JP2009066541A - Hydrothermal reaction treatment apparatus and hydrothermal reaction treatment method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enable efficient and ecofriendly material denaturation and reutilization of a variety of particulate substances, especially organic solid particles by means of hydrothermal reaction treatment without using a large quantity of chemical substances except water. <P>SOLUTION: Disclosed are a hydrothermal reaction treatment apparatus being a flow-type hydrothermal reaction treatment apparatus consisting essentially of a slurry reserve tank, a pressure pump, a heating part, a cooling apparatus, a pressure regulator, and a receiving tank, wherein these members are connected to each other through a cylindrical pipe, and a hydrothermal treatment reactor constituted from a cylindrical pipe having a degree of descending inclination corresponding to an inclination angle of 5-30° is installed in the heating part and a hydrothermal reaction treatment method. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention provides an apparatus for efficiently performing a hydrothermal reaction of a particulate solid and an efficient hydrothermal reaction treatment method using the apparatus. Specifically, a fluid-type hydrothermal reaction treatment apparatus equipped with a hydrothermal treatment reactor composed of a cylindrical tube having a specific downward slope in the flow path, and a particulate solid adjusted to a slurry at room temperature and atmospheric pressure An apparatus for recovering a product by efficiently performing a hydrothermal reaction treatment by continuously injecting the product into the hydrothermal reaction reactor, and subjecting the hydrothermal reaction reactor to pressure heat treatment under flow in the flow; It is about the method.

  Pressurized water can be used as a liquid even at 100 ° C. or higher, and is useful as a modification treatment medium for various substances. The treatment with liquid water pressurized and heated in this way is hereinafter referred to as “hydrothermal reaction treatment”. For example, it is already known that water-soluble polymers such as proteins are reduced in molecular weight or hydrolyzed to amino acids by hydrothermal reaction treatment. Such a phenomenon is particularly safe when used below the critical temperature and below the critical pressure, because it is chemically safe because of non-oxidation treatment, consumes less energy, and excessively decomposes the material to be treated. Therefore, industrial applications are expected such that useful materials can be efficiently recovered and reused.

The hydrothermal reaction treatment is possible in principle when the object to be treated is liquid, and can contribute to downsizing and efficiency of the apparatus. On the other hand, when trying to perform a hydrothermal reaction process on a solid material, a batch process that is difficult to reduce in size must be applied, which is unsatisfactory in terms of efficiency and practical use. In addition, a conventional continuous processing apparatus using supercritical water or subcritical water and a method for hydrolyzing an organic slurry using the same are known (see Patent Document 1), but it is applied to efficient hydrothermal reaction processing of hardly decomposed substances. Therefore, a more appropriate hydrothermal reaction treatment apparatus and treatment method are required.
Japanese Patent Laying-Open No. 2005-034808 JP 2000-309663 A

  As a result of various studies conducted by the present inventors to solve the above-mentioned problems, a fluid type hydrothermal reaction processing apparatus provided with a hydrothermal treatment reactor composed of a cylindrical tube having a specific downward slope in the flow path is used. Thus, the inventors have found that efficient treatment is possible by performing hydrothermal reaction treatment under specific hydrothermal reaction treatment conditions, and the present invention has been achieved.

  That is, the gist of the present invention is a fluid-type hydrothermal reaction treatment apparatus including at least a slurry storage tank, a pressurized liquid feeder, a heating unit, a cooler, a pressure regulator, and a receiving tank, and these devices are connected by a cylindrical tube. The hydrothermal reaction treatment apparatus is characterized in that a hydrothermal treatment reactor composed of a cylindrical tube having a descending inclination with an inclination angle of 5 to 30 ° is installed in the heating section.

  Another aspect of the present invention is a method for hydrothermal reaction treatment of a particulate solid, wherein the particulate solid having a major axis of 4 mm or less is supplied as a water slurry from a slurry storage tank, and at least a pressurized liquid feeder, a heating unit, Hydrothermal treatment reactor having a downward slope with an inclination angle of 5 to 30 °, which is press-fitted into a fluid-type hydrothermal reaction treatment apparatus in which a cooler, a pressure regulator section and a receiving tank are connected by a cylindrical tube. In a hydrothermal reaction treatment method characterized by hydrothermal treatment at

  According to the present invention, it is possible to efficiently decompose a variety of particulate substances, particularly organic solid particles without using a large amount of chemical substances other than water, so that environmentally friendly substance modification / reuse is possible. Become.

  Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 is a schematic view of a hydrothermal reaction treatment apparatus according to an embodiment of the present invention, and FIG. 2 is a schematic view of a hydrothermal reaction treatment apparatus according to another embodiment of the present invention.

  In FIG. 1, 1 is a slurry storage tank, 2 is a pressurized liquid feeder, 3 is a heating unit, 3-1 is a hydrothermal treatment reactor, 4 is a cooler, 5 is a pressure regulator, and 6 is a receiving tank. It is a hydrothermal reaction processing apparatus connected by a cylindrical tube 7.

  The slurry storage tank 1 is a container that stably holds a particulate solid material to be treated as a water slurry. Although the shape of the said container is arbitrary, it is desirable to have a stirring function for holding the slurry uniformly in the tank.

  In order to keep the aqueous slurry of particulate solids uniform, the size of the particulate solids is a maximum of 4 mm at maximum, preferably 3 mm or less, particularly preferably 2 mm or less. If the diameter is too large, it is difficult to slurry, which causes blockage of the flow path. In addition, reducing the particle size does not adversely affect the hydrothermal reaction treatment, but it is uneconomical and inefficient because it requires a step for making the solid particles finer.

  As such particle solids, artificial organic polymers such as plastics, and natural products such as plants, seeds, fish and shellfish, meat, livestock bones or modified products thereof are particularly preferable.

  As a method for keeping the aqueous slurry of particulate solids uniform, a small amount of a water-soluble polymer substance can be added to water. The polymer substance has an effect of increasing the viscosity and decreasing the sedimentation or floating speed of the particulate solid, and also has a function of preventing the particulate solid from aggregating into large particles. It is also effective to adjust the temperature of the slurry storage tank 1 in order to keep the slurry uniform.

  The pressurized liquid feeder 2 inserts the water slurry of the particulate solid material under pressure from the slurry storage tank 1 toward the hydrothermal treatment reactor 3-1 installed in the heating unit 3 (hereinafter referred to as press-fitting). Equipment. A pump of any type and shape can be used for liquid feeding, but it is preferable to reduce pulsation by the pump. A known device or method can be applied to this. For example, it is possible to employ a method of installing a plurality of plunger-type pumps and operating with a phase shift, or installing a damper at the pump outlet.

  The heating unit 3 is a device that performs a hydrothermal reaction process. The water slurry of the particulate solid material press-fitted into the hydrothermal reactor 3-1 (detailed structure will be described later) installed in the heating unit 3 is heated at this site, so that the hydrothermal reaction under flow It is processed. The heating method is arbitrary, and electric heating, combustion heat, heating medium heating, high-frequency heating, or the like can be used.

  The hydrothermal reactor 3-1 is constituted by a cylindrical tube, and it is necessary to have a tube diameter that allows the water slurry of the particulate solid to flow in the cylindrical tube while maintaining a uniform solid concentration. The inner diameter of this cylindrical tube is preferably 4 to 50 mm, particularly preferably 5 to 30 mm. In this case, if the diameter is too small, the flow rate of the slurry cannot be increased, resulting in inefficiency, and inconvenience such as blockage of the flow path is likely to occur. On the other hand, if the diameter is too large, the heating efficiency is likely to be impaired, and the hydrothermal reaction treatment is not completed.

  The cylindrical tube constituting the hydrothermal reactor 3-1 preferably has a gentle downward slope. Thereby, the flow of the particulate solid matter in the forward direction of the flow path is promoted by its own weight, and the hydrothermal reaction treatment can be performed efficiently. The descending inclination is preferably 3 to 45 °, particularly preferably 5 to 30 °. If the slope is too small, stagnation of particulate solids may occur, causing flow path blockage. If the slope is too large, the sedimentation of particulate solids will exceed the slurry flow rate, reducing the efficiency of hydrothermal reaction treatment. It is not preferable.

  The cylindrical tube constituting the hydrothermal reactor 3-1 may have a linearly inclined structure, but the helical space and the inclined structure can increase the space efficiency of the reactor. At the same time, the heating efficiency can be improved. The curvature of the spiral does not need to be strictly constant and may include a straight portion, but the curvature radius is preferably 50 mm or more at any curved portion of the cylindrical tube, and particularly preferably 60 mm or more. If this radius of curvature is too small, the channel will be blocked.

  Here, the weight of the particulate solid material press-fitted from the pressurized liquid feeder 2 is preferably 5 to 50% of the total slurry weight. In order for the slurry to maintain a fluidized state, it must not be larger than the weight of water as a dispersion, and therefore the maximum is 50%. On the other hand, if the weight of the particulate solid is too small compared to the total slurry weight, most of the heat energy in the heating unit is consumed for heating the water in the slurry, which is inefficient.

  Moreover, it is preferable to set the amount of pressurization per hour of the water slurry of the particulate solid injected into the hydrothermal reactor 3-1 to 30 to 400% of the hydrothermal reactor capacity. It is preferable to adjust the treatment time of the slurry in the reactor to be about 15 minutes to 3 hours in practice. Accordingly, the slurry supply rate is optimally about 4 to 1/3 times the capacity of the hydrothermal reactor.

  Further, in order to always maintain the fluid state of the particulate solid water slurry in the hydrothermal reactor 3-1, the temperature is set to 370 ° C. or lower lower than the critical temperature of water and 23 MPa or lower lower than the critical pressure of water. It is preferable. By adopting these numerical values, the water in the slurry is maintained in a liquid state even in the hydrothermal reaction processor 3-1.

  The cooler 4 removes the water slurry of the particulate solid material that has undergone the hydrothermal reaction treatment in the hydrothermal reaction treatment device 3-1 installed in the heating unit 3 to a boiling point (100 ° C.) or less of water at room temperature. Equipment. Any shape and type of heat exchanger can be used. The water slurry of the particulate solid removed by the cooler 4 to 100 ° C. or less is sent to the pressure regulator 5.

  The pressure regulator 5 is a device that adjusts the liquid pressure in the flow path to reduce it to normal pressure (atmospheric pressure). For this, an existing pressure reducing valve or the like can be used.

  The receiving tank 6 is an apparatus that stores and collects a water slurry of particulate solid material that has been heat-removed to 100 ° C. or less through a hydrothermal reaction treatment. It can be installed at the outlet of the pressure regulator 5 or between the cooler 4 and the pressure regulator 5.

  The hydrothermal reaction treatment product of the particulate solid water slurry thus obtained becomes a final form as it is or after additional processing by existing techniques such as filtration and separation.

  FIG. 2 shows another embodiment of the present invention, in which high-pressure water is sent from a pump 9 to a preheater 10. High-pressure hot water is supplementarily supplied to the water slurry of the particulate solid matter sent out, and these liquid feeds are uniformly stirred by the static mixer 8 and sent to the heating unit 3.

In FIG. 2, a pressurized liquid feeder 2 is configured by arranging two commercially available high-pressure plunger pumps so as to alternately discharge in a half-cycle phase. A stainless steel tube 7 having an inner diameter of 6.4 mm was connected to the discharge side of the pressurized liquid feeder 2.
Also, a stainless steel cylindrical tube having an inner diameter of 6.4 mm is used to form a perfect circular spiral tube having a winding diameter of 136 mm and 22 turns, the axial height of the spiral tube is 470 mm, and the inclination angle of the spiral tube is 8.4. A hydrothermal treatment reactor 3-1 was manufactured. The manufactured hydrothermal reactor 3-1 was installed in an electric furnace to constitute the heating unit 3.

Similarly, a spiral tube having a winding diameter of 136 mm and a winding number of 20 was manufactured and installed in another electric furnace to constitute the preheater 10. The preheater 10 was connected to a commercially available high-pressure liquid chromatograph high-pressure pump 9 on the inflow side, and a stainless steel tube 11 having an inner diameter of 6.4 mm was connected to the outflow side of the preheater 10.
Further, using a cylindrical T joint having an inner diameter of 6.4 mm, the other end of the stainless steel tube 7 is provided on one side of the joint, and the other end of the stainless steel tube 11 is provided on the two sides of the joint. Were connected to the inflow side of the static mixer 8.
Further, the outlet of the hydrothermal treatment reactor 3-1 is connected to the inflow side of a stainless steel pipe having an inner diameter of 6.4 mm constituting the cooler 4, and the outflow side of the pipe is connected to the receiving tank 6 through the pressure regulator 5. Connected to.

  A suspension containing 200 g of porcine-derived insoluble collagen particles (average diameter 0.5 mm, molecular weight of 100,000 or more) and 800 g of water was prepared and placed in a 10 L aluminum storage tank 1 to obtain a raw material slurry. Hydrothermal treatment was performed at a pressure of 12 MPa while maintaining the hydrothermal reactor 3-1 at 240 ° C. and supplying the slurry at 20 mL / min and preheated water at 20 mL / min.

  The treatment station solution obtained in the receiving tank 6 was uniform and had no solid content. When the dissolved content was analyzed by gel permeation chromatography, only a compound having a molecular weight of 5000 was detected. This indicates that the insoluble collagen was totally converted into the collagen peptide without any catalyst in water.

The schematic diagram of the hydrothermal reaction processing apparatus of the Example of this invention. The schematic diagram of the hydrothermal reaction processing apparatus of the other Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Slurry storage tank 2 Pressurized liquid feeder 3 Heating part 3-1 Hydrothermal treatment reactor 4 Cooler 5 Pressure regulator 6 Receiving tank 7 Cylindrical pipe 8 Static mixer 9 Pump 10 Preheater 11 Pipe

Claims (10)

  It is a fluid-type hydrothermal reaction processing apparatus comprising at least a slurry storage tank, a pressurized liquid feeder, a heating unit, a cooler, a pressure regulator, and a receiving tank, and these devices are connected by a cylindrical tube. A hydrothermal reaction treatment apparatus comprising a hydrothermal treatment reactor composed of a cylindrical tube having a downward slope of 5 to 30 °.   2. The hydrothermal reaction treatment apparatus according to claim 1, wherein the hydrothermal treatment reactor is a cylindrical tube having an inner diameter of 5 mm or more, and has a spiral shape with a curvature radius of a curved portion of 50 mm or more.   A method for hydrothermal reaction treatment of particulate solids, in which particulate solids having a major axis of 4 mm or less are supplied as slurry from a slurry storage tank, and at least a pressurized liquid feeder, a heating unit, a cooler, a pressure regulator, and a receiving tank It is characterized in that it is press-fitted into a fluid-type hydrothermal reaction treatment apparatus connected by a cylindrical tube, and hydrothermally treated in a hydrothermal treatment reactor having a downward inclination with an inclination angle of 5 to 30 ° installed in the heating section. Hydrothermal reaction treatment method.   4. The hydrothermal reaction treatment method according to claim 3, wherein the aqueous slurry of the particulate solid is a mixture of the particulate solid and water or an aqueous polymer solution.   The hydrothermal reaction treatment method according to claim 3 or 4, wherein the particulate solid is an organic polymer.   The hydrothermal reaction treatment method according to claim 3 or 4, wherein the particulate solid is a crushed product of a plant, seed, seafood, carnivorous meat, livestock bone, or a modified product thereof.   The hydrothermal heat according to claim 3 or 4, wherein the aqueous slurry of particulate solid is stirred in a slurry storage tank, and the slurry is press-fitted into a hydrothermal reactor while maintaining a uniform slurry concentration. Reaction processing method.   The hydrothermal reaction treatment method according to any one of claims 3 to 7, wherein the weight of the particulate solid is 5 to 50% of the total slurry weight.   The hydrothermal reaction treatment method according to any one of claims 3 to 8, wherein the amount of pressurization per hour of the aqueous slurry of the particulate solid is 30 to 400% of the hydrothermal treatment reactor capacity.   The hydrothermal reaction treatment method according to claim 3, wherein the hydrothermal treatment reaction is performed at 370 ° C. or lower and 23 MPa or lower.

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