JP5818628B2 - Non-liquid substance manufacturing method and non-liquid substance manufacturing apparatus - Google Patents

Description

  The present invention relates to a method for producing a non-liquid substance, and an apparatus for producing a non-liquid substance.

Silica can be roughly classified into natural products and synthetic products, and crystalline silica or amorphous silica exists. Although these are used in various fields, amorphous silica is used as a functional filler material in various applications such as ink thickeners, paper fillers, rubber and plastic fillers. . Recently, it is also used as a raw material for silicon for solar cells and silicon carbide for power semiconductors.
As a general method for producing amorphous silica, there is a wet method using a neutralization reaction between an alkali silicate aqueous solution and a mineral acid. Among wet methods, it is well known that the sedimentation method is easy to perform operations such as filtration and is excellent in production cost.
Here, the sedimentation method refers to precipitation and sedimentation of amorphous silica as particles by controlling so that an agar-like silicate gel does not occur when neutralizing an alkali silicate aqueous solution and a mineral acid. Is the method.
As a production method using the precipitation method, for example, a step of obtaining a precipitated silica by dropping an aqueous alkali silicate solution or the like from a nozzle or a hose into a reaction solution or the like, and a separation step of separating the synthesized precipitated silica and the aqueous solution And a production method including a drying step of drying the precipitated silica (Patent Document 1 and Patent Document 2).

JP 11-228126 A JP 2000-351618 A

A method of producing a reaction product (precipitated silica) by dropping a liquid (alkali silicate aqueous solution or the like) into a reaction solution or the like using a nozzle or a hose as described above is performed when the viscosity of the dropped liquid increases (for example, In the above sedimentation method, when the concentration of an aqueous alkali silicate solution is increased in order to increase productivity, when a light specific gravity carbon or inorganic filler is mixed with an aqueous alkali silicate solution, or in the winter, an aqueous alkali silicate solution Etc.), it is difficult to drop the liquid from a nozzle or a hose.
In addition, a problem that the reaction product covers the surface of the reaction solution and the reaction is inhibited (for example, in the above precipitation method, when the dropping rate of an aqueous alkali silicate solution or the like is increased in order to increase production efficiency, In some cases, air was mixed into the alkali silicate aqueous solution or the like as the viscosity increased.
The object of the present invention has been made in view of the above circumstances, and provides a method for producing a non-liquid substance by making a liquid into droplets and mixing it with another liquid even if the viscosity of the liquid is high. There is.
Another object of the present invention is to produce a non-liquid substance that can be efficiently mixed into another liquid and mixed with another liquid to produce a non-liquid substance, and mixing is not inhibited by the non-liquid substance. It is to provide a way to do.

As a result of intensive studies to solve the above-mentioned problems, the inventors have determined that the first liquid is the inner liquid so that the inner peripheral surface of the cylindrical water hole forming portion is covered with the first liquid. The liquid of the second liquid flows from the liquid droplet forming section (having a plurality of specific holes) that flows down along the peripheral surface and is installed in the internal space of the cylindrical water hole forming section. The droplets are ejected using centrifugal force, and the droplets and the first liquid are mixed on the inner peripheral surface to generate a non-liquid substance formed by the reaction between the first liquid and the second liquid. The inventors have found that the object of the present invention can be achieved by the method to make the present invention, and have completed the present invention.
That is, the present invention provides the following [1] to [5].
[1] A method for producing a non-liquid substance obtained by mixing a first liquid and a second liquid and reacting the first liquid and the second liquid, wherein The first liquid is allowed to flow along the inner peripheral surface so that the inner peripheral surface is covered with the first liquid, and is installed in the internal space of the cylindrical water hole forming portion in the horizontal direction. A rotating liquid droplet forming section , which has a plurality of holes having a diameter of 1 to 10 mm on a side surface facing the inner peripheral surface of the cylindrical water hole forming section, and a second liquid liquid The droplets are ejected using centrifugal force, and the droplets and the first liquid are mixed on the inner peripheral surface to generate a non-liquid substance formed by the reaction between the first liquid and the second liquid. A method for producing a non-liquid substance, characterized by comprising:
[2] In the above [1], the first liquid is a mineral acid, and the second liquid is an aqueous alkali silicate solution, and amorphous silica is precipitated by mixing these two liquids. The manufacturing method of the non-liquid substance of description.
[3] An apparatus for producing a non-liquid substance obtained by mixing a first liquid and a second liquid and reacting the first liquid and the second liquid, and storing the first liquid. A storage tank for liquid,
A supply path for supplying the first liquid to the liquid storage tank, and a cylindrical water installed in the liquid storage tank for allowing the first liquid to flow down from the liquid storage tank along the inner peripheral surface. A plurality of holes having a diameter of 1 to 10 mm are provided on a side surface facing the inner peripheral surface of the hole forming portion and the cylindrical water hole forming portion and facing the inner peripheral surface of the cylindrical water hole forming portion. A droplet forming unit for discharging a droplet of the second liquid using a centrifugal force generated by horizontal rotation, a motor for rotating the droplet forming unit in the horizontal direction, and the droplet forming unit. And a supply path for supplying a second liquid to the apparatus.
[4] Furthermore, it has a recovery tank for recovering the first liquid and a non-liquid substance formed by the reaction of the first liquid and the second liquid, and supplies the first liquid to the liquid storage tank The apparatus for producing a non-liquid substance according to [3], wherein the first liquid recovered in the recovery tank is supplied to the liquid storage tank through a supply path for performing the operation.
[5] The above-mentioned [3] or [3], wherein the first liquid is a mineral acid and the second liquid is an aqueous alkali silicate solution, and amorphous silica is precipitated by mixing these two liquids. The apparatus for producing a non-liquid substance according to [4].

The method for producing a non-liquid substance of the present invention can produce a non-liquid substance by making a liquid into droplets and mixing it with another liquid even if the viscosity of the liquid is high.
In addition, the non-liquid substance manufacturing method of the present invention can efficiently produce a non-liquid substance by making a liquid into droplets and mixing with another liquid, and the non-liquid substance product inhibits mixing. It will not be done.

It is sectional drawing of an example of the manufacturing apparatus of a non-liquid substance. It is a top view of an example of the manufacturing apparatus of a non-liquid substance. It is sectional drawing which shows that the amorphous silica has precipitated in the water hole formation part. It is sectional drawing (a) of an example of a droplet formation part, and a top view (b). It is sectional drawing (a) of an example of a droplet formation part, and a top view (b). It is a figure which shows an example of a nozzle type dripping apparatus.

The method for producing a non-liquid substance according to the present invention allows the first liquid to flow down along the inner peripheral surface so that the inner peripheral surface of the cylindrical water hole forming portion is covered with the first liquid. The liquid droplet forming portion that is installed in the internal space of the cylindrical water hole forming portion and that rotates in the horizontal direction has a diameter of 1 to the side facing the inner peripheral surface of the cylindrical water hole forming portion. From the droplet forming portion having a plurality of 10 mm holes , the second liquid droplet is discharged using centrifugal force, and the droplet and the first liquid are mixed on the inner peripheral surface, A non-liquid substance formed by a reaction between the first liquid and the second liquid is generated.
The non-liquid substance manufacturing apparatus of the present invention includes a liquid storage tank for storing the first liquid, a supply path for supplying the first liquid to the liquid storage tank, and the liquid storage tank. Installed in the cylindrical water hole forming part for flowing down the first liquid from the liquid storage tank along the inner peripheral surface, and installed in the internal space of the cylindrical water hole forming part, and In order to discharge a second liquid droplet using centrifugal force generated by horizontal rotation, having a plurality of holes with a diameter of 1 to 10 mm on the side surface facing the inner peripheral surface of the cylindrical water hole forming portion. A droplet forming section, a motor for rotating the droplet forming section in the horizontal direction, and a supply path for supplying a second liquid to the droplet forming section.
In the present invention, the first liquid and the second liquid are not particularly limited, and may be a solution in which a solid, liquid or gas is dissolved in a solvent, or may be in a slurry form. Moreover, the non-liquid substance formed by the reaction between the first liquid and the second liquid is not particularly limited.
The viscosity of the second liquid is not particularly limited, but is preferably 0.25 to 10 Pa · S, more preferably 0.25 to 7 Pa · S.

Hereinafter, it demonstrates, referring an example of the manufacturing apparatus of the non-liquid substance of this invention of FIGS.
In this specification, a mineral acid is used as the first liquid and an aqueous alkali silicate solution is used as the second liquid, but the first liquid and the second liquid are not limited to these.
By mixing the droplets of the aqueous alkali silicate solution and the mineral acid, a neutralization reaction occurs and amorphous silica can be precipitated. The method for producing a non-liquid substance and the apparatus for producing a non-liquid substance of the present invention are suitable for producing amorphous silica.
1-4, the non-liquid substance manufacturing apparatus 10 of the present invention includes a liquid storage tank 3 for storing mineral acid, a supply path 7 for supplying mineral acid to the liquid storage tank, A cylindrical water hole forming portion 5 installed in the liquid storage tank, a droplet forming portion 6 installed in the internal space 19 of the water hole forming portion, and the droplet forming portion for rotating in the horizontal direction. Motor 1 and a supply passage 9 for supplying an aqueous alkali silicate solution to the droplet supply section.

The motor 1 is a device for rotating the droplet forming unit 6 in the horizontal direction, and is connected to the droplet forming unit 6 via the stirring rod 2. The motor 1 preferably has a function of freely changing the rotation speed.
The stirrer 2 connects the motor 1 and the droplet forming unit 6 and the material thereof is not particularly limited, but is preferably one that has been subjected to corrosion prevention. Specific examples include those made of resin, synthetic resin coating or rubber coating.
The liquid storage tank 3 is a tank for temporarily storing a mineral acid in order to form a water hole. The material is not particularly limited, but a material subjected to corrosion prevention is preferable. Specific examples include those made of resin, synthetic resin coating or rubber coating.
The shape of the water storage tank is not particularly limited, such as a circle or a quadrangle, but is preferably a circle from the viewpoint of preventing corner accumulation.
The production apparatus of the present invention is a mixture of the first liquid (mineral acid) and the second liquid (alkali silicate aqueous solution) in the water hole portion, and the first liquid and the second liquid react. You may have the collection tank 4 which collect | recovers non-liquid substances (amorphous silica) and the remaining 1st liquid after reaction. In the collection tank, the precipitated amorphous silica can be collected by a collection net or the like. The material is not particularly limited, but a material subjected to corrosion prevention is preferable. Specific examples include those made of resin, synthetic resin coating or rubber coating.
The shape of the collection tank is not particularly limited, such as a circle or a rectangle, but a circle is preferable from the viewpoint of preventing corner accumulation.

As shown in FIGS. 1 and 2, the water hole forming portion 5 is a cylindrical portion formed so as to penetrate the bottom surface of the liquid storage tank 3. The shape is not particularly limited, and may be a cylindrical shape, a square tube shape, or the like, but a cylindrical shape is preferable from the viewpoint of preventing corner accumulation. Further, the material is not particularly limited, but a material subjected to corrosion prevention is preferable. Specific examples include those made of resin, synthetic resin coating or rubber coating.
Although the mineral acid 11 is stored in the liquid storage tank 3, when the mineral acid is further supplied through the supply path 7 and the liquid level of the mineral acid becomes higher than the upper end of the water hole forming unit 5, So that the inner peripheral surface of the water-hole forming portion 5 is covered with mineral acid, the mineral acid overflows from the upper storage tank 3 and flows down vertically along the inner peripheral surface to form a water hole portion. To do.
A droplet forming unit 6 is installed in the internal space 19 of the cylindrical water hole forming unit 5, and droplets of the alkali silicate aqueous solution discharged from the droplet forming device 6 are mixed with mineral acid in the water hole unit. Then, particulate amorphous silica is precipitated by the neutralization reaction. The precipitated amorphous silica flows down along the inner peripheral surface together with the remaining mineral acid (see FIG. 3), so even if the number of droplets of the alkali silicate aqueous solution is increased, the surface of the mineral acid is precipitated. It is not covered with silica and the silica yield does not decrease. Moreover, it is preferable to install a droplet formation part so that it may have a rotating shaft which corresponds with the centerline of a cylindrical water formation part from a viewpoint of obtaining the amorphous silica of uniform shape.

The droplet forming unit 6 is rotated in the horizontal direction by the motor 1, and the alkali silicate aqueous solution supplied from the supply path 9 for supplying the alkali silicate aqueous solution is supplied from the hole 16 formed on the side surface to the water hole forming unit 5. Toward the mineral acid 23 flowing down the inner peripheral surface of the liquid by a centrifugal force in the state of droplets 13 (see FIG. 3).
Since the liquid droplets are ejected by centrifugal force, the liquid droplets can be ejected by adjusting the rotational speed even when the viscosity of the alkali silicate aqueous solution is high.
The shape of the droplet forming portion is not particularly limited, and examples thereof include a cylinder, a quadrangular column, a cone, and a quadrangular pyramid. From the viewpoint of preventing corner accumulation, a cylindrical shape is preferable.
FIG. 4 shows an example of a droplet forming unit. A hole 16 is formed in the side surface of the droplet forming unit 6. The size, shape, etc. of the pores are formed in accordance with the desired particle diameter of the amorphous silica, but are preferably circular with a diameter of 1 to 10 mm, more preferably 2 to 8 mm. Further, from the viewpoint of forming a plurality of droplets at the same time and mixing them efficiently, it is preferable that a plurality of holes are formed on the entire side surface of the droplet forming portion facing the inner peripheral surface of the water hole forming portion. Further, a tube or the like may be connected to the hole.
Further, a cover 15 having a hole 17 may be installed outside the droplet forming unit 6. The cover is fixed, and when the hole 16 formed in the rotating droplet forming unit 6 and the hole 17 of the cover are aligned, the droplet of the alkali silicate aqueous solution is discharged, The droplets can be prevented from contacting each other and can be discharged one by one.
A partition plate 20 is formed in the droplet forming unit 6 for the purpose of ejecting the droplets uniformly from the respective holes provided in the droplet forming unit 6. The number of partition plates is two or more, preferably 2 to 8. Although the shape of a partition plate is not specifically limited, A square, a triangle, a trapezoid, etc. are mentioned.
A barb 21 may be provided above the droplet forming unit 6 so that the aqueous alkali silicate solution does not flow outside due to the centrifugal force during rotation.
The material of the droplet forming portion is not particularly limited, but a material with corrosion prevention is preferable. Specific examples include those made of resin, synthetic resin coating or rubber coating.
Further, the shape of the amorphous silica can be controlled by adjusting the clearance between the droplet forming portion 6 and the mineral acid covering the inner peripheral surface of the water hole forming portion 5. For example, when the clearance is large, the obtained amorphous silica becomes flaky.

The supply path 7 is for supplying mineral acid to the upper storage tank. As shown in FIG. 1, the mineral acid in the recovery tank 4 may be transferred to the upper liquid storage tank 3. The material is not particularly limited, but a material excellent in corrosivity is preferable. Further, the mineral acid may be filtered during the transfer.
The supply path 9 is for supplying an alkali silicate aqueous solution to the droplet supply unit 6. The material is not particularly limited, but a material excellent in corrosivity is preferable.

The alkaline silicate aqueous solution in the specification refers to an alkaline aqueous solution containing a substance containing silicic acid (SiO2) in the chemical formula. Specifically, water glass etc. are mentioned. Commercially available water glass can be used, and in addition to Nos. 1, 2, and 3 specified by the JIS standard, products that are manufactured and sold by each water glass manufacturer must also be used. Can do.
The concentration of Si contained in the alkali silicate aqueous solution is preferably 10.0% by mass or more, more preferably 12.5% by mass or more, and particularly preferably 20.0% by mass or more.
The temperature of the alkali silicate aqueous solution is preferably 0 to 50 ° C, more preferably 10 to 30 ° C.
The viscosity of the aqueous alkali silicate solution is preferably 0.25 to 10 Pa · S, more preferably 0.25 to 7 Pa · S.
The alkali silicate aqueous solution may be mixed with carbon, a functional filler, and the like. By mixing carbon or the like with the alkali silicate aqueous solution, amorphous silica containing carbon or the like can be produced.

Examples of the mineral acid used in this step include sulfuric acid, hydrochloric acid, nitric acid and the like, and it is preferable to use sulfuric acid for the reason of reducing the chemical cost.
The concentration of the mineral acid is sufficient if the particulate amorphous silica is precipitated when the neutralization reaction with the alkali silicate aqueous solution is performed, preferably 10% by volume or more, more preferably 15% by volume or more, and particularly preferably. Is 20% by volume or more. When the concentration of the mineral acid is less than the above range, particulate amorphous silica may not be produced, or both particulate amorphous silica and gel silica may be produced.
It is desirable to maintain the pH at which the droplets of the alkali silicate aqueous solution and the mineral acid are in contact with each other, preferably 1.0 or less, more preferably 0.9 or less. If the pH exceeds 1.0, silica may precipitate in a gel form.
The precipitation temperature of the amorphous silica when the aqueous alkali silicate droplets and the mineral acid are neutralized is not particularly limited, but is preferably 10 to 80 ° C, more preferably 15 to 40 ° C, Especially preferably, it is 20-30 degreeC, and it is normal temperature (for example, 10-40 degreeC) normally. When the temperature exceeds 80 ° C., the energy cost increases and the equipment is easily corroded.

Hereinafter, the present invention will be described based on an embodiment using a prototype device. As a prototype device, the one shown in FIG. 1 was adopted. Further, the droplet forming unit shown in FIG. 5 was used.
Moreover, the nozzle type dripping apparatus was used as a comparative example. In addition, this invention is not limited by these Examples, The change of various embodiment is possible within the range as described in a claim.
[1. Element]
The followings were used as members of the non-liquid substance manufacturing apparatus.
(A) Motor (stirrer): Tornado stirrer (manufactured by ASONE, SM-104)
(B) Stirring bar: accessory of tornado stirrer SM-104 (length 400 mm, diameter 8 mm)
(C) Liquid storage tank: large container box (capacity 46.2 liters, length x width x depth = 580 mm x 364 mm x 274 mm)
(D) Recovery tank: Dylite tank (capacity 500 liters, diameter 1000 mm)
(E) Water hole forming part: Commercially available polyvinyl chloride pipe (inner diameter 110 mm, length 300 mm)
(F) Droplet formation part: Commercially available polyvinyl chloride pipe (diameter 56 mm, height 70 mm)
(G) Pump: Chemical solution transfer handy pump (manufactured by AS ONE, HP-201 type)
(H) Nozzle type dripping device; circle flow nozzle kit of coolant nozzle (hole diameter 6.3 mm) (see FIG. 6)
[2. raw materials]
The raw materials used in the examples were as shown below.
(I) Water glass: Water glass No. 3 manufactured by Fuji Chemical Co., Ltd. (J) Sulfuric acid: Industrial sulfuric acid (K) Carbon: Show black N550 manufactured by Cabot Japan

Using the above-mentioned members, a non-liquid substance manufacturing apparatus of the present invention as shown in FIG. 1 was prototyped.
The water hole forming section 5 cuts a commercially available pipe made of polyvinyl chloride having an inner diameter of 110 mm into a length of 300 mm, and bonds the cut pipe to a liquid storage tank 3 having a hole in the bottom using a special adhesive. In addition, the joint was prepared by fixing with a sealing agent.
As shown in FIG. 5, the droplet forming unit 6 is prepared by bonding an acrylic plate to the bottom of a commercially available polyvinyl chloride pipe having a length of 70 mm and an inner diameter of 56 mm, and then 10 mm in the vertical direction on the side surface. It was produced by drilling holes of φ6 mm at intervals. The droplet forming unit 6 was screwed to the shaft of a stirrer (Tornado stirrer, product name SM-104 manufactured by AS ONE).

[Example 1]
Using the amorphous silica production apparatus 10 shown in FIG. 1, water glass droplets whose liquid temperature is adjusted to 10 ° C. are brought into contact with sulfuric acid flowing down along the inner peripheral surface of the water hole forming portion 5. Thus, amorphous silica was produced. As a result, the non-liquid substance production apparatus of the present invention was able to produce amorphous silica by smoothly ejecting liquid droplets from the rotating liquid droplet forming section 6.
The reason for setting the liquid temperature to 10 ° C. is that winter is assumed.
[Comparative Example 1]
Using a coolant nozzle (see FIG. 6), water glass whose liquid temperature was adjusted to 10 ° C. was dropped into sulfuric acid to produce amorphous silica. However, liquid was not discharged from the holes, and amorphous silica could not be produced.

[Examples 2 and 3]
Carbon is previously mixed with water glass at a content rate described in Table 1, and using the apparatus shown in FIG. The amorphous silica containing carbon was produced by contacting with sulfuric acid flowing down along the inner peripheral surface of (). As a result, the non-liquid substance manufacturing apparatus of the present invention was able to manufacture amorphous silica by smoothly discharging droplets from the rotating droplet forming section (6).
[Comparative Example 2]
Preparation of amorphous silica containing carbon by mixing carbon with water glass in advance at a content described in Table 1 and using a coolant nozzle to drop water glass adjusted to a liquid temperature of 20 ° C. into sulfuric acid. Went. However, liquid was not discharged from the holes, and amorphous silica could not be produced.

DESCRIPTION OF SYMBOLS 1 Motor 2 Stirring bar 3 Liquid storage tank 4 Recovery tank 5 Water hole formation part 6 Droplet formation part 7 Supply path 8 Acrylic resin 9 Supply path 10 Non-liquid substance production apparatus 11 Mineral acid 12 Mineral acid 13 Alkali silicate aqueous solution 14 Amorphous silica 15 Cover 16 Hole 17 Hole 18 Screwing 19 Internal space 20 Partition plate 21 Maple 22 Mineral acid 23 Mineral acid 24 Alkaline silicate aqueous solution 25 Coolant nozzle

Claims (5)

A method of producing a non-liquid substance obtained by mixing a first liquid and a second liquid and reacting the first liquid and the second liquid,
The first liquid is allowed to flow along the inner peripheral surface so that the inner peripheral surface of the cylindrical water hole forming portion is covered with the first liquid,
A droplet forming part that rotates in the horizontal direction and is installed in the internal space of the cylindrical water hole forming part, and has a diameter of 1 to 10 mm on the side surface facing the inner peripheral surface of the cylindrical water hole forming part. The second liquid droplets are ejected from the droplet forming portion having a plurality of holes using centrifugal force, and the droplets and the first liquid are mixed on the inner peripheral surface. A method for producing a non-liquid substance, comprising producing a non-liquid substance formed by a reaction between one liquid and a second liquid.   The non-liquid according to claim 1, wherein the first liquid is a mineral acid, and the second liquid is an aqueous alkali silicate solution, and amorphous silica is precipitated by mixing these two liquids. A method for producing a substance. An apparatus for producing a non-liquid substance obtained by mixing a first liquid and a second liquid and reacting the first liquid and the second liquid,
A liquid storage tank for storing the first liquid;
A supply path for supplying a first liquid to the liquid storage tank;
A cylindrical water hole forming part that is installed in the liquid storage tank and allows the first liquid to flow down from the liquid storage tank along the inner peripheral surface;
Horizontal rotation that is installed in the internal space of the cylindrical water hole forming portion and has a plurality of holes having a diameter of 1 to 10 mm on the side surface facing the inner peripheral surface of the cylindrical water hole forming portion. A droplet forming portion for discharging a droplet of the second liquid using a centrifugal force by ;
A motor for rotating the droplet forming part in the horizontal direction;
A supply path for supplying a second liquid to the droplet forming section;
An apparatus for producing a non-liquid substance. Furthermore, it has a collection tank for collecting the first liquid and the non-liquid substance formed by the reaction between the first liquid and the second liquid,
The apparatus for producing a non-liquid substance according to claim 3, wherein the first liquid recovered in the recovery tank is supplied to the liquid storage tank by a supply path for supplying the first liquid to the liquid storage tank.   5. The method according to claim 3, wherein the first liquid is a mineral acid, and the second liquid is an aqueous alkali silicate solution, and amorphous silica is precipitated by mixing these two liquids. Non-liquid substance production equipment.

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