JP2010012384A - Apparatus and method for producing biomass-liquefied organic material, and apparatus and method for producing polymer composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technique for producing a biomass-liquefied organic material which is obtained by pulverizing biomass into highly-fine and uniform particles, dispersing the fine and uniform particles in an organic solvent or a synthetic polymer and decreasing the residual water content and which has excellent quality, and to provide a technique for producing a polymer composite material. <P>SOLUTION: An apparatus for producing the biomass-liquefied organic material is provided with: a first feeding means (20) for feeding an organic solvent-mixed suspension liquid into a biomass-pulverized material; a kneading means (30) for kneading the fed suspension liquid in a hermetically sealed state at preset temperature to obtain a kneaded material in which biomass is uniformly dispersed; a volatilizing means (40) for exposing the kneaded material to the atmosphere of the preset pressure lower than the saturated vapor pressure (Pz) at the preset temperature (Tz) to volatilize the moisture content; and a taking-out means (60) for taking out the dehydrated kneaded material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention belongs to a technical field related to a suspension in which biomass is finely dispersed in an organic solvent, and a composite in which biomass is finely dispersed in a synthetic polymer. It relates to the manufacturing method.

Here, the biomass (biological resource) refers to an organic resource that can be regenerated among animals and plants that grow by solar energy.
Specifically, lignocellulose or plant-based biomass mainly composed of cellulose (such as thinning and building demolition materials such as wood industry and pulp industry) , Etc.), starchy biomass mainly composed of amylose or amylopectin (rice, wheat, corn, potato, sweet potato, tapioca, etc.), chitin (or chitosan) based biomass derived from crustacean animals Gala etc.).
Furthermore, the food waste which contains many protein components, such as liquor grounds, coffee grounds, and juice pomace discharged | emitted in the process of food processing, is also mentioned.

Currently, by combining these biomass-derived components and synthetic polymers, the amount of synthetic polymers produced from fossil resources can be reduced, contributing to the preservation of the global environment, Research is underway to create polymer composite materials that can be expressed. In such a polymer composite material, how to finely and uniformly disperse the components of the biomass in the matrix of the synthetic polymer is an important examination subject.
Further, a technique for reducing the volume and stably storing for a long period of time has been studied by refining a bulky and easily rotted biomass and suspending it in a solvent.

  However, biomass has high crystallinity based on strong hydrogen bonds between molecules and has a higher-order structure such as three-dimensional crosslinking. Moreover, even when mechanically pulverized, the biomass powder has a property of easily agglomerating. For this reason, it is generally not easy to finely and uniformly disperse biomass in a solid phase of a synthetic polymer or in an organic solvent.

As a conventional technique for the above-mentioned problem, the starchy biomass is synthesized by subjecting the starchy starch to gelatinization (alpha) by heating and kneading it together with the main component of the synthetic polymer after performing a hydrous treatment on the biomass. A technique for finely and uniformly dispersing in a solid phase of a polymer is known (for example, Patent Document 1).
In the case of grassy biomass and chitinous biomass, a technique is known in which a high-pressure homogenizer or the like is used to refine these biomasses in an aqueous solvent to produce a homogeneous suspension. And the technique of disperse | distributing biomass finely uniformly in the solid phase of a synthetic polymer by heat kneading this suspension with the main ingredient of a synthetic polymer is known (for example, patent document 2). .

JP 2006-21502 A JP 2006-289164 A

However, in the above-described conventional technology, after the biomass is kneaded with the synthetic polymer and refined and uniformly dispersed, the dehydration process is insufficient and the quality is deteriorated even after the dehydration process of volatilizing water from the kneaded body. was there. For this reason, it is desired to create a biomass suspension and composite with as little residual moisture as possible. However, the constituents of biomass are generally highly hydrophilic and it is difficult to improve the degree of dehydration.
In addition, the prepared biomass suspension has a problem that the decay of components easily proceeds in an aqueous solvent and lacks storage stability.

  An object of the present invention is to solve the above-mentioned problems, and to make biomass highly refined and homogenized to disperse it in an organic solvent or a synthetic polymer, and to reduce residual moisture and to improve the quality of the organic liquefied biomass And a technique for producing a polymer composite material.

  In order to solve the above-mentioned problems, the present invention provides a biomass organic liquefaction production apparatus, wherein a first charging means for charging a pulverized biomass and an organic solvent, and the charged pulverized material and the organic solvent are set in a sealed state. A kneading means for kneading at a temperature to form a kneaded body in which biomass is finely dispersed, a volatilizing means for exposing the kneaded body to an atmosphere set at a pressure lower than the saturated vapor pressure at the set temperature, and volatilizing water contained therein, and dehydration And a take-out means for taking out the kneaded body in a state where the biomass is homogeneously and finely dispersed.

  In the present invention constituted by such means, biomass previously pulverized by a known method is used as a starting material. And when the refinement | miniaturization of biomass progresses by knead | mixing the pulverized material of a biomass, the water | moisture content contained in this pulverized material, and the organic solvent in sealed space, the homogenization in a micro level will progress and fluidity | liquidity will also improve. In this process, when the organic solvent is taken into the molecular structure of the biomass, the adsorbed water is released and taken into the solvent, and the volatilization of the water in the volatilization means is promoted. Thereby, it is suppressed that a biomass component re-agglomerates, and the state of the biomass organic liquefied material dispersed homogeneously and finely is maintained stably.

  Furthermore, the polymer composite material manufacturing apparatus of the present invention is provided with a second charging means for charging a single or precursor of a synthetic polymer in the manufacturing apparatus of the present invention, and the kneading means is configured to supply the synthetic polymer that has been charged. Is vaporized together with the organic solvent which has a higher vapor pressure than water and is soluble in water at an arbitrary ratio, and the pulverized product, and the volatilizing means volatilizes the organic solvent together with the moisture from the kneaded body, and takes out the organic solvent. Is characterized in that the kneaded body in a state where it is dehydrated and the biomass is homogeneously and finely dispersed in the synthetic polymer is taken out.

  By constructing the present invention from such means, first, the synthetic polymer, the pulverized biomass and the organic solvent are uniformly mixed at a macro level, and when the synthetic polymer is fluidized at a set temperature, the micro level The homogenization progresses. In this process, the moisture inherently contained in the biomass is dissolved in the organic solvent. And since the vapor pressure of the mixture of the organic solvent having the above-described properties and water is generally higher than the vapor pressure of water alone, the moisture contained in the biomass is removed together with the organic solvent with high efficiency by the volatilization means. It will be. Thereby, the biomass component is finely dispersed without being re-agglomerated, and a high-quality polymer composite material can be obtained.

  According to the present invention, biomass is highly refined and homogenized and dispersed in a solid phase of an organic solvent or a synthetic polymer, and residual organic matter is reduced, and a stable and excellent quality biomass organic liquefied material, and a polymer composite material Techniques for manufacturing are provided.

Embodiments of the present invention will be described below with reference to the drawings.
(Description of biomass organic liquefaction manufacturing equipment)
FIG. 1 (a) is a longitudinal sectional view showing an embodiment of a biomass organic liquefaction production apparatus 10A (hereinafter simply referred to as “organic liquefaction apparatus 10A”) according to the present invention.
This organic liquefaction apparatus 10A has a first charging means 20 for charging a suspension obtained by mixing an organic solvent into a pulverized product obtained by pulverizing biomass in an aqueous solvent, and the charged suspension is set in a sealed state. The kneading means 30A (30) which kneads at a temperature to make a kneaded body in which the biomass is finely dispersed, and the kneaded body has a lower pressure (Pa or Pb) than the saturated vapor pressure Pz at the set temperature Tz (see FIG. 4A). The volatilizing means 40 that volatilizes the moisture contained in the atmosphere set to 1 and the take-out means 60 for taking out the kneaded body that has been dehydrated and in which the biomass is uniformly and finely dispersed.
Such an organic liquefaction apparatus 10A is a batch-type production apparatus that intermittently produces a biomass organic liquefied product by sequentially repeating a raw material charging process, a kneading process, and a kneaded body taking process.

Here, as a method of pulverizing biomass in an aqueous solvent, in addition to the case where the biomass is physically pulverized in water using a high-pressure homogenizer such as that described in Patent Document 2, chemical treatment, depending on microorganisms A method of forming by processing can also be used.
As described above, the biomass is mechanically, chemically, or microbially pulverized or refined in an aqueous solvent, and then the suspension mixed with the organic solvent is stored in the liquid reservoir 23. In addition, before mixing the organic solvent, the organic solvent may be mixed (replaced) after roughly removing water in advance by a known method such as filtration or centrifugation.

  In addition, the pulverized biomass may be subjected to one or more swelling treatments selected from immersion in an alkaline aqueous solution, addition of an alkali metal salt, or rapid freezing at any time before being input to the first input means 20. It is desirable to be made. Thereby, refinement | miniaturization of the biomass in a kneading | mixing stage is accelerated | stimulated.

The organic solvent to be mixed is not particularly limited, but alcohols such as methanol, ethanol, propanol, and butanol are suitable for lignocellulose or a herbaceous biomass mainly composed of cellulose, and an alcohol carbon chain. It is known that solubilization is promoted as the number increases. In particular, the solubilization is promoted by using a catalyst.
In addition, the organic solvent used in the organic liquefaction apparatus 10A is not limited to the case where the vapor pressure is higher than water, unlike the organic solvent used in the polymer composite material production apparatus 10B described later. It may be volatile. Moreover, this organic solvent is not limited to the case where it has a property soluble in water in an arbitrary ratio, and may have an insoluble property.

Biomass liquefied biomass in which biomass is solubilized in an organic solvent can obtain a urethane-like resin by reacting with an isocyanate when the organic solvent is mainly a monohydric alcohol, as a foam or an adhesive. It can be used suitably.
In addition, when the biomass contains lignin and the organic solvent is phenols, this biomass organic liquefaction product can obtain a novolak-like resin when an acid catalyst is added, and further, a cellulose-based biomass and a curing agent are mixed. By doing so, it can be used as a molding material having excellent heat resistance. When an alkali catalyst is added, a resol-like resin can be obtained and can be suitably used for a shell mold.
Further, when the biomass is a herb or / and algae and methanol or / and ethanol is an organic solvent, the biomass organic liquefaction can be suitably used for a liquid fuel. At this time, if a surfactant is added, it can be used more suitably. In addition, when these liquid fuels are distributed with a means for proving the biomass ratio, they can also be used for conversion of carbon dioxide emission reduction.

The first charging means 20 is a liquid reservoir 23 filled with a suspension obtained by mixing a pulverized biomass, water and an organic solvent, and a drive for injecting the suspension from the liquid reservoir 23 toward the kneading means 30. The motor 22 is provided with a force, the check valve 24 prevents the backflow of the injected suspension, and the throttle valve 25 adjusts the amount of suspension injected into the cylinder 31.
The time when the first charging means 20 charges the suspension is not limited to the first time when the organic liquefying apparatus 10A starts the kneading operation, and can be in the middle of the kneading operation.
Further, the configuration of the first charging means 20 is not limited to the configuration in which the pulverized biomass and the organic solvent are mixed in advance, and the pulverized product and the organic solvent are separately added. It is also possible to adopt a configuration for input. Further, the pulverized product of biomass is not limited to those obtained by wet pulverization of the biomass with an aqueous solvent or other solvent as described above, and can also be obtained by employing a known dry pulverization.

The kneading means 30A (30) includes a drive means (not shown), a casing 31 having a sealed space inside, and a rotor 32 that rotates in the sealed space. The cross sections shown in FIGS. 1A to 1C are cross sections orthogonal to the rotation axis of the rotor 32, and are different along the longitudinal direction (first input means 20, volatilization means 40, and extraction means, respectively). A cross-sectional view of the kneading means 30A (including 60) is shown.
The kneading means 30A is for kneading the suspension (mixture of biomass, mixture of water and organic solvent) charged from the first charging means 20 with stirring at a set kneading temperature. In this way, the kneading means 30A (30) kneads the suspension of the pulverized biomass, water and organic solvent mixed, further refines and homogenizes them, and the volatilization means 40 selectively selects moisture from the kneaded body. After removal (priority), the take-out means 60 is opened and taken out.

  The rotor 32 rotates in the sealed space W of the casing 31 that is set in a sealed space and set to the kneading temperature, and kneads the suspension. 3, the rotor 32 is rotated so that two rotating bodies whose rotation directions are opposite to each other in FIG. 3 entrain the input material from the first input means 20 and push out the kneaded material to the extraction means 60. However, the present invention is not limited to such an embodiment, and known ones can be applied.

  As shown in FIG. 1B, the volatilizing means 40 includes a throttle valve 41, a filter plate 42, an exterior chamber 43, and a pressure gauge 44. The volatilizing means 40 is provided at the opening of the sealed space W formed in the casing 31, and adjusts the pressure of the sealed space W, and executes dehydration of the kneaded body with the adjusted pressure.

The filter plate 42 separates the sealed space W of the casing 31 and the outside and selectively filters the solvent component by blocking the passage of the solute component contained in the kneaded body. Such a configuration of the filter plate 42 includes a plate surface provided with a large number of holes, and the plate surface is fixed along the inner wall surface of the casing 31.
The exterior chamber 43 is formed with a vaporization space V communicating with the sealed space W through the filter plate 42 and provided with a throttle valve 41. The exterior chamber 43 is fixed to the casing 31 while contacting the filter plate 42 so that the bottomed container substantially coincides with the opening provided in the casing 31. The exterior chamber 43 blocks the vaporization space V from the atmosphere and vaporizes the water filtered by the filter plate 42 in the vaporization space V.

The throttle valve 41 adjusts the atmospheric pressure of the vaporization space V while referring to the measurement value of the pressure gauge 44, and sets the pressure of the closed space W that communicates. If the throttle valve 41 is completely closed, the atmospheric pressure in the vaporization space V is set to the saturated vapor pressure at the set temperature, and if the throttle valve 41 is fully opened, it is set to atmospheric pressure. Then, by adjusting the opening of the throttle valve 41, the flow resistance is imparted to the vapor released from the vaporization space V to the atmosphere in a variable manner, and the vapor pressure of the vaporization space V is set to a saturated vapor pressure higher than the atmospheric pressure and at a set temperature. Is set to an arbitrary lower pressure. Furthermore, it can connect to the suction means 51 (refer Fig.2 (a)), and can set the atmospheric pressure of the vaporization space V below atmospheric pressure.
The volatilizing means 40 does not provide the filter plate 42 and the exterior chamber 43 as shown in FIG. 1B, and regards a part of the sealed space W as the vaporizing space V and directly provides the throttle valve 41 in the casing 31. A configuration is also possible.

Here, the operation of the first volatilization means 40 in the case where a hardly volatile solvent is used as the organic solvent will be described with reference to the graph of the saturated vapor pressure at each temperature in FIG. The saturated vapor pressure of the hardly volatile solvent is indicated by a broken line in the graph, and water is indicated by a thick line.
The kneading temperature Tz is set, and the throttle valve 41 is adjusted so that the pressure gauge 44 indicates the pressure value Pb. Then, the pressure value Pb of the vaporization space V at the temperature Tz is smaller than the vapor pressure of water and higher than the vapor pressure of the hardly volatile solvent. Therefore, from the 1st volatilization means 40, a water | moisture content will volatilize selectively rather than a hardly volatile solvent, and spin-drying | dehydration of a kneaded body will be accelerated | stimulated.

Next, the operation of the first volatilization means 40 when an easily volatile solvent is used as the organic solvent will be described. Here, FIG. 5 is a graph showing a water / ethanol vapor-liquid equilibrium state where a representative volatile solvent is ethanol. As shown in this graph, ethanol is preferentially volatilized in a water / ethanol solution having a low ethanol concentration. However, as the ethanol concentration increases, the composition of the vapor approaches the composition of the mixed solution, and at the point where the azeotropic point (ethanol concentration 90 mol%) is exceeded, the water is preferentially volatilized.
Therefore, when an easily volatile solvent is used as the organic solvent, it may be necessary to add more organic solvent than the final composition of the organic solvent and to add additional organic solvent as needed during kneading. Desirably, an organic solvent is blended so as to have a liquid composition exceeding the azeotropic point.
Further, after the biomass is solubilized, excess water and organic solvent can be volatilized and recovered.

(Description of polymer composite material manufacturing equipment)
Next, an embodiment of a polymer composite material manufacturing apparatus 10B (hereinafter simply referred to as “composite material manufacturing apparatus 10B”) according to the present invention will be described with reference to a cross-sectional view shown in FIG. Unlike the batch type apparatus illustrated in FIG. 1, the composite material manufacturing apparatus 10 </ b> B is a continuous polymer composite in which the raw material charging process, the kneading process, and the kneading body extraction process proceed simultaneously without being interrupted. It is a continuous device for producing materials.

The composite material manufacturing apparatus 10B includes a first input unit 20, a second input unit 21, a kneading unit 30B (30), a first volatilizing unit 40, a second volatilizing unit 50, an extraction unit 60, a squeezing unit, The liquid means 70, the first condensing means 80, and the second condensing means 90 are configured.
When the manufacturing apparatus 10 is configured in this way, when the raw material of the polymer composite material (synthetic polymer, biomass) containing moisture and the organic solvent is input by the first input unit 20 and the second input unit 21, These are kneaded by the screw 32 rotating in the cylinder 31 and dehydrated by the squeezing means 70, the first volatilizing means 40, and the second volatilizing means 50, and finely mixed in the molten polymer composite material. The kneaded body in which the converted biomass is uniformly dispersed is taken out from the take-out means 60.

With this composite material manufacturing apparatus 10B, when the biomass is cellulose and finely pulverized with a high-pressure homogenizer, microfibrillated cellulose and synthetic polymer nanocomposites can be obtained.
In addition, when a precursor of a synthetic polymer is added, the precursor is graft-polymerized to fine cellulose by appropriately adding a polymerization initiator, and further polymerized therefrom. Thereby, a nanocomposite obtained by grafting microfibrillated cellulose onto a synthetic polymer can be obtained.
In addition, a nanocomposite can be easily obtained also when the fermentation residue of a cellulose biomass is used.
Furthermore, when the biomass is a fibrillated fiber, a biomass fiber reinforced composite material having high rigidity and excellent impact strength can be suitably obtained.

With such a composite material manufacturing apparatus 10B, a polymer composite material obtained by combining a synthetic polymer and biomass can be continuously produced.
In the following, components having the same functions as those already described with reference to FIG.

Here, the first charging means 20 charges a kneading means 30B with a suspension composed of a pulverized biomass, a mixture of water and an organic solvent.
Unlike the organic liquefaction apparatus 10A described above, the organic solvent used in the composite material manufacturing apparatus 10B is limited to a solvent having a vapor pressure higher than water and soluble in water at an arbitrary ratio. Specifically, methanol, ethanol, 1-propanol, and 2-propanol can be mentioned.

  In this first charging means 20, since the synthetic polymer charged from the second charging means 21 located upstream thereof is in a pressurized state, the pulverized biomass is uniformly distributed in the kneaded body at a constant ratio. The suspension is pressurized and charged for charging. The organic solvent is finally removed together with moisture contained in the suspension, that is, artificially added when the biomass is pulverized, and moisture inherently contained in the biomass itself. .

The second charging means 21 is for charging a synthetic polymer alone or precursor into the cylinder 31. As the synthetic polymer introduced here, any of a thermoplastic resin that melts by heating and a thermosetting resin that cures by heating can be employed.
In the thermosetting polymer employed, since the monomer at the time of introduction (before the polymerization reaction) is a low molecular weight compound, it can take liquid, solid, or semi-solid properties.
Further, the synthetic polymer to be added is not limited to the resin simple substance constituting the polymer composite material to be produced, and includes a case where it is a precursor of the resin simple substance before chemical synthesis.
In addition, if the synthetic polymer simple substance or precursor has water-soluble properties, it contributes to improving the homogeneity of biomass dispersed in the matrix of the synthetic polymer.

  The kneading means 30 (30B) is composed of a cylinder 31 and a screw 32, and kneaded by kneading a synthetic polymer and a suspension (a mixture of pulverized biomass, water and an organic solvent) at a set temperature in a sealed state. It ’s what you make.

One end of the screw 32 is connected to the rotation driving means 34, and a spiral flight 33 is formed around the axis of the screw 32. When the shaft 32 rotates inside the cylinder 31, the flight 33 applies pressure to the kneaded body. It pushes from the upstream side to the downstream side.
In FIG. 2, only one screw 32 is shown, but the manufacturing apparatus 10 is not limited to such a uniaxial one, and many screws 32 are arranged in parallel. The case of an axis is also included.

As an example of the arrangement of the multiaxial screws 32, the sealed space in which these screws are arranged is formed into a cylindrical shape in a cross-sectional view, and a plurality of screws whose diameters are substantially matched to the thickness of the cylindrical shape are circulated in the sealed space. Thus, the one arranged in a rosary manner in a cross-sectional view is mentioned.
According to such a configuration in which such multi-axial screws 32 are arranged in a daisy chain, a plurality of volatilizing means 40, 50 can be provided around the group of the screws 32, and the kneaded body can be efficiently provided in the vaporization space V. Dehydration performance is improved by exposure.

  The cylinder 31 includes, from the upstream side, a synthetic polymer charging section A2 in which the second charging means 21 is provided, a suspension charging section A1 in which the first charging means 20 is provided, and a squeezing section in which the squeezing means 70 is provided. B, a heating and kneading section C for heating and kneading the synthetic polymer and the suspension, a first volatilization section D1 in which the first volatilization means 40 is provided, and a second volatilization section D2 in which the second volatilization means 50 is provided, The re-pressurizing section E for re-pressurizing the dehydrated kneaded body and the take-out means 60 provided on the most downstream side are configured.

  In the suspension charging section A1, in a state of high fluidity containing a large amount of water and liquid components of organic solvent, the charged synthetic polymer tablets, pulverized biomass, water, and organic solvent are roughly made uniform. . In this process, the moisture inherently contained in the biomass is solubilized with the organic solvent.

As shown in FIG. 2A, the squeezed section B is formed so that the shaft diameter of the screw 32 increases as it goes from upstream to downstream. When the screw 32 takes such a configuration, the kneaded body is pressurized as it proceeds from upstream to downstream, and the liquid components (solubilized water and organic solvent) are removed by the squeezing means 70. And even if this liquid component is removed and the volume of the kneaded body is reduced, the pressure applied to the kneaded body is maintained.
Moreover, as shown in FIG.2 (b), the expression area B may be formed so that the pitch of the flight 33 of the screw 32 may become narrow as it goes downstream. When the pitch of the flight 33 changes narrowly, the pressure applied to the kneaded body increases. Conversely, when the pitch changes widely, the pressure applied to the kneaded body decreases. When the screw 32 takes such a configuration, the same effect as that obtained when the shaft diameter is changed can be obtained.

  Here, as shown in FIG. 3A, the squeezing means 70 separates the opening / closing valve 71 that discharges the liquid accumulated in the liquid reservoir space U from the outside of the cylinder 31, and the kneaded body. A filter plate 72 that selectively filters the moisture and organic solvent contained in the plate surface through a number of holes provided in the plate surface, an exterior chamber 73 that forms a liquid storage space U, and openings in the filter plate 72 are opened. And an opening adjusting means 75 for adjusting the degree of passage of moisture and organic solvent by adjusting the degree.

The squeezing means 70 configured as described above is for squeezing the organic solvent and water contained by pressurizing the kneaded body with the screw 32 whose shaft diameter or pitch of the flight 33 changes. The squeezing means 70 adjusts the organic solvent and moisture to be squeezed by adjusting the opening adjusting means 75 as appropriate, optimizes the viscosity of the kneaded body sent to the downstream heating and kneading section C, and refines and uniformly disperses the biomass. To promote.
Further, if all the organic solvent and water contained in the kneaded body are removed by the downstream volatilization means 40 and 50, a large amount of energy is consumed to vaporize the mixed liquid. However, if the liquid mixture 70 can be removed in advance by the squeezing means 70, energy consumption can be reduced.

  The heating and kneading section C is a section in which the synthetic polymer and biomass are kneaded at a temperature at which the synthetic polymer is fluidized. As a result, the biomass is refined in the kneaded body and is uniformly dispersed in the molten synthetic polymer matrix.

The first volatilization section D1 is provided with first volatilization means 40 (refer to FIG. 1 (b) as appropriate), and the kneaded body is pressed against the filter plate 42 by the pressure applied from the screw 32, and the contained moisture. The organic solvent selectively passes through the filter plate 42 and accumulates in the vaporization space V.
In the vaporization space V set to a pressure Pa lower than the saturated vapor pressure Pz, the temperature of the water and the organic solvent accumulated in the vaporization space V is the same as the kneading temperature Tz (see FIG. 4A). This accumulated liquid mixture will volatilize. The volatilized liquid mixture (steam) passes through the throttle valve 41 and is released to the atmosphere.

In the first volatile means 40a on the upstream side, since the differential pressure between the vapor pressure Pz and the set pressure Pa at the set temperature Tz is small, the kneaded body does not volatilize rapidly, and the water content is reduced. Then, it is pushed out to the first volatilization means 40b on the downstream side while being kneaded.
Similarly, in the next first volatilization means 40b, the water accumulated in the vaporization space V set to a pressure Pb lower than the saturated vapor pressure Pz is vaporized and released to the atmosphere.
Thereby, since it is suppressed that the liquid mixture of water and an organic solvent volatilizes rapidly at the preset temperature higher than a boiling point, re-aggregation of the dispersed biomass can be prevented.

Here, FIG. 4 (a) shows the saturated vapor pressure of water at each temperature with a thick line, and the saturated vapor pressure of ethanol as a representative of an organic solvent that is compatible with this water at an arbitrary ratio and has a high vapor pressure. Is shown.
And FIG.4 (b) has shown the boiling point in each composition of water-ethanol in atmospheric pressure P0. As described above, a mixed liquid in which an organic solvent that has a higher vapor pressure (lower boiling point) than water and is soluble in water at an arbitrary ratio is shown by a one-dot chain line in FIG. In general, the vapor pressure is higher (boiling point is lower) than water. Therefore, when such an organic solvent mediates, moisture contained in the biomass can be easily discharged out of the system together with the organic solvent.

  By the way, as shown in the water-ethanol vapor-liquid equilibrium curve in each composition of FIG. 5, in the mixed solution having an ethanol concentration equal to or lower than the azeotropic point, the contained ethanol preferentially volatilizes. Therefore, as shown in FIG. 2, when a plurality (two in the figure) of the first volatilizing means 40 are arranged along the axis, the ethanol concentration decreases as going downstream. That is, as the ethanol concentration decreases, the saturated vapor pressure of the mixed liquid also decreases, so the set pressure of the first volatilizing means 40 needs to be set smaller as it goes downstream.

  By performing dehydration treatment at such set pressures Pa and Pb, the kneaded body is further kneaded while gradually reducing the water content, not abruptly. Thereby, the refined and dispersed biomass in the kneaded body is further refined and dispersed while suppressing reaggregation.

  The first condensing unit 80 includes a container 81 provided with an introduction path 82 connected to the first volatilizing unit 40 as shown in FIG. 6A, and the container 81 as shown in FIG. 6B. An inner cylinder 83 that guides the steam introduced concentrically and introduced from the introduction path 82 to swirl along the inner side surface of the container 81, and a flow path along the central axis inside the inner cylinder 83 is defined. And an outlet 88 for discharging the liquid accumulated on the bottom of the container 81 to the outside. Since the first condensing means 80 is configured in this way, the flow path is configured so that the introduced steam flows along the central axis thereof after swirling along the inner surface of the container 81. The flow path for cooling by flowing the vapor of the mixture of the organic solvent and water can be long and can be condensed into the liquid with high efficiency, and is configured with a low pressure loss and a low volume.

Further, the first condensing means 80 is provided with a discharge path 85 at the end of the container 81, and allows the vapor not condensed inside the container 81 to pass through. The discharge path 85 is cooled by a refrigerant whose outer periphery passes through the cooling pipe 86. In addition, since the discharge channel 85 has a constricted shape, the vapor passing therethrough is cooled by being repeatedly compressed and expanded to change into droplets and adhere to the inner wall of the discharge channel 85. Eventually, it will be captured by the filter 87. As a result, the volatilized organic solvent is prevented from being scattered in the atmosphere and contaminating the environment, and the volatilized organic solvent can be recovered and reused for manufacturing the suspension.
Although not shown, the inner cylinder 83 and the inner partition wall 84 may be provided with a flow path through which a coolant for cooling the inner cylinder 83 and the inner partition wall 84 flows.

Returning to FIG. 2, the description will be continued.
The second volatilization section D2 is provided with a second volatilization unit 50 to which the suction unit 51 is connected, and volatilizes the water contained in the atmosphere together with the organic solvent by exposing the kneaded body to an atmosphere set to a pressure lower than the atmospheric pressure. Is.
The configuration of the second volatilization unit 50 is the same as that of the first volatilization unit 40, and is different in that the outlet of the throttle valve 41 is opened to the pressure-pickup unit 51 or open to the atmosphere.
By performing the dehydration process at a set pressure Pc (see FIG. 4A) lower than the atmospheric pressure, the removal of moisture contained in the kneaded body is promoted and the atmospheric pressure is taken out from the take-out means 60. It is possible to prevent the residual moisture from evaporating immediately after being exposed and forming bubbles inside the kneaded body.

As shown in FIG. 7, the second condensing unit 90 includes an introduction path 92 into which exhaust from the second volatilization unit 50 is introduced, and a refrigerant that cools the introduction path 92 and condenses the vapor contained in the exhaust. A cooling pipe 93 through which the liquid is passed, a liquid reservoir tank 94 that is held at a pressure lower than the atmospheric pressure by the suction means 51 and that induces and accumulates condensate, and a cooling tank 95 that cools the liquid reservoir tank 94. ing.
The first condensing means 80 configured as described above allows the components volatilized by the second volatilizing means 50 to be collected from the outlet 96 after being liquefied and reused without being released into the atmosphere. is there.

Returning to FIG. 2, the description will be continued.
The re-pressurization section E is a portion that continuously kneads the kneaded body after the dehydration process and applies a pressure necessary for re-pressurization and taking out from the take-out means 60.
That is, in the repressurizing section D, the screw 32 is repressurized so that the shaft diameter becomes larger or the pitch of the flights 33 is narrowed so that the dehydrated kneaded body can be taken out from the takeout means 60. .
As a result, the polymer composite material in which the biomass is finely dispersed is taken out from the take-out means 60.
The kneaded body of the polymer composite material is discharged in a bundle through a die (not shown) provided in the take-out means 60 and having dozens of small holes. Further, after solidifying through the cooling bath, it is drawn into a pelletizer (not shown) and cut into rice granular pellets.

In the above description, the batch type manufacturing apparatus is shown as the biomass organic liquefied product manufacturing apparatus 10A, and the continuous manufacturing apparatus is exemplified as the polymer composite material manufacturing apparatus 10B. However, the present invention is not limited to these, and the above-described continuous-type production apparatus may be configured by providing the above-described batch-type production apparatus 10A with the second introduction means 21 for introducing the synthetic polymer into the polymer composite material production apparatus. It is also possible to remove the second charging means 21 from the manufacturing apparatus 10B and make a biomass organic liquefied product manufacturing apparatus.
In addition, using existing equipment, necessary processes are appropriately shared and combined to produce a biomass-containing composition such as a biomass organic liquefied material or a polymer composite material obtained by combining a synthetic polymer and biomass. Can do.

It is sectional drawing which shows embodiment of the organic liquefaction apparatus of the biomass which concerns on this invention, (a) (b) (c) has each shown a different cross section. (A) is a longitudinal cross-sectional view which shows embodiment of the manufacturing apparatus of the polymer composite material which concerns on this invention, (b) is a longitudinal cross-sectional view which shows the modification of this embodiment. (A) is a longitudinal cross-sectional view which shows embodiment of the squeezing means applied to this invention, (b) is the elements on larger scale explaining operation | movement of an opening adjustment means. (A) is a graph which shows the saturated vapor pressure of water, ethanol, ethanol aqueous solution, and a hardly-volatile solution with respect to temperature, (b) is a graph which shows the boiling point with respect to the arbitrary compositions of the ethanol aqueous solution in 1 atmosphere. It is a graph which shows the vapor-liquid equilibrium curve of ethanol aqueous solution. (A) is a longitudinal cross-sectional view of the 1st condensing means applied to this invention, (b) is a horizontal sectional view. It is a longitudinal cross-sectional view of the 2nd condensing means applied to this invention.

Explanation of symbols

10A Organic Liquefaction Equipment (Biomass Organic Liquefaction Production Equipment (Production Equipment))
10B Composite material manufacturing equipment (Polymer composite material manufacturing equipment (manufacturing equipment))
20 First input means 21 Second input means 25, 24 Throttle valve 30, 30A, 30B Kneading means 33 Flight 40, 40a, 40b First volatilization means 42, 72 Filter plate 43, 73 Exterior chamber 44 Pressure gauge 50 Second volatilization Means 51 Pulling means 60 Extraction means 70 Squeezing means 75 Opening adjustment means 80 First condensing means 81 Container 90 Second condensing means U Liquid storage space V Vaporization space W Sealed space

Claims (14)

A first charging means for charging a pulverized biomass and an organic solvent;
A kneading means for kneading the charged pulverized product and organic solvent at a set temperature in a sealed state to form a kneaded body in which the biomass is finely dispersed;
Volatilizing means for volatilizing water contained by exposing the kneaded body to an atmosphere set to a pressure lower than the saturated vapor pressure at the set temperature;
An apparatus for producing a biomass organic liquefied product, comprising: a take-out means for taking out the kneaded body in a state where the biomass is uniformly and finely dispersed after being dehydrated. The manufacturing apparatus according to claim 1,
Providing a second charging means for charging a single or precursor synthetic polymer;
The kneading means kneads the charged synthetic polymer together with the organic solvent having a vapor pressure higher than water and soluble in water at an arbitrary ratio and the pulverized product,
The volatilizing means volatilizes the organic solvent together with the moisture from the kneaded body,
The take-out means takes out the kneaded body in a state where the biomass is dehydrated and the biomass is uniformly and finely dispersed in the synthetic polymer. In the manufacturing apparatus according to claim 1 or 2,
The pulverized product is a product obtained by pulverizing the biomass in an aqueous solvent. In the manufacturing apparatus of any one of Claims 1-3,
The pulverized product and the organic solvent are mixed in advance and charged into the first charging means in a suspended state. In the manufacturing apparatus according to any one of claims 1 to 4,
At least one of the volatile means provided in a singular or plural number is:
A manufacturing apparatus comprising: a first volatilizing unit having a throttle valve that sets the atmosphere to a pressure lower than a saturated vapor pressure at the set temperature and higher than an atmospheric pressure. The manufacturing apparatus according to claim 5, wherein
At least one of the plurality of volatilization means provided is:
2. A manufacturing apparatus comprising: a second volatilizing unit having a pulling unit that sets the atmosphere to a pressure lower than the atmospheric pressure. In the manufacturing apparatus according to any one of claims 1 to 6,
The kneading means includes
A cylinder in which the first input means is provided on the upstream side and the take-out means is provided on the downstream side;
And a screw for rotating the shaft inside the cylinder to push the kneaded body from the upstream side to the downstream side. The manufacturing apparatus according to claim 7, wherein
A manufacturing apparatus comprising a squeezing means that pressurizes the kneaded body before being treated by the volatilizing means to squeeze out the organic solvent and moisture. The manufacturing apparatus according to any one of claims 1 to 8,
The said volatilization means is connected to the condensation means to condense the vaporized said organic solvent and water vapor | steam into a liquid, The manufacturing apparatus characterized by the above-mentioned. A first charging stage for charging a pulverized biomass and an organic solvent;
A kneading step of kneading the charged pulverized product and the organic solvent in a sealed state at a set temperature to form a kneaded body in which the biomass is finely dispersed;
A volatilization stage in which the kneaded body is exposed to an atmosphere set to a pressure lower than the saturated vapor pressure at the set temperature to volatilize the contained water;
A method for producing a biomass organic liquefied product, comprising: taking out the kneaded body that has been dehydrated and in which the biomass is uniformly and finely dispersed. In the manufacturing method of Claim 10,
Including a second charging step of charging the single or precursor of the synthetic polymer before the kneading step,
In the kneading step, the charged synthetic polymer is kneaded with the organic solvent having a vapor pressure higher than water and soluble in water at an arbitrary ratio and the pulverized product,
The volatilization stage volatilizes the organic solvent together with the moisture from the kneaded body,
In the extraction step, the kneaded body in a state in which the biomass is dehydrated and homogeneously dispersed in the synthetic polymer is extracted. In the manufacturing method of Claim 10 or Claim 11,
A manufacturing method comprising a pulverization step of pulverizing the biomass in an aqueous solvent to form the pulverized product before the first charging step. In the manufacturing method according to any one of claims 10 to 12,
Prior to the first charging step, the production method includes a suspending step in which the pulverized product and the organic solvent are mixed in advance to form a suspension.   A biomass-containing composition in which biomass obtained by the production method according to claim 10 is finely dispersed.

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