or more, or when the pressure in the pipe becomes 26.0 MPa or more), the peeling device 250 is preferably operated. A specific example of the peeling device 250 is as described in the description of FIG. 1, FIG. 2, or FIG.

  The biomass slurry supplied to the reactor 160 is introduced into the reactor 160 and hydrothermally treated under the conditions of a predetermined pressure and a predetermined temperature in the presence of the nonmetallic catalyst supplied with the biomass. The conditions for the hydrothermal treatment are not particularly limited as long as the temperature is 374 ° C. or higher and the pressure is 22.1 MPa or higher, but the generation of tar and char is suppressed and the reaction efficiency is increased. It is preferable to carry out under the temperature (600 degreeC) and pressure (within the range of 25-35 MPa) which can be performed, and it is especially preferable to carry out at 600 degreeC and 25 MPa from a viewpoint of the burden of equipment, deterioration prevention, and energy saving. In addition, when it is desired to control the ratio of components in the fuel gas converted from biomass, the temperature and pressure conditions are adjusted, and the fluid density and reaction time (the residence time of biomass in the reactor 160) It becomes possible by controlling the above. In addition, during the hydrothermal treatment, it is preferable to prevent the biomass slurry from adhering to the reactor 160 by appropriately operating the peeling device 250 provided in the reactor 160. Specifically, when the pressure in the reactor 160 is measured and rises above the pressure before operating the reactor 160 (for example, when the pressure in the reactor 160 becomes 26.0 MPa or more), It is preferable to operate the peeling device 250. A specific example of the peeling apparatus 250 is as described in the description of FIG.

  Thus, by reacting the biomass slurry body with supercritical water, it becomes possible to generate combustion gas from the biomass slurry body. In addition, by reducing the biomass from a polymer in advance, the contact efficiency with water or a non-metallic catalyst can be increased, and furthermore, the gasification reaction time of the biomass can be shortened. Fuel gas such as hydrogen gas, methane, ethane, and ethylene can be generated more efficiently from the slurry body.

  The product gas generated by hydrothermally treating the biomass slurry in the reactor 160 is discharged from the reactor 160. This discharged material is supplied to the reactor 160 by the second heat exchanger 131 from the slurry supply device 150, and then supplies heat to the biomass slurry including the nonmetallic catalyst, and then the cooler 170 and the decompressor 171. It is cooled and decompressed and transferred to the gas-liquid separator 180. The exhaust gas supplied to the gas-liquid separator 180 is separated into product gas (gas component) containing fuel gas and water or a mixed solution (liquid component) containing water, ash, non-metallic catalyst, etc. The generated gas is stored in the gas tank 181. If the mixed liquid separated by the gas-liquid separator 180 contains ash other than water, a nonmetallic catalyst, or the like, the mixed liquid is removed by the catalyst recovery unit 182 and the nonmetallic catalyst, ash, and Each may be separated into water to recover the nonmetallic catalyst. Thereby, it becomes possible to reuse the nonmetallic catalyst. Further, the liquid component (including ash) separated by the gas-liquid separator 180 or the ash separated by the catalyst recovery unit 182 is used in the following “phosphate recovery method”, and phosphorus containing hydroxyapatite is used. The acid salt can also be recovered.

  The generated gas (fuel gas) stored in the gas tank 181 is supplied to the power generator 190 and the heaters 161 and 163. The power generation device 190 generates power using the supplied generated gas and provides power. Also, the heaters 161 and 163 burn the supplied product gas in a gas containing oxygen to heat the reactor 160 and the preheater 162, and heat the slurry body to a predetermined temperature.

  The exhaust gas discharged from the power generation device 190 when the power generation device 190 generates power using the generated gas as fuel is supplied to the pretreatment device 140 and the preheater 164, and the mixture supplied from the supply pump 120 to the pretreatment device 140 is heated. In the preheater 164, heat is supplied to the gas containing oxygen used in the heaters 161 and 163.

  Further, the exhaust gas obtained by burning the product gas in a gas containing oxygen by the heater 163 is supplied to the reactor 160 to provide heat to the slurry body. The exhaust gas provided with heat by the reactor 160 and the exhaust gas obtained by burning the product gas in a gas containing oxygen by the heater 161 are supplied to the pretreatment device 140 and the preheater 164 and supplied to the supply pump 120. The heat is supplied to the mixture supplied to the pre-processing device 140, or the preheater 164 supplies heat to the oxygen-containing gas used in the heaters 161 and 163.

  In addition, as a nonmetallic catalyst used in this Embodiment, activated carbon, a zeolite, these mixtures etc. can be mentioned, for example. In this way, by using a non-metal catalyst instead of an alkali metal catalyst, it is possible to prevent deterioration due to corrosion of equipment or piping caused by the alkali metal catalyst, and a biomass gasification system with a biomass adhesion prevention function 200 long-term use can be realized. In addition, a processing step for neutralizing the alkali metal catalyst is not required, and the efficiency of workability can be improved. As the non-metallic catalyst, it is preferable to use a powder having an average particle size of 200 μm or less, and more preferably porous. By using such a nonmetallic catalyst, the surface area is increased to increase the reaction efficiency, and the clogging of equipment, piping, etc. in the biomass gasification system 200 with a biomass adhesion preventing function by the nonmetallic catalyst is prevented. Can do.

  In addition, when the biomass to be treated in the present embodiment is wastewater sludge or manure containing foreign substances such as sand, before and after hydrothermal treatment of biomass in the pretreatment device 140, a known separation technique (for example, Foreign substances such as sand contained in the biomass may be removed by a separation method using a strainer or a separation method using a sediment layer. As a result, troubles caused by foreign matters such as sand can be prevented.

=== Configuration of the collection system ===
FIG. 16 is a schematic configuration diagram of a collection system 500 described as an embodiment of the present invention.
The recovery system 500 of this embodiment includes a hydrochloric acid reaction device 510, a filtration device 520, a sodium hydroxide reaction device 530, a recovery device 540, and control valves 550 to 554.

  The hydrochloric acid reaction device 510 is a device that reacts the liquid component containing the ash separated by the gas-liquid separator 180 or the ash separated by the catalyst recovery device 182 with hydrochloric acid. The recovery system 500 may include only one or both of the gas-liquid separator 180 and the catalyst recovery unit 182, but in FIG. 16, the gas-liquid separator 180-catalyst recovery unit 182 is included. The case where both are provided in this order is shown. The hydrochloric acid reactor 510 that can be used here can react the liquid component containing the ash separated by the gas-liquid separator 180 or the ash separated by the catalyst recovery unit 182 with hydrochloric acid, and the material thereof is There is no particular limitation as long as it does not react with hydrochloric acid (for example, Hastelloy B). Further, in order to efficiently obtain ash from the gas-liquid separator 180 and the catalyst collector 182, the hydrochloric acid reactor 510 is preferably in communication with the gas-liquid separator 180 or the catalyst collector 182. The hydrochloric acid reaction device 510 may include a shaker in order to mix the ash and hydrochloric acid evenly.

  Filtration device 520 is a device that filters hydrochloric acid after reacting with ash in hydrochloric acid reaction device 510. The filtration device 520 that can be used here may be anything as long as it has a device capable of filtering hydrochloric acid after reacting with ash in the hydrochloric acid reaction device 510, and examples thereof include a centrifuge, a belt press, and a screw press. It is done. Further, in order to efficiently obtain hydrochloric acid after reacting with ash from the hydrochloric acid reactor 510, the filtration device 520 is preferably in communication with the hydrochloric acid reactor 510.

  The sodium hydroxide reaction device 530 is a device for reacting the filtrate obtained in the filtration device 520 with an aqueous sodium hydroxide solution. The sodium hydroxide reaction device 530 that can be used here can react the filtrate filtered from the filtration device 520 with an aqueous sodium hydroxide solution and does not react with hydrochloric acid or sodium hydroxide (for example, Hastelloy B). If it consists of, it will not specifically limit. In order to efficiently obtain the filtrate from the filtration device 520, the sodium hydroxide reaction device 530 is preferably in communication with the filtration device 520. The sodium hydroxide reaction device 530 may include a shaker in order to mix the filtrate and the aqueous sodium hydroxide solution evenly.

  The recovery device 540 is a device that recovers a precipitate generated by reacting the filtrate with an aqueous sodium hydroxide solution in the sodium hydroxide reaction device 530. The recovery device 540 that can be used here may be anything as long as it can recover the sediment precipitated in the sodium hydroxide reaction device 530. For example, a membrane filter of 0.2 μm to 1.0 μm is provided for recovery. It may be. Further, the recovery device 540 is preferably in communication with the sodium hydroxide reaction device 530.

  It should be noted that the liquid flow rate is between the gas-liquid separator 180 or the catalyst recovery unit 182 and the hydrochloric acid reaction device 510, between the hydrochloric acid reaction device 510 and the filtration device 520, and between the filtration device and the sodium hydroxide reaction device 530. Control valves 550 to 554 and the like may be provided as an example of means for controlling the above.

=== Phosphate recovery method ===
Hereinafter, a method for recovering phosphate from a by-product generated in the biomass gasification system 200 with the biomass adhesion preventing function using the recovery system 500 will be described. In the initial state, all the control valves 550 to 554 are closed.

First, the control valves 550 and 552 or 551 are opened, and the liquid component containing the ash separated by the gas-liquid separator 180 or the ash separated by the catalyst recovery unit 182 is supplied to the hydrochloric acid reactor 510. Here, the amount of ash supplied to the hydrochloric acid reactor 510 is preferably such that the liquid / solid (L / S) ratio is 5 ml / g to 10 ml / g. The ash and hydrochloric acid are preferably mixed well using a shaker.
Next, the control valve 553 is opened, the mixture is supplied to the filtration device 520, and hydrochloric acid after reacting with ash is filtered.

Next, the control valve 554 is opened, and the filtrate obtained by filtering hydrochloric acid is supplied to the sodium hydroxide reactor 530. And the pH of a filtrate is adjusted to 4.0-9.0 using sodium hydroxide aqueous solution, and a phosphate is deposited. For example, when the pH of the filtrate is 4.0, calcium monohydrogen phosphate, and when the pH is 6.0-9.0, monetite (dicalcium phosphate) (FIG. 14), hydroxyapatite (FIG. 13), or these Of the mixture (monetite and hydroxyapatite).
Finally, in the recovery device 540, the precipitate (phosphate) present in the sodium hydroxide reaction device 530 is recovered.

  Here, as a condition for starting the recovery system 500, for example, when the amount of liquid components including ash accumulated in the gas-liquid separator 180 reaches a predetermined level, or when the ash content recovered by the catalyst recovery device 182 is reached. This may be done when the amount reaches a predetermined level.

  Further, for example, each of the control valves 550 to 554 is an electromagnetic valve, and a control line for controlling each electromagnetic valve is connected to a computer, and the computer hardware and control software operating on the hardware are used to The electromagnetic valve may be remotely controlled.

  As described above, the biomass gasification system 200 with the biomass adhesion preventing function is the second heat exchanger 131, the pipe connecting the preheater 162 and the reactor 160, or the peeling device 250 provided in the reactor 160. Can be continuously supplied from the second heat exchanger 131 to the reactor 160. Here, the phosphate collection | recovery system of this embodiment is collect | recovering phosphate from the by-product produced | generated in the biomass gasification system 200 with a biomass adhesion prevention function. Thus, according to the phosphate recovery system of the present embodiment, the phosphate is efficiently produced from the by-product generated in the biomass gasification system 200 with the biomass adhesion preventing function using biomass containing phosphorus such as chicken manure as a raw material. It can be recovered well. Therefore, the phosphate recovery system of the present embodiment can recover a desired amount of phosphate in a shorter time, and is economically superior in terms of costs for operating the system. I can say that.

  Hydroxyapatite is known to be used for biofunctional materials such as artificial bones and dental fillers. According to the phosphate recovery system of this embodiment, it is also possible to efficiently recover economically effective hydroxyapatite from by-products generated in a biomass power generation system using biomass containing phosphorus such as chicken manure as a raw material It becomes.

  Thus, if the phosphate recovery system of the present invention is used, it is possible to recover phosphorus, which is said to be a resource that will be depleted in the future, from biomass.

  The description of the above embodiment is intended to facilitate understanding of the present invention and does not limit the present invention. It goes without saying that the present invention can be changed and improved without departing from the gist thereof, and that the present invention includes equivalents thereof.

  Hereinafter, the present invention will be specifically described by way of examples. These examples are for explaining the present invention, and do not limit the scope of the present invention.

[Example 1]
The following experiment was conducted using the biomass gasification system shown in FIG.
A biomass slurry obtained by stirring and mixing 97.6 parts by mass of water, 2 parts by mass of chicken dung, and 0.4 parts by mass of activated carbon having a particle size of 20 μm and hydrothermally treated at 180 ° C. and 1.1 MPa was used as a high-pressure pump. Was pressed into a tubular reactor, and a reaction with supercritical water was performed under conditions of 600 ° C. and 25 MPa. As a control experiment, a gasification reaction with supercritical water was similarly performed without adding activated carbon. As a result, it is clear that the carbon gasification rate is 73% when no activated carbon is added, whereas the carbon gasification rate increases to 88% when 0.4 parts by mass of activated carbon is added. Became.

[Example 2]
Next, 80 parts by mass of water, 20 parts by mass of cellulose powder, and 20 parts by mass of activated carbon having an average particle size of 100 μm were stirred and mixed to prepare a slurry. Thereafter, 40 ml of the slurry was poured into a 167 ml autoclave equipped with a stirrer, and the temperature was raised to 400 ° C. while stirring at a pressure of 25 MPa and held for 1 hour to perform a gasification reaction with supercritical water. After the reaction, the reaction mixture was cooled to room temperature, and the product gas was recovered to determine the carbon gasification rate. As a control experiment, the same treatment was performed without adding activated carbon. As a result, it was found that the carbon gasification rate was 10% when no activated carbon was added, whereas the carbon gasification rate increased to 30% when activated carbon was added.
From the above, it has become clear that the gasification efficiency can be increased by adding a nonmetallic catalyst.

[Example 3]
As shown in FIG. 3, a dispersion plate (net) is provided below a fluidized bed reactor 160 (φ12.3 mm × 2400 mm) provided with an inlet 210 and an outlet 220, and alumina balls having an average particle diameter of 1 mm are flowed. Installed as a medium. In this fluidized bed reactor 160, a mixture of alumina particles (average particle size of 180 to 250 μm or average particle size of 250 to 300 μm) mixed with water instead of biomass (ash) or non-metallic catalyst is mixed with alumina. The particles were ejected and introduced from the inlet 210 at a flow rate (0.19 m / s to 0.60 m / s) at which the alumina balls as the fluid medium did not eject, and the alumina particles discharged from the outlet 220 were collected.

  As a result, when alumina particles having an average particle diameter of 180 to 250 μm are introduced into the fluidized bed reactor 160, 97.5% alumina particles can be recovered, and alumina particles having an average particle diameter of 250 to 300 μm are recovered. When introduced into the fluidized bed reactor 60, it was found that 98.9% alumina particles could be recovered. From this, a slurry body of biomass (average particle size is 300 μm or less) containing a nonmetallic catalyst is supplied to the fluidized bed reactor 160 as described above at a predetermined flow rate (for example, the maximum at which the fluidized medium does not jump out from the discharge port). The generated product gas and ash as well as the nonmetallic catalyst and water (supercritical water) are obtained by performing a hydrothermal reaction at a predetermined temperature and a predetermined pressure while being introduced from the inlet 210 at a flow rate). It was shown that it can be discharged from the outlet 220.

[Example 4]
The following experiment was conducted using the biomass gasification system shown in FIG.
A biomass slurry obtained by stirring and mixing 97.6 parts by mass of water, 2 parts by mass of chicken dung, and 0.4 parts by mass of activated carbon having a particle size of 20 μm and hydrothermally treated at 180 ° C. and 1.1 MPa was used as a high-pressure pump. Was introduced into the second heat exchanger 131.

  As shown in FIG. 9, the pressure in the second heat exchanger 131 before operating the biomass gasification system was 25.0 MPa, but from about 2 hours after the biomass gasification system 200 was operated. The pressure started to increase, and after about 2 hours and 45 minutes, the pressure reached 26.0 MPa. At this time, the frequency in the slurry supply apparatus 150 was 44.4 Hz. Therefore, an air knocker (seishin corporation, product) against the outer surface (jacket side) of the piping at the inlet portion of the second heat exchanger 131 and the inner surface (tube side) of the piping at the inlet portion of the second heat exchanger 131. No .: SK air knocker).

  As a result, as shown in FIG. 9, the pressure in the second heat exchanger 131 gradually decreased from 26.0 MPa to 25 MPa. In addition, the frequency in the slurry supply apparatus 150 at this time was 39.0 Hz (refer FIG. 9). On the other hand, the pressure in the cooler 170 did not increase from 25.0 MPa.

  Thus, by giving an impact to the inner surface of the second heat exchanger 131 to which the biomass slurry is adhered, the biomass slurry adhered to the inner surface is peeled off from the inner surface of the second heat exchanger 131, and the preheater 162. Was supplied to. Accordingly, if an impact can be applied to the inner surface of the second heat exchanger 131 to which the biomass slurry body is adhered, the blockage of the second heat exchanger 131 due to the biomass slurry body is eliminated, and as a result, the biomass gasification system Can be operated continuously.

[Example 5]
The following experiment was conducted using the biomass gasification system shown in FIG.
A biomass slurry obtained by stirring and mixing 97.6 parts by mass of water, 2 parts by mass of chicken dung, and 0.4 parts by mass of activated carbon having a particle size of 20 μm and hydrothermally treated at 180 ° C. and 1.1 MPa was used as a high-pressure pump. Was introduced into the second heat exchanger 131, the temperature was raised to 600 ° C. while stirring at a pressure of 25 MPa, and the gasification reaction with supercritical water was carried out for 1 hour. After the reaction, the reactor was cooled to room temperature, and X-ray analysis (XRD) was performed on the biomass slurry adhered to the inner surface of the tube of the tubular reactor 160. FIG. 10 shows a comparison of XRD patterns of the biomass slurry attached to the inner surface of the tube of the tubular reactor 160 and hydroxyapatite.

  It was confirmed that the biomass slurry adhered to the inner surface of the tube of the tubular reactor 160 was hydroxyapatite. From this, it was shown that the cause of the blockage in the biomass gasification system is mainly hydroxyapatite. Here, the exhaust discharged from the outlet 220 of the reactor 160 is introduced into the second heat exchanger 131. Therefore, it was shown that the cause of the blockage of the second heat exchanger 131 was mainly hydroxyapatite.

[Example 6]
(I) Preparation of Experimental Samples 85 parts by mass of water, 10 parts by mass of chicken manure, and 5 parts by mass of activated carbon having a particle size of 10 to 100 μm were stirred and mixed, and a slurry of biomass hydrothermally treated at 180 ° C. and 1.1 MPa. The body was press-fitted into a tubular reactor with a high-pressure pump, and a gasification reaction with supercritical water was performed under conditions of 600 ° C. and 25 MPa. As a control experiment, a gasification reaction with supercritical water was similarly performed without adding activated carbon. A solid obtained by this gasification reaction (mixed ash and activated carbon: hereinafter referred to as “supercritical water gasification byproduct”) dried at 105 ° C. was used in the following experiment.

First, 1000 ml of 1N hydrochloric acid is added to 100.0 g of the supercritical water gasification byproduct (L / S ratio = 10 [ml / g]), shaken at room temperature for 1 hour (200 rpm), and phosphorus is removed from the supercritical water gasification byproduct. Elute. Next, the suspension was filtered with a filter paper (No. 5C) to obtain an activated carbon-like solid (hereinafter referred to as substance A) and a phosphorus eluate. A sodium hydroxide aqueous solution was added to the phosphorus eluate to adjust the pH to 7.5, and the resulting white precipitate (hereinafter referred to as “substance B”) was filtered through a membrane filter (pore diameter: 1.0 μm). Finally, substance A and substance B were dried at 105 ° C. (see FIG. 11).
When the substances A and B were weighed, the substance A was 69.3 g and the substance B was 28.0 g. Moreover, the color of the substance B was white.

(Ii) Fluorescence X-ray analysis Next, in order to compare the components contained in the supercritical water gasification by-product and the substance A, the fluorescence X for the main five components (C, Ca, P, Si, Mg). Line analysis was performed.

From Table 1, it was found that the three main components of the supercritical water gasification by-product were C (57%), CaO (21%) and P ₂ O ₅ (12%). In substance A, the C content increased to 73%, but P was not present in the five main components, and the Ca content also decreased. From this, it became clear that phosphorus and calcium were removed from the supercritical water gasification by-product, and that the purity of the activated carbon in the substance A was increased.

(Iii) X-ray analysis (XRD)
In Chemical Industry Daily “15107 Chemical Products” (2007), calcium monohydrogen phosphate is 400-550 yen per kg, calcium dihydrogen phosphate is 460-800 yen per kg, and tricalcium phosphate is 600-kg per kg. 650 yen, hydroxyapatite is described as 10,000 yen per kg. Therefore, X-ray analysis was performed to determine whether the phosphorus eluate contained hydroxyapatite. FIG. 12 shows a comparison of XRD patterns of substance B and hydroxyapatite.

  It was confirmed that the main component of the substance B was hydroxyapatite. From this, it was shown that hydroxyapatite can be recovered from supercritical water gasification by-products using chicken manure. In addition, the chicken manure used as a raw material does not contain hydroxyapatite (FIG. 13).

[Example 7]
(I) Preparation of Experimental Samples 85 parts by mass of water, 10 parts by mass of chicken manure, and 5 parts by mass of activated carbon having a particle size of 10 to 100 μm were stirred and mixed, and a slurry of biomass hydrothermally treated at 180 ° C. and 1.1 MPa. The body was press-fitted into a tubular reactor with a high-pressure pump, and a gasification reaction with supercritical water was performed under conditions of 600 ° C. and 25 MPa. As a control experiment, a gasification reaction with supercritical water was similarly performed without adding activated carbon. A solid obtained by this gasification reaction (mixed ash and activated carbon: hereinafter referred to as “supercritical water gasification byproduct”) dried at 105 ° C. was used in the following experiment.

  First, 1000 ml of 1N hydrochloric acid is added to 100.0 g of the supercritical water gasification byproduct (L / S ratio = 10 [ml / g]), shaken at room temperature for 1 hour (200 rpm), and phosphorus is removed from the supercritical water gasification byproduct. Elute. Next, the suspension was filtered with a filter paper (No. 5C) to obtain an activated carbon-like solid and a phosphorus eluate. A sodium hydroxide aqueous solution was added to the phosphorus eluate to adjust the pH to 6.0, and the resulting white precipitate was filtered through a membrane filter (pore size: 1.0 μm). Finally, the obtained white precipitate was dried at 105 ° C. and subjected to X-ray analysis.

(Ii) X-ray analysis (XRD)
FIG. 14 shows the XRD pattern of the white precipitate.
It was confirmed that the white precipitate obtained at pH 6.0 was monetite (FIG. 14). From this, it was shown that monetite can be recovered from supercritical water gasification by-products using chicken manure.
On the other hand, an aqueous solution of sodium hydroxide was added to the phosphorus eluate to adjust the pH to 13.1, and the resulting white precipitate was filtered through a membrane filter (pore size: 1.0 μm). After drying at 0 ° C., X-ray analysis was performed. As a result, this white precipitate was found to be calcium carbonate (FIG. 15).

It is a figure which shows the whole structure of the biomass gasification system 200 with a biomass adhesion prevention function demonstrated as one Embodiment of this invention. In one Embodiment of this invention, it is a figure which shows schematic structure of the tubular reactor 160. FIG. In one Embodiment of this invention, it is a figure which shows schematic structure of the fluidized bed reactor 160 in which a continuous operation is possible. It is a figure which shows schematic structure of the slurry supply apparatus 150 demonstrated as one Embodiment of this invention. It is a figure which shows schematic structure of the catalyst collection | recovery device 182 demonstrated as one Embodiment of this invention. In one Embodiment of this invention, it is a figure which shows schematic structure of the 2nd heat exchanger 131 which provided the peeling apparatus 250. FIG. In one Embodiment of this invention, it is a figure which shows the whole structure of the biomass gasification system 200 with a biomass adhesion prevention function in case the waste heat temperature of an electric power generating apparatus is higher than the reaction temperature in a reactor. In one embodiment of the present invention, the entire biomass gasification system with a biomass adhesion preventing function when the temperature of the exhaust heat of the power generator 190 is lower than the reaction temperature in the reactor 160 and higher than the treatment temperature in the pretreatment device 140. It is a figure which shows a structure. In one Embodiment of this invention, it is a figure which shows the measurement result of the pressure (MPa) near the 2nd heat exchanger 131 exit with respect to the starting time of the biomass gasification system 200 with a biomass adhesion prevention function. It is the figure which compared the XRD pattern of the slurry body of biomass adhering to the inner surface of the pipe | tube of the tubular reactor 160 in one Example of this invention, and a hydroxyapatite. It is a figure which shows the experimental flow in one Embodiment of this invention. It is the figure which compared the XRD pattern of the substance B and hydroxyapatite in one Example of this invention. It is the figure which compared the XRD pattern of the chicken manure which is the raw material in one Example of this invention, and a hydroxyapatite. Is a diagram showing an XRD pattern of monetite (CaPO ₃ (OH)) according to an embodiment of the present invention. It is the figure which showed the XRD pattern of the calcium carbonate in one Example of this invention. It is a figure which shows schematic structure of the phosphate collection | recovery system which consists of a biomass power generation system and collection | recovery system demonstrated as one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Adjustment tank 110 Crusher 120 Supply pump 130 1st heat exchanger 131 2nd heat exchanger 140 Pretreatment apparatus 150 Slurry supply apparatus 160 Reactor 161 Heater 162 Preheater 163 Heater 164 Preheater 170 Cooler 171 Depressor 180 Gas-liquid separator 181 Gas tank 182 Catalyst recovery unit 190 Power generation device 200 Biomass gasification system with biomass adhesion prevention function 210, 211 Inlet 220, 221 Discharge port 230 Fluid medium 240 Dispersing unit 250 Peeling device 310, 320 Cylinder 330 Shaft 331, 332 Piston 340 Stirrer 350 Stirrer 360 Water injection device 361-364 Valve 371, 372 Three-way valve 373-376 Valve 380, 381 Pressure accumulator 410 Mixed liquid injection part 420 Water tank 421 Discharge port 422, 423 Activated carbon receiving part 424 Drain port 425, 426 籠 430 Circulation pump 440 Supply pipe 450 Ash receiving part 451 籠 460, 461, 470 Valve 500 Recovery system 510 Hydrochloric acid reactor 520 Filtration device 530 Sodium hydroxide reaction device 540 Recovery device 550-554 valve

Claims (29)

It is a method of treating biomass containing phosphorus with a high-temperature and high-pressure gas and recovering phosphate from the treated reactant,
In the presence of a non-metallic catalyst, the biomass is hydrothermally treated under conditions of a temperature in the range of 100 to 250 ° C. and a pressure in the range of 0.1 to 4 MPa,
The biomass slurry containing the non-metallic catalyst obtained by hydrothermal treatment is introduced into a heater and heated,
The heated biomass slurry is introduced into a preheater and preheated,
The preheated biomass slurry is introduced into a reactor and hydrothermally treated under conditions of a temperature of 374 ° C. or higher and a pressure of 22.1 MPa or higher,
The ash produced by the hydrothermal treatment is reacted with hydrochloric acid,
Filtering the hydrochloric acid after reacting with the ash,
The filtrate obtained by filtering the hydrochloric acid is reacted with an aqueous sodium hydroxide solution,
Collecting a precipitate formed after reacting the filtrate with the aqueous sodium hydroxide solution;
Including
By applying an impact to at least one inner surface of the heater to which the biomass slurry is attached, a pipe connecting the preheater and the reactor, or an inner surface of the reactor, Peeling the slurry body from the inner surface;
A phosphate recovery method characterized by the above.   2. The phosphate recovery method according to claim 1, wherein the step of applying an impact to the inner surface includes a step of applying vibration to the inner surface or a step of spraying a gas onto the inner surface.   The phosphate recovery method according to claim 1 or 2, wherein an impact is applied to the inner surface when the pressure in the heater becomes 26.0 MPa or more.   Separating the product gas, ash, non-metallic catalyst, and water produced by hydrothermal treatment into the product gas and a mixed solution containing the ash, the non-metallic catalyst, and water, The phosphate recovery method according to any one of claims 1 to 3, wherein the ash is reacted with hydrochloric acid by reacting the mixed solution with hydrochloric acid. Wherein the pH of the filtrate becomes 6.0 to 9.0, the phosphate recovery method according to any one of claims 1 to 4, characterized in that is reacted with sodium hydroxide solution.   The phosphate recovery method according to claim 1, wherein the precipitate is monetite and / or hydroxyapatite. The biomass containing phosphorus is heated by using exhaust heat of a power generation device that generates electric power using the generated gas or heat of exhaust gas obtained by burning the generated gas with the heater. The phosphate recovery method according to claim 4 . In the step of heating the slurry body by introducing it into a heater, the slurry body is heated by burning a part of the generated gas in a gas containing oxygen,
The oxygen-containing gas is preheated using exhaust heat of a power generation device that generates power using the generated gas or heat of exhaust gas obtained by burning the generated gas with the heater. The phosphate recovery method according to claim 4 . A pretreatment apparatus for hydrothermally treating phosphorus-containing biomass in the presence of a nonmetallic catalyst under conditions of a temperature in the range of 100 to 250 ° C and a pressure in the range of 0.1 to 4 MPa;
Reaction of hydrothermally treating the biomass slurry containing the nonmetallic catalyst obtained by hydrothermal treatment in the pretreatment apparatus under conditions of a temperature of 374 ° C. or higher and a pressure of 22.1 MPa or higher And
A power generation device that generates power using the generated gas generated by hydrothermal treatment in the reactor;
A heater for burning a part of the product gas in a gas containing oxygen to heat the slurry body in the reactor;
A preheater that preheats the oxygen-containing gas used in the heater using exhaust heat of the power generation device;
A hydrochloric acid reactor for reacting the ash produced by the hydrothermal treatment with hydrochloric acid;
A filtration device for filtering the hydrochloric acid after reacting with the ash;
A sodium hydroxide reactor for reacting the filtrate obtained by filtering the hydrochloric acid with an aqueous sodium hydroxide solution;
A recovery device for recovering a precipitate generated by reacting the filtrate with the aqueous sodium hydroxide solution;
With
In the reactor, the heater, or the pipe, a peeling device that peels off the biomass slurry adhered to the inner surface of the pipe that connects the preheater and the reactor to the reactor, the heater, or the pipe. Having at least one,
Phosphate recovery system characterized by   The phosphate recovery system according to claim 9, wherein the peeling device is a vibration device or a gas injection device.   A gas-liquid separator that separates the product gas, ash, non-metallic catalyst, and water discharged from the reactor into the product gas and a mixed solution containing the ash, the non-metallic catalyst, and water. The phosphate recovery system according to claim 9 or 10, further comprising:   The phosphate recovery system according to any one of claims 9 to 11, further comprising a power generation device that generates electric power using a generated gas generated by hydrothermal treatment in the reactor.   13. The apparatus according to claim 9, further comprising a heater that burns a part of the product gas discharged from the reactor in a gas containing oxygen to heat the slurry body in the reactor. The phosphate recovery system according to item 1.   The phosphate recovery system according to claim 10, further comprising a preheater that preheats the oxygen-containing gas used in the heater.   It reacts with sodium hydroxide aqueous solution so that pH of the said filtrate may be 6.0-9.0, The phosphate recovery system of any one of Claims 9-14 characterized by the above-mentioned.   The phosphate recovery system according to any one of claims 9 to 15, wherein the precipitate is monetite and / or hydroxyapatite.   The pretreatment device includes means for heating the biomass containing phosphorus using exhaust heat of the power generation device or heat of exhaust gas obtained by burning the product gas with the heater. The phosphate recovery system according to any one of claims 9 to 16.   The preheater includes means for preheating the gas containing oxygen using exhaust heat of the power generation device or heat of exhaust gas obtained by burning the generated gas with the heater. The phosphate recovery system according to any one of claims 9 to 17.   The heat exchanger which preheats the said slurry body hydrothermally processed with the said reactor using the heat | fever of the said production | generation gas discharged | emitted from the said reactor is provided, The heat exchanger of any one of Claims 9-18 characterized by the above-mentioned. The phosphate recovery system according to item.   The heat exchanger which preheats the biomass containing the said phosphorus which is hydrothermally processed with the said pre-processing apparatus using the heat | fever of the said slurry body hydrothermally processed with the said reactor, It is characterized by the above-mentioned. The phosphate collection | recovery system of any one of -19.   A heat exchanger for preheating the biomass containing phosphorus that is hydrothermally treated in the pretreatment device using heat of the product gas discharged from the reactor is provided. 21. The phosphate recovery system according to any one of 20 above. A slurry supply device for receiving the slurry body from the pretreatment device and supplying the slurry body to the reactor;
A first pressure accumulator arranged between the pretreatment device and the slurry supply device and accumulating the slurry body received in the slurry supply device;
A second pressure accumulator that is disposed between the slurry supply device and the reactor and accumulates the slurry body supplied from the slurry supply device;
Further comprising
The slurry supply apparatus includes:
An inlet for injecting water, an outlet for discharging the injected water, an inlet for receiving the slurry body from the pretreatment device, and a supply port for supplying the received slurry body to the reactor. Two cylinders with
A piston arranged to partition the water and the slurry body in each cylinder;
A shaft with each piston at both ends;
A stirrer for stirring the slurry body in each cylinder;
The second cylinder is adapted to receive the slurry body from the pretreatment device into the first cylinder and to supply the slurry body received from the pretreatment device to the second cylinder to the reactor. Supplying the slurry body received in the first cylinder to the reactor, and receiving the slurry body from the pretreatment device in the second cylinder; A water injection device for alternately switching the second step of injecting the water into the first cylinder;
The phosphate recovery system according to any one of claims 9 to 21, wherein the phosphate recovery system is provided.   23. The phosphate recovery system according to claim 22, wherein the shaft further includes contact prevention means for preventing contact between the piston and the stirrer.   The phosphate recovery system according to claim 22 or 23, wherein the water injection device injects water at a constant flow rate to each cylinder. The reactor is
An inlet for introducing the slurry body into the reactor from below;
A product gas and ash produced by hydrothermal treatment in the reactor, and a discharge port for discharging the nonmetallic catalyst and water from the top to the outside of the reactor;
A fluidized medium that forms a fluidized bed in the reactor by introducing the slurry body;
A dispersion part for dispersing the slurry introduced from the introduction port below the fluidized bed;
With
The phosphate recovery system according to any one of claims 9 to 24, wherein the fluid medium has a shape that is not discharged at an introduction speed of the slurry body.   26. The phosphate recovery system according to claim 25, wherein the fluid medium is an alumina ball.   27. The phosphate recovery system according to claim 25 or 26, wherein the dispersion part is formed by stacking alumina balls. The phosphate recovery system according to claim 11 , further comprising means for recovering the nonmetallic catalyst in the mixed solution.   The phosphate recovery system according to any one of claims 9 to 28, further comprising a crusher that crushes in advance the biomass containing phosphorus that is hydrothermally treated by the pretreatment device.