JP2014208809A - Method of producing amorphous cellulose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing an amorphous cellulose which enables converting a cellulose-containing raw material, efficiently in a short time, into an amorphous cellulose.SOLUTION: Multi-row of teeth which extend in parallel in the direction intersecting the circumferential direction of a relative rotation at intervals of a pitch P are provided in the surface which forms a gap between one and the other members, and teeth of these individual members intersect mutually in the surface forming the gap to form a lattice of the pitch p. The teeth are rotated relatively through the gap by driving a motor, and a cellulose-containing raw material is charged into the gap by applying a shear force under the conditions that the scale parameter Sdefined by the following equation (where Wis the consumption power of the motor; Ris the outer radius (m) of a crushing part; Ris an inner radius (m) from the center of the relative rotation to the crushing part; and ω is the rotation number of the relative rotation) is 300 or greater and that the gap is 10 μm or smaller.

Description

  The present invention relates to a method for producing amorphized cellulose.

  In recent years, from the viewpoint of depletion of fossil fuels and environmental problems, interest in woody biomass resources, which are renewable organic resources, has increased.

  However, when considered as an industrial material, cellulose, which is a main component of woody biomass, has a very complex and strong crystal structure, and therefore has poor applicability. Therefore, when used for bioethanol or the like, it must be amorphized in advance.

  Amorphous materials obtained from these woody biomass resources are expected to have a wide range of applications from the industrial field to the food field in addition to bioethanol.

  As conventional techniques related to cellulose amorphization, for example, Patent Documents 1 and 2 propose that a cellulose-containing raw material is amorphized using a medium pulverizer or the like.

  However, the existing amorphization technology is desired to further reduce the cost and improve the productivity, and a new technology capable of efficiently amorphizing cellulose in a short time is required.

  In such a background, the present inventors put a cellulose-containing raw material into the gap between the upper die and the lower die, and pulverize the cellulose by applying a shearing force by the relative rotation of the upper die and the lower die. It succeeded in making it amorphous in a short time (nonpatent literature 1).

Japanese Patent No. 4160108 Japanese Patent No. 4160109

Applied Glucose Science, Vol. 1, No. 3, 2011 (Abstracts of the 19th Symposium on Enzyme Chemistry Related to Glycobiology in 2011 (60th Annual Meeting)), July 20, 2011, Japan Society for Applied Glycoscience

  However, in the technique of Non-Patent Document 1 developed by the present inventors, the conditions under which amorphization can be achieved are limited, and in many cases, even if the cellulose-containing raw material is shear pulverized between gaps, it cannot be amorphized. . Non-Patent Document 1 mainly examines the temperature condition, but the details of the structure of the surface forming the gap and the correlation with factors such as the power for rotationally driving the die have not been clarified.

  As described above, although Non-Patent Document 1 achieves non-crystallization, depending on conditions, non-amorphization of cellulose does not occur, and establishment of a technique capable of amorphizing cellulose with high reproducibility has been desired. .

  The present invention has been made in view of the circumstances as described above, and it is an object of the present invention to provide a method for producing amorphous cellulose that can easily and efficiently amorphousize a cellulose-containing raw material in a short time. It is said.

In order to solve the above-described problems, the method for producing amorphous cellulose according to the present invention uses one member and the other member, which rotate relative to each other through a gap, to introduce a cellulose-containing raw material into the gap and to apply a shear force. Is produced by pulverizing and amorphizing the cellulose, wherein one member and the other member are pitched in a direction intersecting the circumferential direction of the relative rotation on the surface forming the gap. Plural teeth extending in parallel at intervals of P are provided, and the teeth of one member and the other member intersect with each other on the plane forming the gap to form a lattice of pitch P, and one member and the other member A motor that rotates by transmitting torque to at least one of them is driven to rotate them relative to each other through a gap, and a cellulose-containing raw material is introduced into this gap. A scale parameter S _{p1 of the} following formula:

(W ^* is the motor power consumption (W), P is the pitch of the grid (mm), and ω is the relative rotation speed (rpm).) Shear force under the condition of 2 or more and a gap of 10 μm or less It is characterized in that it is pulverized to render the cellulose amorphous.

Further, the method for producing amorphous cellulose according to the present invention uses one member and the other member that rotate relative to each other through a gap, and puts a cellulose-containing raw material into the gap and applies a shearing force to pulverize the cellulose. A method for producing non-crystalline cellulose, wherein one member and the other member are parallel to each other at a pitch P in a direction intersecting a circumferential direction of relative rotation on a surface forming a gap. The teeth of the strips are provided, and the teeth of one member and the other member intersect each other on the surface forming the gap to form a lattice of pitch P, and transmit torque to at least one of the one member and the other member. And rotating them relative to each other through a gap. A cellulose-containing raw material is introduced into the gap, and a scale parameter S _{p2 of the} following formula:

(W ^* is the motor power consumption (W), R ₂ is the outer radius (m) of the grinding part, R ₁ is the inner radius (m) from the center of the relative rotation to the grinding part, and ω is the rotation of the relative rotation. The number (rpm) is 300 or more and a gap is 10 μm or less.

  According to the present invention, a cellulose-containing raw material can be amorphized simply and efficiently in a short time.

It is the figure which showed typically one member and the other member used for the method of this invention, (a) is a longitudinal cross-sectional view, (b) is one member and the other in the surface which forms a gap. It is the figure which showed the state which the tooth | gear of this member crossed and formed the grating | lattice. It is a diagram illustrating a grinding unit and its inner radius R ₁ and outer radius R _2. BRIEF DESCRIPTION OF THE DRAWINGS It is the figure (top is a top view, the bottom is a side view) which showed typically an example of the cellulose amorphization apparatus for enforcing the method of this invention. It is a longitudinal cross-sectional view of the part of the mortar of the cellulose amorphization apparatus of FIG. 2 is a wide-angle X-ray diffraction profile of a powder obtained by pulverizing a cellulose-containing raw material.

  The present invention is described in detail below.

  The inventors put a cellulose-containing raw material into the gap between the upper die and the lower die, and pulverized the cellulose by applying a shearing force by the relative rotation thereof, thereby making the cellulose amorphous (alpha-ized) in a short time. The technique of Non-Patent Document 1 to be performed was examined in detail. Amorphization is unlikely to occur even if a gap is simply provided and sheared. However, as a result of studying the details of the structure of the surface forming the gap and the correlation with factors such as the rotational driving power, the inventors found the conditions suitable for the occurrence of the amorphous state and completed the present invention. .

  In the present invention, as the cellulose-containing raw material, wood materials such as cypress, cedar, beech and bamboo can be used, and so-called soft cellulose such as paper and grass can also be used.

Moreover, as a cellulose containing raw material, a cellulose simple substance, for example, commercially available crystalline cellulose, can also be used. The cellulose I type crystallinity of commercially available crystalline cellulose is usually 80% or more. Here, the cellulose I-type crystallinity is calculated by the Segal method from the diffraction intensity value by the X-ray diffraction method, and is defined by the following equation.
Cellulose type I crystallinity (%) = [(I 22.6−I 18.5) / I 22.6] × 100
Here, I 22.6 represents the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I 18.5 represents the diffraction intensity of the amorphous portion (diffraction angle 2θ = 18.5 °).

  The cellulose I-type crystallinity of the cellulose-containing raw material used in the present invention is preferably 50% or more, and more preferably 70% or more. According to the present invention, the crystallinity of the cellulose-containing raw material having such high crystallinity can be greatly reduced.

  The form of these cellulose-containing raw materials is not particularly limited, and various forms such as chips, fibers, granules, and powders can be used. When using a wood piece as the cellulose-containing raw material, the size is preferably 2 to 5 mm square in the case of a chip-like material, for example. Thereby, grinding can be performed efficiently and easily.

  In the cellulose-containing raw material used in the present invention, the cellulose content (total amount of cellulose and hemicellulose) in the remaining components excluding water is preferably 20% by mass or more, more preferably 40% by mass or more. When a material in such a range is used, an amorphous cellulose roll can be produced efficiently.

  The water content in the cellulose-containing raw material is preferably 0.5 to 20% by mass. If the water content in the cellulose-containing raw material is within this range, it can be easily pulverized and the crystallinity of cellulose can be easily reduced by pulverization.

  In addition, there is no limitation in particular as a method of removing water from a raw material, For example, vacuum drying, drying by dry air, etc. are applicable.

  In the present invention, using one member and the other member that rotate relative to each other through the gap, the cellulose-containing raw material is put into the gap and is pulverized by applying a shearing force to make the cellulose amorphous.

1A and 1B are diagrams schematically showing one member and a part of the other member used in the method of the present invention, wherein FIG. 1A is a longitudinal sectional view, and FIG. It is the figure which showed the state which the tooth | gear of the member and the other member cross | intersected, and formed the grating | lattice. FIG. 2 is a diagram for explaining the pulverized portion and its inner radius R ₁ and outer radius R ₂ .

  In this example, an upper die 2 is used as one member A, and a lower die 3 is used as the other member B. As will be described later, one member A is fixed, and the other member B is rotated by driving by a motor.

  As shown in FIG. 1 (a), one member A has a pitch in a direction intersecting the circumferential direction of relative rotation between one member A and the other member B on a surface 21 that forms a gap 4 with a spacing Δ. A plurality of teeth 24 extending in parallel at intervals of P are provided through grooves 25.

  The other member B also has a plurality of teeth 34 extending in parallel at a pitch P in the direction intersecting the circumferential direction of relative rotation between the one member A and the other member B on the surface 31 forming the gap 4. It is provided via a groove 35.

  As shown in FIG. 1B, the teeth 24 of one member A and the teeth 34 of the other member B intersect on the surface where the gap 4 is formed to form a lattice with a pitch P.

  The lattice of the pitch P is, for example, a parallelogram, and the angle of the parallelogram is preferably an acute angle of 45 degrees or more and less than 90 degrees, more preferably 50 to 80 degrees.

The pitch P of the grating is preferably in the range of 0.5 to 5 mm. Here, the pitch P between one member A and the other member B is defined as follows. When the pitch of one member A and the other member B is equal, this is set as the pitch P, and when they are different, the shorter one is set as the pitch P ₁ and the longer pitch P ₂ is set, P = (P ₁ P ₂ ) ^{1 / 2} . The pitch P ₂ is within 1.5 times the pitch P ₁ , preferably within 1.2 times, more preferably within 1.1 times.

  Then, a motor for transmitting and rotating the torque to the other member B is driven to rotate them relative to each other through the gap 4, and the cellulose-containing raw material is charged into the gap 4.

The cellulose-containing raw material charged into the gap 4 is pulverized in the pulverizing section 20 of FIG. 2, that is, in a region where shearing is performed by relative rotation between one member A and the other member B.
(Embodiment 1: Scale parameter S _p1 )
When the next scale parameter S _p1 is 2 or more and the gap 4 is crushed under a condition of 10 μm or less, the crystallinity of cellulose can be greatly reduced.

Here, W ^* is the power consumption (W) of the motor, P is the pitch of the grid (mm), and ω is the rotational speed (rpm) of the relative rotation.

A technical correlation with cellulose amorphization at the scale parameter S _p1 will be described below.

The amount of work per unit time that is performed on the viscosity of the powder (cellulose-containing raw material) is defined as W. It is assumed that the power W * that is actually required and measured is obtained by integrating the density of the lattice pattern formed by the teeth 24 of the upper die 2 and the teeth 34 of the lower die 3 with this W. Evaluating the density of the lattice with P ^-2 gives

C ₁ is a proportionality constant.

And it is presumed that the amorphous work of cellulose is caused by the total work W _tot made into the powder. This total work W _tot is proportional to the product of the power W * and the powder residence time t.

It is assumed that the powder residence time t increases as the pitch P is shortened and is proportional to P ⁻² . Furthermore, t also depends on the rotational speed ω. Assuming that dependency is ω ⁻¹ , the total work to be performed on the powder, that is, the total work W _{tot to} be performed on the powder for non-crystallization is as follows.

However C ₂ is a proportionality constant.

Thus, assuming that the unknown proportionality constant C ₂ is not changed significantly by the apparatus, the scale parameter S _p1 of the correlates with control of the amorphized.

  When the gap is 10 μm or less, the load due to power consumption is sufficiently applied during pulverization, and the amorphous state can be obtained.

The scale parameter _Sp1 is 2 or more and the upper limit is not particularly limited, but it is preferably in the range of 2 to 20 in consideration of the point of suppressing power consumption.

(Embodiment 2: Scale parameter _Sp2 )
Further, when pulverizing by applying a shearing force under the condition that the next scale parameter _Sp2 is 300 or more and the gap 4 is 10 μm or less, the crystallinity of cellulose can be greatly reduced.

Where W ^* is the motor power consumption (W), R ₂ is the outer radius (m) of the grinding part, R ₁ is the inner radius (m) from the center of the relative rotation to the grinding part, and ω is the rotational speed of the relative rotation. (Rpm).

A technical correlation with cellulose amorphization at the scale parameter S _p2 will be described below.

  The force ds received by the powder (cellulose-containing raw material) occupying the area element dS of the pulverized part (mortar)

Suppose that Here, h is the apparent viscosity, and r is the distance from the origin in polar coordinate display. If the angle in the polar coordinate display is q, dS = r dq dr. Assuming that h becomes larger when pitch P is shortened and h is proportional to P ^-2 , the work dW that the powder occupying area element dS receives per unit time is

It becomes. However, C ₃ is a proportional constant. The work W ^* that the mortar performs per unit time is obtained by integrating dW on the mortar.

It becomes. Suppose this is the power W * that is actually needed and measured.

Then, it is estimated that the amorphous work of cellulose is caused by the total work W _tot that is performed when the powder occupying the area element dS on the die moves from the inner periphery to the outer periphery of the die. W _tot is the product of the force received by the powder and the distance traveled.

It becomes. Comparing these equations, the total work W _tot is calculated by the actual measured power W *

It is represented by C ₄ is a proportionality constant.

As described above, assuming that the unknown proportionality constant C ₄ does not vary greatly depending on the apparatus, the scale parameter S _p2 correlates with the control of the amorphization.

  When the gap is 10 μm or less, the load due to power consumption is sufficiently applied during pulverization, and the amorphous state can be obtained.

The scale parameter _Sp2 is 300 or more and the upper limit is not particularly limited, but it is preferably in the range of 300 to 3000 in view of the point of suppressing power consumption.

  In Embodiment 1 and Embodiment 2 described above, the rotational speed ω of the relative rotation is preferably 50 to 380 rpm, more preferably 50 to 190 rpm. If it is in such a range, the shear rate which the cellulose containing raw material thrown into the gap 4 receives between the fixed upper die 2 and the rotating lower die 3 can be made appropriate.

  Although the time of a shearing process is not specifically limited, From a viewpoint of reducing a crystallinity degree, a shearing process can be performed in 0.01 to 10 hours, for example. However, in the present invention, the shearing process can be performed in a remarkably short processing time as compared with the technique using a ball mill or the like as in Patent Documents 1 and 2, and typically in about 10 to 60 seconds. .

  The degree of crystallinity of the amorphous cellulose obtained by the present invention is preferably less than 50%, more preferably 45% or less, even more preferably 30% or less, and particularly preferably 20% or less in consideration of utilization of industrial materials and the like. .

  The average particle size of the non-crystalline cellulose-containing pulverized product obtained by the present invention is, for example, 10 to 40 μm.

  In addition, the non-crystallized sample subjected to the pulverization treatment of the present invention clearly improves the saccharification characteristics as compared with the untreated sample and the heat pulverized sample. Therefore, the non-crystallized sample which performed the grinding | pulverization process of this invention is excellent also in the saccharification characteristic important in manufacturing bioethanol. In conventional saccharification, cellulose is treated with an organic solvent to reduce the crystallinity of cellulose and increase saccharification, but the amorphous technology of the present invention only pulverizes under temperature-controlled conditions. It is possible to improve saccharification.

  Amorphous cellulose obtained by the present invention can be expected to be used in a wide range of industrial fields such as bioethanol, food, and plastic additives.

  FIG. 3 is a diagram schematically showing an example of a cellulose amorphization apparatus for carrying out the method of the present invention (the top is a top view and the bottom is a side view), and FIG. 4 is the cellulose amorphization of FIG. It is a longitudinal cross-sectional view of the mortar part of an apparatus.

  The cellulose amorphizing apparatus 1 includes an upper die 2 (one member A) fixedly installed and a lower die 3 (the other member) provided rotatably with a predetermined gap 4 between the upper die 2. Member B). These upper mill 2 and lower mill 3 correspond to one member A and the other member B in FIG.

  The upper mill 2 is formed in a ring shape with a raw material inlet 5 for feeding a cellulose-containing raw material at the center. The raw material inlet 5 communicates with the gap 4 on the bottom surface of the upper mill 2. The lower mill 3 is formed in a disk shape having the same outer diameter as the upper mill 2.

  The lower mill 3 is rotated by a motor 40 at a predetermined speed. The computer 60 gives a motor control signal to the motor 40 via the motor control cable 41 and controls the rotation speed of the lower mill 3 by the motor 40. The gap 4 between the upper die 2 and the lower die 3 can be adjusted by the gap adjusting unit 7 and is set within a range of 10 μm or less depending on the cellulose-containing raw material and the size of the desired powder to be obtained after processing. can do.

  The material of the upper die 2 and the lower die 3 is not particularly limited, but temperature control is facilitated by using a material having good thermal conductivity such as metal.

  As shown in FIG. 4, the upper mill 2 has a raw material passage 23 that extends from an inner surface 22 facing the raw material inlet 5 to a bottom surface (surface that forms the gap 4 in FIG. 1) 21 in a sectional view, and in a plan view. It is formed in a spiral shape.

  Since the container 6 expanded by the tapered raw material passage 23 is formed at the lower end of the raw material inlet 5, the cellulose-containing raw material introduced into the raw material inlet 5 enters the gap 4 and is sheared and crushed. Immediately before entering the container 6, it is heated or cooled by heat transfer from the upper die 2.

The outer radius R _{2 of the} pulverizing part 20 and the inner radius R ₁ from the center of relative rotation to the pulverizing part 20 correspond to the ranges shown in FIG.

  As shown in FIG. 1A, the surface 21 forming the gap 4 with the interval Δ, which is the bottom surface of the upper mill 2, intersects the circumferential direction of the relative rotation between one member A and the other member B. A plurality of teeth 24 extending in parallel at intervals of the pitch P are provided through grooves 25.

  On the surface 31 forming the gap 4 which is the upper surface of the lower mill 3, multiple teeth extending in parallel at a pitch P in the direction intersecting the circumferential direction of the relative rotation of one member A and the other member B 34 is provided through the groove 35.

  As shown in FIG. 1B, the teeth 24 of one member A and the teeth 34 of the other member B intersect on the surface where the gap 4 is formed to form a lattice with a pitch P.

  In addition, the surface 21 forming the gap 4 of the upper die 2 and the surface 31 forming the gap 4 of the lower die 3 easily allow the powder containing amorphous cellulose obtained by shear pulverization from the side of the gap 4. For the purpose of recovery, it may be inclined slightly downward from the center toward the side of the gap 4.

  Below the upper mortar 2 and the lower mortar 3, a tray 8 having an inner diameter sufficiently larger than these outer diameters is provided. A dropping port 9 is opened on the bottom surface of the tray 8. The amorphous cellulose after the treatment by the cellulose amorphizing device 1 is dropped from the tray 8 and further passed through a dropping chute 10 to a predetermined container (not shown). ) And so on.

  The temperature at the time of shear pulverization by the cellulose amorphizing apparatus 1 can be controlled by the following temperature control means. For example, the upper die 2 is heated to a temperature set by the temperature controller using a heater 50 formed in a ring shape having substantially the same outer diameter as the upper die 2 and having an opening having the same diameter as the raw material inlet 5. Can be heated. Further, the upper die 2 can be removed from heat or cooled by circulating water or antifreeze liquid whose temperature is controlled by a thermostat (not shown) in the die.

  In addition, in order to control the temperature of the mortar portion with high accuracy, a Peltier temperature control device is configured by installing a Peltier element having substantially the same shape (ring shape) instead of the heater 50 provided in the upper mortar 2. This makes it possible to control the temperature with high accuracy from, for example, -20 ° C to 120 ° C.

  Next, the cellulose amorphization process performed using this cellulose amorphization apparatus 1 is demonstrated. First, the gap 4 between the upper die 2 and the lower die 3 is adjusted as appropriate according to the cellulose-containing raw material, the size of the pulverized material after processing, and the like via the gap adjusting unit 7.

  Further, the temperature control means as described above controls the temperature of the upper die 2 by its heat conduction. For example, cellulose can be made amorphous (alpha) by pulverizing a cellulose-containing raw material under a temperature condition of -5 to 40 ° C. by applying a shearing force.

  Then, the motor 40 is driven by electric power at a rotational speed controlled by the computer 60, and the lower mill 3 is rotated so as to give a predetermined shear rate.

  Next, the cellulose-containing raw material is charged into the raw material charging port 5 to start processing. The cellulose-containing raw material is controlled to the set temperature by the temperature control means as described above while passing through the raw material inlet 5 and further from the raw material passage 23 to the accommodating portion 6. And is pulverized by receiving a shearing force between the fixed upper die 2 and the rotating lower die 3.

  The powder containing amorphous cellulose obtained by shear pulverization is discharged from the side of the gap 4 and accommodated in the receiving tray 8, and is collected in a predetermined container (not shown) through the dropping port 9 and the dropping chute 10. Is done.

  Although the present invention has been described above based on the embodiment, the present invention is not limited to this embodiment, and various modifications can be made without departing from the scope of the invention.

  For example, in the embodiment of FIGS. 3 and 4, one member and the other member are an upper die and a lower die having a plane as a surface forming the gap, and the cellulose-containing raw material is gapd from the raw material input port leading to the gap. The apparatus configuration in which the obtained powder containing amorphous cellulose is collected from the side of the gap is shown in FIG. 3 and FIG. It is only an example that can be used to implement the method of the present invention, and any other device that can perform the method of the present invention may be used.

For example, by using one member and the other member that constantly rotate relative to each other at the rotational speed controlled by the apparatus, a plurality of teeth that form a lattice with a pitch P are provided on the surface on which the gap is formed. If the cellulose-containing raw material introduced into the gap between the members is configured to give a shearing force, it is possible to achieve efficient amorphousization by setting the scale parameters S _p1 and S _p2 and the gap within a specific range. Become. For example, as one member and the other member, in addition to the mortar used in the embodiment of FIGS. 3 and 4, a small-diameter cylindrical or columnar member and a large-diameter cylindrical member that are concentrically arranged may be used. it can.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
<Examples 1-3, Comparative Examples 1-3>
Regarding the amorphization of cellulose, the measurement result of the wide-angle X-ray diffraction of the sample after shear pulverization was evaluated as an index. As shown in FIG. 5, when a plurality of diffraction peaks derived from crystals do not appear, In the case where a plurality of diffraction peaks derived from 現 れ る appeared, it was evaluated as x.

The X-ray diffraction intensity of the sample after shear pulverization was measured under the following conditions using “RINTRAPID” manufactured by Rigaku Corporation.
X-ray source: Cu / Kα-radiation
Tube voltage: 40kV
Tube current: 30mA
Irradiation time: 1200s
Cellulose amorphization apparatus 1 having the structure shown in FIGS. 1 to 4 using cypress wood chips and commercially available high-purity crystalline cellulose fibers (B600 manufactured by Rettenmeier, crystallinity 85 to 87%) as raw materials. Was subjected to a shearing treatment.

  In the cellulose amorphization apparatus 1 used, the upper die 2 and the lower die 3 both have an outer diameter of 90 mm (radius 45 mm), and have a raw material inlet 5 having a diameter of 34 mm at the center.

  The tapered raw material passage 23 of the upper mill 2 is formed over a range of 30 mm from the inner surface 22 (FIG. 4).

  The gap 4 between the dies was set to 10 μm, and shearing was performed at a pulverization temperature of 10 ° C. The rotational speed of the lower mill 3 was 50 to 400 rpm depending on the motor power, and the pitch P between the upper mill 2 and the lower mill 3 was 2 mm.

  The motor power W * was calculated from the voltage V and current I using the following equation.

  The power factor cos θ was calculated as 80% (0.8). Where V is the voltage measured on one lead wire of a three-phase motor with an AC voltmeter or equivalent, and I is the current of one lead wire of a three-phase motor on an AC voltmeter or equivalent. It is the value measured by. GDN8255A manufactured by GOOD WILL INSTRUMENT was used for measurement of each voltage and current.

  The amount of cellulose-containing raw material introduced at one time from the raw material introduction port was about 0.6 to 0.7 g, and the number of times of introduction per minute was 6 to 7 times, whereby the amount of introduction per hour was 216 g to 294 g.

Table 1 shows the results of the scale parameter S _p1 and the degree of amorphization.

From Table 1, in Comparative Examples 1 to 3 in which the shear pulverization was performed under the condition where the scale parameter _Sp1 was less than 2, no significant change was observed in the diffraction peak, and the same high crystallinity as in the case of untreated was shown. However, it was found that, under the conditions of Examples 1 to 3 in which the shear pulverization was performed under the condition where the scale parameter _Sp1 was 2 or more, the diffraction peak was remarkably reduced and low crystallinity was exhibited.

From the above, it was found that cellulose crystallinity can be remarkably reduced by grinding with a scale parameter _Sp1 of 2 or more.
<Examples 4 and 5 and Comparative Examples 4 to 7>
The rotational speed of the lower die was set to 180 rpm as in Example 3, and the gap between the dies was set in the range of 0 to 50 μm. Otherwise, the pulverization was performed under the same conditions as in Example 3.

Table 2 shows the results of the scale parameter S _p1 and the degree of amorphization.

  In Table 2, for the gaps of 0, 10 μm, and 50 μm, the degree of amorphization was confirmed from the measurement results of the wide-angle X-ray diffraction. In other cases, that is, about 20 to 40 μm, it was judged that it was discharged without applying a load during pulverization. Therefore, the degree of non-crystallization was the same as that of the untreated one.

From Table 2, it was found that by setting the gap to 10 μm or less, a sufficient load is applied to the cellulose-containing raw material, and the crystallinity of cellulose can be remarkably reduced under the condition where the scale parameter _Sp1 is 2 or more.

As described above, multiple teeth extending parallel to the direction intersecting the circumferential direction of the relative rotation are provided on the surface forming the gap, and the teeth of the upper and lower dies are crossed with each other on the surface forming the gap. By forming a grid of pitch P, and by setting the scale parameter S _p1 that correlates with the work done on the viscosity of the powder and the gap for loading the powder within a certain range, It was found that amorphousization becomes possible.
<Examples 6-9, Comparative Examples 8-9>
Regarding the amorphization of cellulose, the measurement result of the wide-angle X-ray diffraction of the sample after shear pulverization was evaluated as an index. As shown in FIG. 5, when a plurality of diffraction peaks derived from crystals do not appear, In the case where a plurality of diffraction peaks derived from 現 れ る appeared, it was evaluated as x.

The X-ray diffraction intensity of the sample after shear pulverization was measured under the following conditions using “RINTRAPID” manufactured by Rigaku Corporation.
X-ray source: Cu / Kα-radiation
Tube voltage: 40kV
Tube current: 30mA
Irradiation time: 1200s
Cellulose amorphization apparatus 1 having the structure shown in FIGS. 1 to 4 using cypress wood chips and commercially available high-purity crystalline cellulose fibers (B600 manufactured by Rettenmeier, crystallinity 85 to 87%) as raw materials. Was subjected to a shearing treatment.

  In the cellulose amorphization apparatus 1 used, the upper die 2 and the lower die 3 both have an outer diameter of 90 mm (radius 45 mm), and have a raw material inlet 5 having a diameter of 34 mm at the center.

  The tapered raw material passage 23 of the upper mill 2 is formed over a range of 30 mm from the inner surface 22 (FIG. 4).

The outer radius R ₂ of the grinding part 20 is 45 mm, and the inner radius R ₁ from the center of relative rotation to the grinding part 20 is 20 mm.

  The gap 4 between the dies was set to 10 μm, and shearing was performed at a pulverization temperature of 10 ° C. The rotational speed of the lower mill 3 was 50 to 400 rpm depending on the motor power, and the pitch P between the upper mill 2 and the lower mill 3 was 2 mm.

  Here, W * was measured by connecting a power meter PW-3337 manufactured by Hioki Electric Co., Ltd. directly to a measurement line for a three-phase motor.

  The amount of cellulose-containing raw material introduced at one time from the raw material introduction port was about 0.6 to 0.7 g, and the number of times of introduction per minute was 6 to 7 times, whereby the amount of introduction per hour was 216 g to 294 g.

The results of the degree of scale parameter S _p2 and amorphized shown in Table 3.

From Table 3, in Comparative Examples 1 to 3 in which the shear pulverization was performed under the condition where the scale parameter _Sp2 was less than 300, a large change was not observed in the diffraction peak, and the same high crystallinity as that in the untreated case was shown. However, it was found that, under the conditions of Examples 1 to 3 in which the shear pulverization was performed under the condition where the scale parameter _Sp2 was 300 or more, the diffraction peak was significantly reduced and low crystallinity was exhibited.

From the above, it was found that the cellulose crystallinity can be remarkably reduced by grinding with a scale parameter _Sp2 of 300 or more.
<Example 10, Comparative Examples 10-13>
The rotational speed of the lower die was set to 180 rpm as in Example 8, and the gap between the dies was set in the range of 0 to 50 μm. Otherwise, the pulverization was performed under the same conditions as in Example 8.

The results of the degree of scale parameter S _p2 and amorphized shown in Table 4.

  In Table 4, the degree of amorphization was confirmed from the measurement results of the wide-angle X-ray diffraction for those with a graduated scale having a gap of 10 μm or less. In other cases, that is, about 20 to 50 μm, it was judged that it was discharged without applying a load during pulverization. Therefore, the degree of non-crystallization was the same as that of untreated.

From Table 4, it was found that by setting the gap to 10 μm or less, a sufficient load is applied to the cellulose-containing raw material, and the crystallinity of cellulose can be remarkably reduced under the condition where the scale parameter _Sp is 300 or more.

As described above, multiple teeth extending parallel to the direction intersecting the circumferential direction of the relative rotation are provided on the surface forming the gap, and the teeth of the upper and lower dies are crossed with each other on the surface forming the gap. By forming a grid of pitch P and making the gap for loading the powder within a certain range, the scale parameter S _p2 correlates with the work done on the viscosity of the powder, It was found that amorphousization becomes possible.

DESCRIPTION OF SYMBOLS 1 Cellulose amorphization apparatus A One member 2 Upper die B The other member 3 Lower die 4 Gap 5 Raw material inlet 6 Storage part 7 Gap adjustment part 8 Dish 9 Falling port 10 Falling chute 20 Grinding part 21 The surface which forms a gap (Bottom)
22 Inner surface 23 Raw material passage 24 Teeth 25 Groove 31 Surface for forming a gap (upper surface)
34 tooth 35 groove 40 motor 41 motor control cable 50 heater 60 computer

Claims (7)

This is a method for producing amorphous cellulose in which a cellulose-containing raw material is introduced into a gap and pulverized by applying a shearing force by using one member and the other member that rotate relative to each other through the gap, thereby making the cellulose amorphous. And
One member and the other member are provided with a plurality of teeth extending parallel to each other at a pitch P in the direction intersecting the circumferential direction of the relative rotation on the surface forming the gap. The teeth intersect each other on the surface forming the gap to form a grid with a pitch P,
A motor that transmits and rotates torque to at least one of the one member and the other member is driven to rotate them relative to each other through a gap, and a cellulose-containing raw material is charged into the gap. _p1 :

(W ^* is the motor power consumption (W), P is the pitch of the grid (mm), and ω is the relative rotation speed (rpm).) Shear force under the condition of 2 or more and a gap of 10 μm or less A process for producing amorphous cellulose, which comprises pulverizing and amorphizing cellulose. The method for producing amorphous cellulose according to claim 1, wherein the scale parameter _Sp1 is in the range of 2 to 20. This is a method for producing amorphous cellulose in which a cellulose-containing raw material is introduced into a gap and pulverized by applying a shearing force by using one member and the other member that rotate relative to each other through the gap, thereby making the cellulose amorphous. And
One member and the other member are provided with a plurality of teeth extending parallel to each other at a pitch P in the direction intersecting the circumferential direction of the relative rotation on the surface forming the gap. The teeth intersect each other on the surface forming the gap to form a grid with a pitch P,
A motor that transmits and rotates torque to at least one of the one member and the other member is driven to rotate them relative to each other through a gap, and a cellulose-containing raw material is charged into the gap. _p2 :

(W ^* is the motor power consumption (W), R ₂ is the outer radius (m) of the grinding part, R ₁ is the inner radius (m) from the center of the relative rotation to the grinding part, and ω is the rotation of the relative rotation. A method for producing amorphous cellulose, wherein the cellulose is made amorphous by pulverizing under a condition that the number (rpm) is 300 or more and a gap is 10 μm or less. Amorphization method for producing a cellulose according to the scale parameter S _p2 is claim 3 is in the range of 300 to 3000.   The method for producing amorphous cellulose according to any one of claims 1 to 4, wherein the pitch P of the lattice is in the range of 0.5 to 5 mm.   The method for producing amorphous cellulose according to any one of claims 1 to 5, wherein the rotational speed ω of the relative rotation is in the range of 50 to 190.   One member and the other member are an upper die and a lower die having a plane as a surface to form a gap, and a cellulose-containing raw material is introduced into the gap from a raw material introduction port leading to the gap to give a shearing force and pulverized. The method for producing amorphous cellulose according to any one of claims 1 to 6, wherein the obtained powder containing amorphous cellulose is recovered from the side of the gap.

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