JP2012130886A - Method for moving and/or reacting liquid phase - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for suppressing the biased flow of liquid phase without using a device such as a liquid distributer or a porous material in a packed column-type chemical device.SOLUTION: In the method for moving and/or reacting the liquid phase having a step 1 for surface-treating solid particle and a step 2 in which the liquid phase comes in contact with the surface-treated particle in the packed column after the step 1, the content ratio of the particle having particle size of 0.09 mm or less is 0 to 33 mass% and the content ratio of the particle having particle size larger than 16 mm is 0 to 33 mass% in the particle size distribution of the solid particle. The liquid phase is hydrophilic liquid 1, and the surface-treatment includes a step of bringing the surface of the solid particle into contact with the hydrophilic liquid 2 and a step of drying the hydrophilic liquid 2. In the surface treatment, a spread area increasing ratio is 10 to 10,000% calculated by a standard examination.

Description

  The present invention relates to a liquid phase transfer and / or reaction method in a chemical apparatus using a packed tower.

In chemical industry processes, packed towers packed with solid particulate packing in order to efficiently perform mass transfer between different phases such as gas-liquid, liquid-liquid, and / or catalytic action or adsorption action of solid particles Is used. For example, trickle reactors and absorption towers used as chemical devices for gas-liquid reactions and gas absorption into liquids are used.
The trickle reaction using the trickle reactor is performed in a flow state in which the liquid phase component is called perfusion flow. This perfusion flow is said to occur when the liquid phase component and the gas phase component are in a specific flow rate range, and various reports have been made on the flow rate range (Non-Patent Document 1).
On the other hand, the gas absorption operation in the absorption tower may be performed in the flow state of the perfusate flow as in the trickle reaction, but can be performed in various flow states without being limited to the perfusion flow.
However, in the packed tower, dispersion (hereinafter referred to as a drift phenomenon) occurs in the liquid flow distribution in the horizontal direction of the packed bed formed by filling the solid particles.
The drift phenomenon deteriorates the liquid-solid, gas-liquid or liquid-liquid contact efficiency, and significantly reduces the reaction efficiency. Further, when the solid particles are a catalyst, local heat generation is induced, and the catalyst is deactivated and the inner wall of the packed tower is deteriorated. For this reason, the improvement of the drift in the packed tower is a very big problem in mass transfer between liquid phases or different phases, trickle reaction, gas absorption operation and the like.

As a method for solving this problem, a method of installing a liquid distributor in a liquid introduction portion or a method of introducing a liquid redistributor between layers of a catalyst or a packing is adopted. For example, there is a method (bubble cap method) that increases the dispersibility and redispersibility of the introduction liquid and the drift liquid by installing a cap on the tray to which the riser pipe is attached (Non-patent Document 2).
Also, a method of increasing the gas-liquid contact efficiency by installing a porous material on the side wall of the packed tower and supplying a gas raw material through this porous material for the purpose of preventing a decrease in reaction efficiency due to the drift phenomenon Has been proposed (Patent Document 1).

JP-A-6-277497

Chemical Engineering Vol. 46, No. 4, p. 215 (1982), AIChE Journal Vol. 32, No1, p. 115 (1986) Chemical Engineering Vol. 44, No. 7, p. 415 (1980), Chemical Engineering Vol. 58, No. 11, p. 883 (1994)

However, even if a liquid distributor or a redistributor is used, it is extremely difficult to completely suppress the liquid drift. As a solution, an increase in the number of redistributors can be considered, but the number of installations is limited due to restrictions such as device size, device cost, and handling. As a result, the drift improvement effect in this method is limited.
Further, the method described in Patent Document 1 is preferable from the viewpoint of downsizing and cost reduction of the reactor because the reactor is enlarged and the cost of the reactor main body is increased by using a porous material. That's not true.

  It is an object of the present invention to provide a method for suppressing liquid phase drift without using equipment such as a liquid distributor or a porous material in a packed tower type chemical apparatus.

The present invention includes a step 1 for surface treatment of solid particles, and after step 1,
In a packed tower, a liquid phase transfer and / or reaction method comprising the step 2 of contacting the liquid phase with the surface-treated solid particles,
In the particle size distribution of the solid particles,
The content of particles having a particle size of 0.09 mm or less is 0 to 33% by mass,
The content of particles having a particle diameter exceeding 16 mm is 0 to 33% by mass,
The liquid phase is hydrophilic liquid 1;
The surface treatment includes a step of bringing the surface of the solid particles into contact with the hydrophilic liquid 2 and a step of drying the hydrophilic liquid 2,
It is a movement and / or reaction method which is a surface treatment in which the percentage increase in the area of expansion calculated by the following standard test is 10 to 10,000%.
[Standard test]
(1) A cylindrical container having an inner wall bottom surface and having a height from the inner wall bottom surface to an end facing the inner wall bottom surface of 60 mm,
In the container having a discharge hole for the hydrophilic liquid 1 on the bottom surface of the inner wall and the end portion being an open end,
(2) The solid particles (solid particles B) before the surface treatment are immersed in the hydrophilic liquid 1 at 25 ± 2 ° C. for 1 hour and then filtered through a sieve having a maximum diameter that does not allow the solid particles to pass through. Before the surface dries
From the opening of the container, filling so that the top surface is substantially horizontal from the bottom of the inner wall to a height of 50 mm,
(3) Before the surface of the solid particles was dried, the hydrophilic liquid 1 was attached to the central portion of the end of the container with a syringe needle having an inner diameter of 0.32 mm from a height of 1 cm from the top surface. With a 5 ml syringe, add 2 ml at 1 ml / min,
(4) After completion of the dropping, when the flow of the hydrophilic liquid 1 in the filled solid particles B from the discharge hole stops, the bottom of the inner wall reaches a height of 20 mm, Removing the filled solid particles B;
(5) The spread of the hydrophilic liquid 1 on the substantially horizontal uppermost surface of the filled solid particles B that appears at a height of 20 mm from the bottom surface after the removal,
(6) Take a photograph from a height of 300 mm from the bottom of the inner wall,
The spreading area S _b (the spreading area S _b on the solid particles B) of the hydrophilic liquid 1 on the uppermost surface of the solid particles B is determined based on the photograph.
(7) In the procedure of obtaining the spread area S _b on the solid particles B (1) ~ (6), the solid particles B, wherein the solid particles B of the surface-treated after solid particles (solid particles A) except that was replaced, in the above procedure (1) the same procedure as ~ (6), determining the spread area S _a of the hydrophilic liquid first top surface of the solid particles a.
(8) The spread area increase rate is calculated by the formula [(S _a −S _b ) / S _b ] × 100 (%).

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for suppressing the drift of liquid phase components without using equipment such as a liquid distributor or a porous material in a packed tower type chemical apparatus.

In Test Example 4, photographs for determining the spread area _S a (= 106mm ^2).

The method of the present invention includes a step 1 for surface treatment of solid particles, and after step 1,
In a packed tower, a liquid phase transfer and / or reaction method comprising the step 2 of contacting the liquid phase with the surface-treated solid particles,
In the particle size distribution of the solid particles,
The content of particles having a particle size of 0.09 mm or less is 0 to 33% by mass,
The content of particles having a particle diameter exceeding 16 mm is 0 to 33% by mass,
The liquid phase is a hydrophilic liquid 1, and the surface treatment includes a step of bringing the surface of the solid particles into contact with the hydrophilic liquid 2, and a step of drying the hydrophilic liquid 2,
This is a transfer and / or reaction method that is a surface treatment in which the percentage increase in the area of expansion calculated by a standard test described later is 10 to 10,000%.

The packed column used in the present invention is packed with solid particles or specially designed packing in a vertical column, and is intended to operate liquid-solid, gas-liquid or liquid-liquid contact, preferably trickle reaction. An irrigation packed tower (hereinafter also referred to as a packed tower).
The packed tower is of any shape that forms a flowing state in which the liquid phase flows down vertically while contacting the liquid particles on the surface of the solid particles, preferably solid particles in the liquid phase. What forms the fluid state which does not embed the formed packed bed can be used.
The shape, length, diameter, and material of the reaction apparatus may be appropriately selected according to the type of raw material, reaction type, production amount, handling performance, cost, and the like. In general, the shape is a tube type, the diameter is about 10 to 3000 mm, the length is about 0.1 to 30 m, the material is made of, for example, stainless steel, and a reactor whose inner wall is coated with glass or resin depending on the raw materials or the like. Preferably used.
A multi-tube type can also be used. In that case, for example, a tube having 5 to 1000 tubes having a diameter of about 10 to 300 mm and a length of about 0.1 to 30 m can be preferably used.

The liquid phase (hereinafter also referred to as liquid phase) used in the present invention is a hydrophilic liquid 1 (hereinafter also referred to as hydrophilic liquid 1) typified by a hydrophilic liquid used in packed towers such as trickle reaction. From the viewpoint of ensuring the advantageous effects of the present invention, the hydrophilic liquid 1 is a water-soluble liquid or a solution in which at least a solvent is water-soluble. It may be.
The hydrophilic liquid 1 is preferably water, a water-soluble organic solvent,
Inorganic acids or their aqueous solutions and / or water-soluble organic solvent solutions,
Organic acids or their aqueous solutions and / or water-soluble organic solvent solutions,
Inorganic alkali or an aqueous solution thereof and / or a water-soluble organic solvent solution,
And / or
An organic alkali or an aqueous solution thereof and / or a water-soluble organic solvent solution,
Are mentioned,
Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol glycol, amides such as dimethylformamide, dimethylacetamide, nitriles such as acetonitrile, and the like. Preferably, methanol, ethanol, propanol, dimethylformamide, dimethylacetamide, more preferably methanol, ethanol,
Examples of the inorganic acid include nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid and the like, preferably nitric acid and phosphoric acid,
Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, benzoic acid, phthalic acid, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and fumaric acid. Are formic acid, acetic acid, succinic acid, adipic acid,
Examples of the inorganic alkali include ammonia, hydrazine, hydroxylamine, sodium hydroxide, potassium hydroxide,
Examples of the organic alkali include pyridine and triethylamine.

  The hydrophilic liquid 1 is more preferably water, methanol, ethanol or a solution containing at least one of these as a solvent, and more preferably water or an aqueous solution.

  The viscosity of the hydrophilic liquid 1 is preferably the degree of the viscosity of a normal liquid phase that can pass through the packed tower, and the viscosity of the hydrophilic liquid 1 measured by an Ostwald capillary viscometer at 25 ° C. is preferably 0.01 to 100 cP, more preferably 0.1 to 10 cP, still more preferably 0.1 to 2 cP. When measuring the viscosity using an Ostwald capillary viscometer, measure the flow time of the liquid after the viscometer and the sample liquid reach a sufficient temperature equilibrium.

  The solid particles used in the present invention (hereinafter also referred to as solid particles) are usually packed in a packed column and used as a packed material in contact with the liquid phase in the packed column for interphase mass transfer including the liquid phase. As these phases, inert particles, catalyst particles necessary for the reaction in the packed tower, adsorbent particles for adsorbing the liquid phase or a mixed phase containing the liquid phase, and the like can be used.

From the viewpoint of suitably securing the effects of the present invention by the surface treatment in the present invention (hereinafter also referred to as surface treatment), the solid particles include those containing a hydroxyl group or surface treatment with the hydrophilic liquid 2, for example, on the surface of the solid particles. A Si—O—Si bond or an Al—O—Al bond that is hydrolyzed to form a hydroxyl group is preferred,
Metal oxides, carbides, nitrides or hydroxides that contain or can form hydroxyl groups, or solid organic compounds that contain or do not contain metals, can be used.
Examples of metal oxides containing or capable of forming hydroxyl groups include silica (amorphous silica, etc.), alumina (γ-alumina, etc.), single metal oxides such as zirconium, titania, silica alumina, silica zirconia, zeolite Examples include complex oxides such as compounds.

In terms of the particle size distribution, the particle size of the solid particles is from the viewpoint of handling and blockage in the degree of the normal packing particles used in the packed tower,
The content of particles having a particle size of 0.09 mm or less is 0 to 33% by mass, preferably 0 to 10% by mass, more preferably 0% by mass,
The content of particles having a particle diameter exceeding 16 mm is 0 to 33% by mass, preferably 0 to 10% by mass, and more preferably 0% by mass.
The particle size distribution of the solid particles is based on the percentage under the sieve of the particle size range obtained by the dry screening test method according to JIS Z 8815.
The content of particles having a particle size of 0.09 mm or less is the sum of the percentages under the sieve having a particle size range of 0.09 mm or less,
The content of particles having a particle diameter exceeding 16 mm refers to the sum of the percentages on the sieve having a particle diameter range exceeding 16 mm.
In the following, as a result of the dry sieving test method according to JIS Z 8815 for solid particles, the total particle size under the sieve is 0 to 33% by mass, preferably 0 to 10% by mass, more preferably 0% by mass. If the upper limit of the range is X mm and the total of the percentages on the screen is 0 to 33% by mass, preferably 0 to 10% by mass, more preferably 0% by mass, the lower limit of the particle size range is Ymm. The diameter is said to be “X to Ymm”.

  The shape of the solid particles may be any of powder, molded body, etc., and can be appropriately selected according to the shape of the reaction system, reactor, and packed tower. For example, if it is a molded body, it may be spherical, cylindrical, granular, etc. Can be mentioned.

The hydrophilic liquid 2 (hereinafter, also referred to as hydrophilic liquid 2) to be brought into contact with the solid particles in the surface treatment has a ratio of increase in the area of expansion due to the standard treatment (hereinafter also referred to as the standard test) in the present invention. A water-soluble liquid or a solution in which at least the solvent is water-soluble so as to be in a predetermined range;
Preferably, water, water-soluble organic solvent,
Inorganic acids or their aqueous solutions and / or water-soluble organic solvent solutions,
Organic acids or their aqueous solutions and / or water-soluble organic solvent solutions,
Inorganic alkali or an aqueous solution thereof and / or a water-soluble organic solvent solution,
And / or
An organic alkali or an aqueous solution thereof and / or a water-soluble organic solvent solution,
Are mentioned,
Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol glycol, amides such as dimethylformamide, dimethylacetamide, nitriles such as acetonitrile, and the like. Can be mentioned.
Preferably, methanol, ethanol, propanol, dimethylformamide, dimethylacetamide, more preferably methanol, ethanol, propanol, butanol,
Examples of the inorganic acid include nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, and the like, preferably nitric acid, sulfuric acid, hydrochloric acid, and more preferably nitric acid,
Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, benzoic acid, phthalic acid, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and fumaric acid. Are acetic acid, succinic acid, adipic acid,
Examples of the inorganic alkali include ammonia, hydrazine, hydroxylamine, sodium hydroxide, potassium hydroxide,
Examples of the organic alkali include pyridine and triethylamine.

When the hydrophilic liquid 2 is surface-treated with respect to the surface of the solid particles containing the hydroxyl group or capable of forming the hydroxyl group, the increase ratio of the spread area calculated by the standard test of the present invention falls within a predetermined range. What can be made is preferable.
For example, an oxide, carbide, nitride, or hydroxide of a metal that contains or can form a hydroxyl group, or a solid organic compound that contains or does not contain a metal that contains or can form a hydroxyl group, Single metal oxides such as silica (amorphous silica, etc.), alumina (γ-alumina, etc.), zirconium, titania, etc., silica alumina, silica zirconia, zeolite compounds, which are metal oxides containing or capable of forming hydroxyl groups For complex oxides such as these, the hydrophilic liquid 2 is preferably water, nitric acid, sulfuric acid, hydrochloric acid, acetic acid, succinic acid, or adipic acid, more preferably water, nitric acid, or succinic acid, and even more preferably water.

  However, when the liquid phase comes into contact with the surface-treated solid particles, the effects such as desired reaction or adsorption performed when the liquid phase comes into contact with the solid particles before the surface treatment may be significantly reduced. It is preferable to use those not present.

  The viscosity of the hydrophilic liquid 2 is preferably such that the solid particles can be efficiently contacted with the hydrophilic liquid 2 when the solid particles are immersed in the hydrophilic liquid 2 or when the hydrophilic liquid 2 is refluxed. In order to carry out the surface treatment smoothly in the present invention, it is more preferably 0.01 to 10000 cP, further preferably 0.1 to 5000 cP, further preferably 0.1 to 1000 cP, and further water or other as necessary. You may dilute with the hydrophilic liquid 2 and use it, adjusting a viscosity suitably.

  The surface treatment is carried out by a standard test performed on the solid particles after the surface treatment, and the percentage increase in the spread area described later is 10 to 10,000%, preferably 20 to 5000%, more preferably 30 to 2000%, and still more preferably 30. What is necessary is just to make the hydrophilic liquid 2 and a solid particle contact so that it may become -1500%.

From the viewpoint of efficient surface treatment, after the hydrophilic liquid 2 is heated to around the boiling point of the medium of the hydrophilic liquid 2 and the solid particles are immersed in the hydrophilic liquid 2, preferably the hydrophilic liquid 2 is further refluxed. It is more preferable to carry out by removing the hydrophilic liquid 2 by filtration or decantation, and it is more preferable to dry by heating after that.
From the viewpoint of efficiently performing the surface treatment, the hydrophilic liquid 2 to be brought into contact with the solid particles is preferably 1 to 10000 parts by weight, more preferably 10 to 1000 parts by weight, further preferably 100 parts by weight of the solid particles. Is 50 to 300 parts by weight.

When the hydrophilic liquid 2 is refluxed, the reflux time is preferably 0.1 to 10,000 hours, more preferably 1 to 100 hours, still more preferably 5 to 20 hours, and further preferably 5 to 10 hours.
When the hydrophilic liquid 2 is refluxed, for example, it can be performed using a cooler such as a Liebig condenser or a Dimroth condenser.

In the step of drying the hydrophilic liquid 2, in the air, preferably by heat drying,
Preferably at 30-300 ° C, more preferably at 50-200 ° C, still more preferably at 80-150 ° C,
Preferably it is 0.1 to 1000 hours, More preferably, it is 1 to 100 hours, More preferably, it is 5 to 50 hours, More preferably, it carries out for 10 to 30 hours.
In addition, from the viewpoint of sufficient drying and drying efficiency, it is desirable to perform drying for a relatively short time at a high temperature and for a relatively long time at a low temperature, for example,
In 30-80 degreeC, Preferably it is 10 to 1000 hours, More preferably, it is made to dry for 30 to 100 hours,
80 to 300 ° C., preferably 80 to 200 ° C., more preferably 80 to 150 ° C., preferably 0.1 to 100 hours, more preferably 1 to 50 hours, still more preferably 5 to 50 hours, still more preferably 10 Allow to dry for ~ 30 hours.

The standard test in the present invention (hereinafter also referred to as standard test) is performed under the following conditions.
(1) A cylindrical container having an inner wall bottom surface and having a height from the inner wall bottom surface to an end facing the inner wall bottom surface of 60 mm,
In the container having a discharge hole for the hydrophilic liquid 1 on the bottom surface of the inner wall and the end portion being an open end,
(2) The solid particles before the surface treatment (solid particles B) are immersed in the hydrophilic liquid 1 at 25 ± 2 ° C. for 1 hour and then filtered, and before the surface of the solid particles is dried,
From the opening of the container, filling so that the top surface is substantially horizontal from the bottom of the inner wall to a height of 50 mm,
(3) Before the surface of the solid particles was dried, the hydrophilic liquid 1 was attached to the central portion of the end of the container with a syringe needle having an inner diameter of 0.32 mm from a height of 1 cm from the top surface. With a 5 ml syringe, add 2 ml at 1 ml / min,
(4) After completion of the dropping, when the flow of the hydrophilic liquid 1 in the filled solid particles B from the discharge hole stops, the bottom of the inner wall reaches a height of 20 mm, Removing the filled solid particles B;
(5) The spread of the hydrophilic liquid 1 on the substantially horizontal uppermost surface of the filled solid particles B that appears at a height of 20 mm from the bottom surface after the removal,
(6) Take a photograph from a height of 300 mm from the bottom of the inner wall,
The spreading area S _b (the spreading area S _b on the solid particles B) of the hydrophilic liquid 1 on the uppermost surface of the solid particles B is determined based on the photograph.
(7) In the above said steps (1) to determine the spread area S _b of the solid particles B (6), except that the solid particles B was replaced by the surface-treated after solid particles (solid particles A) , the step (1) to the same procedure (6), determining the spread area S _a of the hydrophilic liquid first top surface of the solid particles a.
(8) The spread area increase rate is calculated by the formula [(S _a −S _b ) / S _b ] × 100 (%).
The standard test is preferably performed under a humidity of 50 ± 5%.

In the above procedure (2), the solid particles before the surface treatment (solid particles B) are immersed in the hydrophilic liquid 1 at 25 ± 2 ° C. for 1 hour and then filtered, preferably within 20 minutes, More preferably within 10 minutes, even more preferably within 5 minutes, the filling is preferably performed so that the top surface is substantially horizontal from the opening of the container to a height of 50 mm from the bottom surface of the inner wall,
In the above step (3), the hydrophilic liquid 1 is placed in the center of the end of the container preferably within 30 minutes, more preferably within 20 minutes, and even more preferably within 10 minutes after the filtration. It is preferable to drop 2 ml at a rate of 1 ml / min with a 5 ml syringe attached with an injection needle having an inner diameter of 0.32 mm from a height of 1 cm from the top surface.

  The dropping of the hydrophilic liquid 1 in the above procedure (3) is preferably carried out by avoiding the void of the uppermost solid particle B or A using a 5 ml syringe equipped with an injection needle having an inner diameter of 0.32 mm.

Above procedure (6) and a spreading area S _a of the hydrophilic liquid first top surface of the spread area S _b and solid particles A of a hydrophilic liquid 1 uppermost surface of the solid particles B in (7), the solid particles B, or The area of the surface of the solid particle A wetted by the hydrophilic liquid 1 in the planar field of view at the height of the photograph taken.

  In the case where the wetted portion can be identified with the naked eye by the hydrophilic liquid 1, the area surrounded by the outline of the wetted portion in the photographed image may be obtained.

  When the portion wetted by the hydrophilic liquid 1 cannot be identified with the naked eye, a dye (possibly fluorescent dye) dissolved in the hydrophilic liquid 1 in advance in the hydrophilic liquid 1 is added to the hydrophilic liquid 1 so that it can be identified with the naked eye. It is advisable to take a photograph after adding it to the extent that the wetting on the surface of the solid particles is not inhibited so that it can be identified with the naked eye. Alternatively, a photograph may be taken after a pigment or the like is sprayed on a portion wetted by the hydrophilic liquid 1 so that the portion can be distinguished from a portion not wetted by the hydrophilic liquid 1. As the dye, for example, Bordeaux S, Brilliant Blue FCF and the like can be suitably used.

  The photograph is preferably photographed so clearly that the area of the wetted portion of the solid particles by the hydrophilic liquid 1 can be measured according to the image analysis conditions described later. From the viewpoint that it is easy to identify the area of the portion wetted by the hydrophilic liquid 1, color photography is preferable.

May be obtained spread area S _a of the hydrophilic liquid first top surface of the spread area S _b and solid particles A of a hydrophilic liquid 1 uppermost surface of the solid particles B using an image analyzer for photos taken.
When using an image analysis apparatus, for example, when analyzing a color photograph using image analysis software Image-J (free software manufactured by the National Institute of Health), the image magnification is preferably 30. -0.05 times, more preferably 10-0.1 times, and even more preferably 3-0.5 times. When the original image is a color image, it is separated into RGB three primary colors, and each obtained RGB image It is preferable to obtain the area by selecting an image with clear colored particles.

  The container used in the standard test (hereinafter also referred to as a container) is such that the spread of the hydrophilic liquid 1 on the uppermost surface of the solid particles B or A observed in the procedures (6) and (7) does not reach the inner wall of the container. And the inner wall cross section may be circular or polygonal, preferably circular. The material of the inner wall of the container is strong enough not to be deformed when solid particles are filled between the inner walls of the container. When the hydrophilic liquid 1 reaches the bottom surface of the inner wall, the hydrophilic liquid 1 penetrates into the inner wall. Any material such as metal, plastic or glass may be used as long as it is a material that can be quickly discharged from the discharge hole on the bottom surface of the inner wall.

  The bottom of the inner wall of the container is provided with a discharge hole so that the hydrophilic liquid 1 dripped in the standard test procedure (3) does not stay on the bottom of the inner wall of the container. In the embodiment, before filling the solid particles, glass beads having a predetermined diameter are filled in the container, and these glass beads function as discharge holes. Thus, the inner wall bottom surface of the container may be an inner wall provided with a discharge hole, or a void that can quickly discharge the hydrophilic liquid 1 from the solid particles may be provided by some means to function as a discharge hole.

[Standard test]
A plastic cylindrical container having an inner diameter of 30 mm was filled with glass beads having a diameter of 5 mm until the height reached 50 mm. The solid particles not subjected to surface treatment in each test example (solid particles B) were immersed in water (room temperature 25 ° C.) for 1 hour and then filtered through a sieve having an aperture of 1.4 mm. Within 2 minutes after filtration) this was filled onto the top surface of the glass beads until it was 50 mm high from the top surface of the glass beads.
While the surface of the solid particles did not dry (within 5 minutes after the filtration), the center of the cylindrical container filled with the solid particles B was colored blue with brilliant blue FCF dissolved at a concentration of 0.01% by weight. 1 ml of water (hydrophilic liquid 1) using a 5 ml syringe (product name: All Plastic Disposable Syringe, manufactured by HSW) equipped with an injection needle (product name: Top Injection Needle, manufactured by Top Company) having an inner diameter of 0.32 mm 2 ml was added dropwise at a rate of 1 minute.
After the completion of the dropping, it was confirmed that the dropping of the liquid into the glass beads was stopped, and then the filled solid particles B were removed from the uppermost surface of the glass beads to a height of 20 mm to the outside of the cylindrical container. Take a picture of the top surface of the solid particles B that appeared 20 mm above the top surface of the glass beads from a height of 300 mm from the top surface of the glass beads, and use image analysis software Image-J (image magnification: 0.75 times) Te was determined the spread area S _b of the water on the top surface of the solid particles B.
Next, in the procedure for obtaining the water spreading area on the uppermost surface of the solid particle B, water on the uppermost surface of the solid particle A is obtained by the same procedure except that the solid particle A is used instead of the solid particle B. I asked the spread area _{S a.}
In each test example, the spread area increase rate was calculated by [(S _a −S _b ) / S _b ] × 100 (%).
The humidity of the test environment was 52%.

[Test Example 1]
70 g of amorphous silica (solid particles, CARIACT Q-10 manufactured by Fuji Silysia Chemical Ltd., particle diameter: 1.7 to 4.0 mm) is added to 140 g of distilled water (hydrophilic liquid 2), and a 300 ml glass flask and a glass cooling tube are added. Surface treatment was performed by refluxing for 8 hours using a reflux apparatus comprising: Next, the amorphous silica was dried (in air, 110 ° C., 15 hours).
The amorphous silica seek _{S b} and _{S a} for a result of calculating the spread area increase ^{_{ratio, S b = 382mm 2, S}} a = 572mm 2, spread area increase ratio was 50%.

[Test Example 2]
Surface treatment was performed in the same manner as in Test Example 1 except that the amorphous silica was changed to γ-alumina (solid particles, KHS-46 manufactured by Sumitomo Chemical Co., Ltd., particle diameter: 4.0 to 6.7 mm).
This γ- alumina seek _{S b} and _{S a,} result of calculating the spread area increase ^{_{ratio, S b = 14mm 2, S}} a = 49mm 2, spread area increase ratio was 250%.

[Test Example 3]
Surface treatment was performed in the same manner as in Test Example 1 except that the amorphous silica was changed to titania (solid particles, CS-200S-46 manufactured by Sakai Chemical Industry Co., Ltd., particle diameter: 4.0 to 6.7 mm).
This obtains the _{S b} and _{S a} for titania, results of calculating the spread area increase ^{_{ratio, S b = 14mm 2, S}} a = 99mm 2, spread area increase ratio was 607%.

[Test Example 4]
Surface treatment was performed in the same manner as in Test Example 2 except that distilled water was changed to 1N nitric acid (hydrophilic liquid 2).
This γ- alumina seek _{S b} and _{S a,} result of calculating the spread area increase ^{_{ratio, S b = 14mm 2, S}} a = 106mm 2, spread area increase ratio was 657%.

[Test Example 5]
Treatment and drying were performed in the same manner as in Test Example 3 except that distilled water was changed to 1N nitric acid (hydrophilic liquid 2).
This obtains the _{S b} and _{S a} for titania, results of calculating the spread area increase ^{_{ratio, S b = 14mm 2, S}} a = 78mm 2, spread area increase ratio was 457%.

[Test Example 6]
Surface treatment was performed in the same manner as in Test Example 2 except that distilled water was changed to 1N oxalic acid (hydrophilic liquid 2).
This γ- alumina seek _{S b} and _{S a,} result of calculating the spread area increase ^{_{ratio, S b = 14mm 2, S}} a = 120mm 2, spread area increase ratio was 757%.

[Test Example 7]
Treatment and drying were performed in the same manner as in Test Example 3 except that distilled water was changed to 1N oxalic acid (hydrophilic liquid 2).
This obtains the _{S b} and _{S a} for titania, results of calculating the spread area increase ^{_{ratio, S b = 14mm 2, S}} a = 155mm 2, spread area increase ratio was 1007%.

[Example 1]
[Measurement of dissolved oxygen amount (C) using packed tower test equipment]
A 100 ml three-necked flask was connected as a liquid receiver with a 6 mm resin tube under a resin pipe (packed tower) having an inner diameter of 52 mm and a height of 400 mm, to which a metal net for supporting solid particles was attached at the bottom. A dissolved oxygen meter sensor was installed in the three-necked flask.
Next, tap water was continuously supplied from above the resin pipe at a rate of 100 ml / min and nitrogen at 1 L / min from the nozzle of a SUS pipe having an outer diameter of 6 mm.
The tap water was dropped toward the center of the wire mesh for supporting the filling so as not to contact the inner wall of the pipe when falling. Since the upper surface of the resin pipe was sealed except for the tap water and the nitrogen supply nozzle, the tap water and nitrogen passed through the resin pipe in a down flow.
While circulating tap water and nitrogen, about 10 ml of the tap water that passed through the pipe was once trapped in the three-necked flask and continuously replaced with nitrogen from the three-necked flask. It was discharged.
The amount of dissolved oxygen in the trapped water was constantly monitored using a dissolved oxygen meter.
The amount of dissolved oxygen became constant at 4.12 (mg / L). And the distribution of tap water and nitrogen was stopped.
Next, the amorphous silica surface-treated in Test Example 1 was immersed in tap water at 25 ° C. for 1 hour, filtered through a sieve having an aperture of 1.4 mm, and then made of the above resin until the height reached 50 mm. The pipe was filled.
Then, the circulation of tap water and nitrogen was started again, and the amount of dissolved oxygen in the tap water trapped in the three-necked flask was constantly monitored.
As a result, the amount of dissolved oxygen became constant at 3.75 (mg / L).
In addition, after stopping the circulation of tap water and nitrogen, by measuring the amount of tap water that naturally falls from the packed bed and then flows down from the pipe, the dynamic hold-up of the tap water in the packed bed (in the packed tower) The total amount of liquid staying in (specifically, closing the tap water supply side valve and the filling tower outlet valve at the same time, waiting for a while (about 2 to 5 minutes) until the natural fall of tap water ends, The outlet valve was opened, and the amount of the liquid that naturally dropped was measured using a graduated cylinder or an electronic balance))). The result was 4.75 ml.
And it was 2.85 second when the residence time of the tap water in the packed bed was computed from this dynamic holdup.
Subsequently, the surface-treated amorphous silica was immersed in tap water for 1 hour, filtered through a sieve having an aperture of 1.4 mm, and additionally filled to a height of 100 mm within 10 minutes.
And the tap water and nitrogen were distribute | circulated by the same method as the case of 50 mm in height, the dissolved oxygen amount measurement, the dynamic holdup measurement of tap water, and the residence time of tap water were calculated. The dissolved oxygen amount was 2.80 (mg / L), the dynamic holdup was 11.81 ml, and the residence time was 7.09 seconds.
This operation was repeated in the same manner with the filler height of 150 mm and 200 mm.
The dissolved oxygen amount, dynamic hold-up, and residence time when the packing height is 150 mm are 2.08 (mg / L), 20.56 ml, 12.34 seconds, and 1.60 (mg when 200 mm, respectively. / L), 26.19 ml, 15.71 seconds.

[Calculation of mass transfer capacity coefficient between gas and liquid (K _L a)]
The mass transfer capacity coefficient (K _L a) between gas and liquid was measured using AIChE Journal Vol. 21, No. 4, p. 706 (1975).
A specific method is shown below.
K _L a is the amount of dissolved oxygen (C ^∞ ) when all the dissolved oxygen in tap water is replaced with nitrogen, the amount of dissolved oxygen (C ₀ ) in tap water before distribution, and tap water captured after passing through the packed bed The amount of dissolved oxygen in water (C) and the residence time (T) of tap water in the packed bed are expressed by the following formula.
_{^{ln {(C ∞ -C 0)}} / (C ∞ -C)} = K L aT
Was the amount of oxygen dissolved in tap water _{(C 0)} was measured to 7.22 (mg / L). ^C∞ is 0 (g / L). C and T have already been determined in the above [Measurement of dissolved oxygen amount using packed tower test apparatus].
These values are substituted into the above equation, the vertical axis _{^{ln {(C ∞ -C 0)}} / (C ∞ -C)}, the horizontal axis is plotted in the graph of T.
Then, to determine the K _{L a} from the slope of the depicted linear equations by the least squares method. As a result, K _L a was 0.061 (1 / s).

[Calculation of average value of mass transfer capacity coefficient (K _L a) between gas and liquid]
When [Measurement of dissolved oxygen amount (C) using packed tower test apparatus] and [Calculation of mass transfer capacity coefficient between gas and liquid (K _L a)] were repeated three times, the second K _L a was 0.065 (1 / s) The third K _L a was 0.068 (1 / s). _{K L} a mean value of these three became 0.065 (1 / s).

[Comparative Example 1]
[Measurement of dissolved oxygen amount (C) using packed tower test equipment]
Performed in the same manner as in Example 1 except that the amorphous silica subjected to the surface treatment and drying was changed to the amorphous silica before the surface treatment, and the dissolved oxygen amount, dynamic holdup, and residence time at each filling height were measured. And calculated.

[Calculation of mass transfer capacity coefficient between gas and liquid (K _L a)]
K _L a was calculated in the same manner as in Example 1 using the dissolved oxygen amount and residence time values obtained by measuring the dissolved oxygen amount (C). As a result, the first time was 0.056 (1 / s).

[Calculation of average value of mass transfer capacity coefficient (K _L a) between gas and liquid]
When [Measurement of dissolved oxygen amount (C) using packed tower test apparatus] and [Calculation of mass transfer capacity coefficient between gas and liquid (K _L a)] were repeated three times, the second K _L a was 0.060 (1 / s) The third K _L a was 0.057 (1 / s). _{K L} a mean value of these three became 0.058 (1 / s).

In the above test, tap water (liquid phase) in which a saturated amount of oxygen (C ₀ ) is dissolved flows down in contact with the amorphous silica (solid particles) in the packed tower, and in the process of flowing down, nitrogen (gas phase) , Nitrogen (gas phase) moves to tap water (liquid phase) and is replaced with oxygen dissolved in tap water. The average value of the mass transfer capacity coefficient (K _L a) is calculated as a measure of the degree of substitution.
Dissolved oxygen amount when all oxygen dissolved in tap water is replaced with nitrogen (C ^∞ is 0 ml / L, so if it is the dissolved oxygen amount (C) in tap water captured after passing from the packed bed,
_{K L a = ln {(C} ∞ -C 0) / (C ∞ -C)} / T = ln {(- C 0) / (- C)} / T
_{= Ln {C 0 / C}} / T = (lnC 0 -lnC) / T
Accordingly, as nitrogen (gas phase) moves to tap water (liquid phase) and is replaced with dissolved oxygen, the amount of dissolved oxygen C decreases and K _L a increases.
In the above examples and comparative examples, the average value of the mass transfer capacity coefficient K _L a between the gas and liquid is respectively
When the solid particles subjected to the surface treatment of the present invention are used, 0.065 (1 / s) is obtained.
When solid particles not subjected to the surface treatment of the present invention are used, the result is 0.058 (1 / s).
As a result, when the liquid phase (tap water) passes through the solid particles (amorphous silica) which is the packing of the packed tower subjected to the surface treatment of the present invention, the liquid phase drifts between the solid particles subjected to the surface treatment. Is improved, the liquid phase wets and spreads on the surface of the solid particles, and the contact area with the gas phase (nitrogen) is increased. It shows that it was done more efficiently than when it was used.
Further, if the solid particles are a catalyst, when the liquid phase passes through the solid particles (catalyst) which is the packing of the packed tower subjected to the surface treatment of the present invention, the solid particles (catalyst) between the surface treated The liquid phase drift is improved, the liquid phase wets and spreads on the surface of the solid particles (catalyst), for example, the contact area between the gas phase or other liquid phase and the catalyst increases, and the gas phase or other liquid phase, This reaction with the liquid phase is carried out more efficiently than when solid particles (catalyst) not subjected to the surface treatment of the present invention are used.

Claims (6)

After step 1 for surface treatment of solid particles and after step 1,
In a packed tower, a liquid phase transfer and / or reaction method comprising the step 2 of contacting the liquid phase with the surface-treated solid particles,
In the particle size distribution of the solid particles,
The content of particles having a particle size of 0.09 mm or less is 0 to 33% by mass,
The content of particles having a particle diameter exceeding 16 mm is 0 to 33% by mass,
The liquid phase is hydrophilic liquid 1;
The surface treatment includes a step of bringing the surface of the solid particles into contact with the hydrophilic liquid 2 and a step of drying the hydrophilic liquid 2,
A migration and / or reaction method which is a surface treatment in which the percentage increase in the area of expansion calculated by the following standard test is 10 to 10,000%.
[Standard test]
(1) A cylindrical container having an inner wall bottom surface and having a height from the inner wall bottom surface to an end facing the inner wall bottom surface of 60 mm,
In the container having a discharge hole for the hydrophilic liquid 1 on the bottom surface of the inner wall and the end portion being an open end,
(2) The solid particles (solid particles B) before the surface treatment are immersed in the hydrophilic liquid 1 at 25 ± 2 ° C. for 1 hour and then filtered through a sieve having a maximum diameter that does not allow the solid particles to pass through. Before the surface dries
From the opening of the container, filling so that the top surface is substantially horizontal from the bottom of the inner wall to a height of 50 mm,
(3) Before the surface of the solid particles was dried, the hydrophilic liquid 1 was attached to the central portion of the end of the container with a syringe needle having an inner diameter of 0.32 mm from a height of 1 cm from the top surface. With a 5 ml syringe, add 2 ml at 1 ml / min,
(4) After completion of the dropping, when the flow of the hydrophilic liquid 1 in the filled solid particles B from the discharge hole stops, the bottom of the inner wall reaches a height of 20 mm, Removing the filled solid particles B;
(5) The spread of the hydrophilic liquid 1 on the substantially horizontal uppermost surface of the filled solid particles B that appears at a height of 20 mm from the bottom surface after the removal,
(6) Take a photograph from a height of 300 mm from the bottom of the inner wall,
The spreading area S _b (the spreading area S _b on the solid particles B) of the hydrophilic liquid 1 on the uppermost surface of the solid particles B is determined based on the photograph.
(7) In the procedure of obtaining the spread area S _b on the solid particles B (1) ~ (6), the solid particles B, wherein the solid particles B of the surface-treated after solid particles (solid particles A) except that was replaced, in the above procedure (1) the same procedure as ~ (6), determining the spread area S _a of the hydrophilic liquid first top surface of the solid particles a.
(8) The spread area increase rate is calculated by the formula [(S _a −S _b ) / S _b ] × 100 (%).   2. The liquid phase transfer and / or reaction method according to claim 1, wherein the surface treatment is performed by immersing the solid particles in the liquid and bringing the hydrophilic liquid 2 into reflux for contact.   The liquid phase transfer according to claim 1 or 2, wherein the surface treatment removes the hydrophilic liquid 2 by filtration, decantation and / or drying after contacting the solid particles with the hydrophilic liquid 2. And / or reaction method.   The liquid phase transfer and / or reaction method according to claim 1, wherein the reaction is a gas-liquid reaction performed between the liquid phase and a gas phase.   The liquid phase transfer and / or reaction method according to claim 1, wherein the hydrophilic liquid 1 is water or an aqueous solution.   The liquid phase transfer and / or reaction method according to claim 1, wherein the solid particles are a catalyst for the reaction.