JPH0873307A - Production of bordeaux mixture and device therefor - Google Patents

Abstract

PURPOSE: To provide technology having fine, uniform and stable particle diameters, capable of producing preservable Bordeaux mixture on an industrial scale. CONSTITUTION: In this method for producing Bordeaux mixture by blending and reacting 3 milk of lime 1 with a solution of copper sulfate 2 to give a stock solution of Bordeaux mixture and grinding 5 the Bordeaux mixture in a wet state, the addition rate of the solution of copper sulfate to the milk of lime is controlled to 0.001-0.03mol/minute copper (Cu) in the solution of copper sulfate based on 1mol (Ca) in the milk of lime or water at 15-35 deg.C is used as the water for preparing the milk of lime or the solution of copper sulfate or the milk of lime is mixed wit the solution of copper sulfate and stirring is successively continued for >=30 minutes after the completion of the mixing or the temperature of the Bordeaux mixture at the outlet of a grinding machine for pulverizing in a wet state is regulated at 15-40 deg.C or the slurry of the Bordeaux mixture from the outlet of the grinding machine is stirred for >=5 minutes.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for producing a Bordeaux liquid having a fine particle diameter, a uniform particle diameter, a stable particle diameter, and a stable reservoir.

[0002]

2. Description of the Related Art Bordeaux solution has been used for a long time as a pesticide for preventing insects and fungi of various agricultural products such as apples, pears and grapes. The production (adjustment) of the Bordeaux liquid is performed by separately making copper sulfate and quick lime (or slaked lime) into an aqueous solution or dispersion, and then gradually injecting the aqueous copper sulfate solution while stirring lime milk at room temperature. . However, the Bordeaux liquid thus obtained must be used as soon as possible. The reason is that when lime milk and an aqueous solution of copper sulfate are mixed, a bordeaux reaction occurs, but with the passage of time, the reaction gradually progresses, the crystal particles gradually grow and the particle size increases, and they are dispersed. This is because the spreadability to agricultural products at that time becomes poor, the nozzle of the sprayer is clogged at the time of spraying, and the concentration changes due to precipitation in the container, making it impossible to spray uniformly and effectively. or,
Create a Bordeaux solution (Bordeaux slurry) with a high concentration,
If water is added later to dilute it, the effect as a pesticide becomes smaller, and it was not considered to make and store Bordeaux liquid or Bordeaux slurry.

As a method of solving this, Japanese Patent Laid-Open No. 2-27
There is a technical idea of 9611. This technical idea is to wet-mill the prepared undiluted Bordeaux liquid. It is said that this wet pulverization gives a Bordeaux solution that is uniform and stable, and does not impair the effect even when diluted with water.

[0004]

However, the above-mentioned publication only discloses the technique in the laboratory stage of about 500 g per batch, and the findings in the case of manufacturing this on an industrial scale are completely described. There is no. For this reason, when it was attempted to carry out on an industrial scale, various problems occurred and it was impossible to carry out on an industrial scale.

Therefore, the present invention is to provide a technique capable of producing a Bordeaux liquid having a fine particle size, uniform and stable, and capable of being made and stored on an industrial scale.

[0006]

The above-mentioned object of the present invention is a method for producing a Bordeaux liquid by wet pulverizing a stock solution of Bordeaux liquid obtained by mixing and reacting lime milk and a copper sulfate solution. The addition rate of the copper sulfate solution is controlled so that the copper (Cu) of the copper sulfate solution is 0.001 to 0.03 mol / min relative to 1 mol of calcium (Ca) in the lime milk. This is achieved by the manufacturing method.

The preferred range of addition rate is 0.005 to 0.03 mol / min, more preferably 0.01 to 0.03 mol / min of copper (Cu) in a copper sulfate solution per 1 mol of calcium (Ca) in lime milk. It is 0.03 mol / min. Further, in a method for producing a Bordeaux liquid in which a stock solution of a Bordeaux liquid obtained by mixing and reacting lime milk and a copper sulfate solution is wet-milled, water used for preparing the lime milk and the copper sulfate solution has a temperature of This is achieved by a method for producing a Bordeaux liquid, which comprises using water at 15 ° C to 35 ° C.

The preferable water temperature range is 20 to 35.
C., more preferably 25 to 33.degree. Further, a method of producing a Bordeaux liquid in which a stock solution of a Bordeaux liquid obtained by mixing and reacting lime milk and a copper sulfate solution is wet-milled, and after mixing the lime milk and the copper sulfate solution, the mixing is continued. It is achieved by a method for producing a Bordeaux solution, which comprises stirring for 30 minutes or more.

The preferable stirring time range is 40 to 8
It is 0 minutes, more preferably 40 to 60 minutes. Further, a method for producing a Bordeaux liquid by wet pulverizing a stock solution of a Bordeaux liquid obtained by mixing and reacting lime milk and a copper sulfate solution,
The wet slurry temperature at the grinder outlet is 15
It is achieved by a method for producing a Bordeaux liquid, which is characterized in that the temperature is controlled to be 40 ° C to 40 ° C.

The preferred range of the temperature of the bould slurry at the exit of the pulverizer is 15 ° C to 39 ° C, more preferably 15 ° C.
~ 37 ° C. A method for producing a Bordeaux liquid in which a stock solution of a Bordeaux liquid obtained by mixing and reacting lime milk and a copper sulfate solution is wet-milled, and stirring the Bord slurry from the outlet of the wet-milled grinder for 5 minutes or more. This is achieved by the characteristic method for producing Bordeaux liquid.

The stirring time of the bord slurry from the outlet of the crusher is preferably 5 to 20 minutes, more preferably 10 to 10.
15 minutes. Further, the above inventions can be arbitrarily combined. For example, the invention according to claim 1 and claim 2
The invention of claim 5 is combined with the invention of claim 2, the invention of claim 3 is combined with any of the inventions of claims 3 to 5, the invention of claim 3 is combined with the invention of claim 3. The invention of claim 4 is combined with the invention of claim 5, or the invention of claim 1 is combined with the invention of claim 1. The invention and any one of the inventions described in claims 3 to 5 can be combined as appropriate, and can be appropriately combined. It is most preferable that the invention of claim 1, the invention of claim 2, the invention of claim 3, the invention of claim 4 and the invention of claim 5 are combined. Will be things.

Further, there is provided a Bordeaux liquid production apparatus for wet crushing a stock solution of Bordeaux liquid obtained by mixing and reacting lime milk and a copper sulfate solution, in which lime milk and a copper sulfate solution are mixed,
A reaction tank for reaction, an intermediate tank provided with a stirring means provided in a post process of the reaction tank, a wet pulverizing means provided in a post process of the intermediate tank, and a post process of the wet pulverization means And a tank provided with a stirring means.

It is preferable that the wet crushing means is provided with a temperature control means. In the present invention, the addition rate of the copper sulfate solution to lime milk is 0.001 to 0.03 mol / min of copper (Cu) in the copper sulfate solution to 1 mol of calcium (Ca) in lime milk. For the following reasons. A higher injection rate of the copper sulfate solution is preferable because it shortens the production time. However, it has been found that when the injection speed is high, the reaction rapidly occurs, the slurry viscosity increases, stirring becomes impossible, and the manufacturing process is stopped. Then, when the relationship between the injection rate of the copper sulfate solution and the slurry viscosity was investigated, the results shown in FIGS. 1 and 2 were obtained. FIG. 1 is a graph showing changes in the viscosity of the slurry as the copper sulfate solution injection proceeds (horizontal axis: copper sulfate solution injection amount (%),
Vertical axis: slurry viscosity (cp)). According to this
Even when different kinds of Bordeaux solutions are produced, it is found that the viscosity similarly increases as the copper sulfate aqueous solution is injected. FIG. 2 is a graph showing the relationship between the slurry viscosity and the injection speed after 15 minutes from the end of injection when the viscosity becomes highest (horizontal axis: copper sulfate solution injection speed (Cu · mol / min / Ca · mol),
Vertical axis: slurry viscosity (cp)). It can be seen that the viscosity increases sharply as the injection rate increases. by the way,
It has been found that in a Bordeaux liquid production apparatus, the viscosity at which the stirring of the transport pipe for transporting the liquid makes it impossible to stir is about 20,000 cp. Therefore, it was found that the upper limit of the injection rate should be 0.03 mol / min or less per 1 mol of calcium in lime milk. On the other hand, if the injection speed is too slow, it takes too much time for production, which is not suitable for mass production (industrial production). That is, considering economic efficiency, it is preferably 0.001 mol / min or more.

In the present invention, water having a water temperature of 15 ° C. to 35 ° C. is used for producing the lime milk and the copper sulfate solution for the following reason. The higher the temperature in the reaction tank in which lime milk and the copper sulfate solution are mixed and reacted,
The reaction proceeds quickly and the efficiency is good. However, if the temperature in the reaction tank is too high, the reaction proceeds too fast, the viscosity of the slurry increases, stirring becomes impossible, and copper sulfide is produced, and the product does not become a product. Then, when the temperature in the reaction tank was changed and investigated, the upper limit of the temperature in the reaction tank was 45 ° C, preferably 42 ° C or less. Then, as a method for controlling this temperature (45 ° C., preferably 42 ° C. or lower), various factors were examined, and as a result, temperature control was found to be the highest in heat capacity of lime milk and copper sulfate among the raw materials entering the reaction tank. It has been found that this can be achieved by controlling the water temperature when producing an aqueous solution. Examining the relationship between the temperature of this water and the final temperature of the reaction tank, the graph in Fig. 3 (horizontal axis:
Water temperature (° C), vertical axis: final slurry temperature (° C). From this result, when the temperature of slaked lime is 20 ° C, the temperature of water is 35 ° C or lower, preferably 32 ° C or lower, more preferably 29 ° C or lower in the case of 4-12 bordeaux, and in the case of 4-8 bordeaux. , The temperature of water is 35 ° C or lower, preferably 31 ° C or lower, more preferably 28 ° C or lower, and in the case of 6-6 Bordeaux, the temperature of water is 35 ° C or lower, preferably 28 ° C or lower, more preferably 25 ° C. It turned out to be: Fine adjustment is required depending on the temperature of slaked lime. And, considering many factors in total, in case of 4-12 Bordeaux, the water temperature is 19 ° C to 35 ° C.
℃, 4-8 Bordeaux, water temperature is 17 ℃ ~ 34
℃, 6-6 Bordeaux, water temperature is 15 ℃ ~ 31 ℃
Was the best.

In the present invention, the reason why the lime milk and the copper sulfate solution are mixed and then stirred for 30 minutes or more even after the mixing is completed is as follows. Even after the lime milk and the copper sulfate aqueous solution are mixed in the reaction tank, the bordeaux reaction proceeds continuously. If the reaction is applied to the pulverizer halfway, a rapid reaction occurs in the pulverizer, the viscosity of the slurry increases, and the operation becomes impossible. Therefore, when the relationship between the reaction time and the slurry viscosity was investigated, the graph of FIG. 4 (horizontal axis: stirring time (minutes), vertical axis: slurry viscosity (c
p)). Since the time when the slurry viscosity becomes stable is the end of the reaction for the time being, it is 60 minutes or more in the case of 4-12 Bordeaux, 55 minutes or more in the case of 4-8 Bordeaux, and 40 minutes in the case of 6-6 Bordeaux. It can be seen that the above stirring is preferable. By doing so, it was possible to prevent a rapid increase in viscosity in the crusher and solve the problem of falling into an inoperable state.

In the present invention, the temperature of the bould slurry at the outlet of the pulverizer for wet pulverization is controlled to be 15 to 40 ° C. for the following reason. Although pulverization by a pulverizer is wet pulverization, heat is also generated at this time and the temperature rises.
By the way, when the temperature rises, the viscosity of the slurry increases and the formation of copper sulfide begins, so it is better to lower the temperature. Therefore, it is preferable to provide a cooling device to lower the temperature. However, it is advantageous in terms of cost to raise the temperature. Therefore, it is preferable to have a temperature control means. As described above, the formation of copper sulfide can be suppressed by keeping the temperature below 45 ° C. However, crushing at this temperature increases the viscosity of the slurry, making the crusher inoperable. Therefore, the relationship between the crusher outlet temperature and the slurry viscosity was investigated. The results are shown in the graph of FIG. 5 (horizontal axis: mill outlet slurry temperature (° C.), vertical axis: slurry viscosity (c
p)). There is no problem with the viscosity of the crusher, which is 2
Since it is 5,000 cp to 30,000 cp or less, it is understood that the temperature of the crusher outlet should be controlled to 40 ° C. or lower, preferably 39 ° C. or lower, more preferably 37 ° C. or lower by using a temperature controller. The lower limit temperature was set to 15 ° C., which is the limit temperature at which unreacted copper sulfate becomes saturated and crystals do not precipitate.

In the present invention, the reason why the wet slurry pulverized from the pulverizer outlet is stirred for 5 minutes or more is as follows. It has been found that the slurry discharged from the pulverizer has an increased viscosity due to the progress of the reaction even if the temperature is controlled, and is not suitable for transportation or other purposes as it is. However, it has been found that the viscosity can be reduced by stirring the slurry in advance. When the relationship between the re-stirring time after crushing and the viscosity was examined, the graph in FIG. 6 (horizontal axis:
The results shown in the re-stirring time (min) and the vertical axis: slurry viscosity (cp) were obtained. It was found that the viscosity suitable for economical transportation and storage was 20,000 cp or less, so that the viscosity was decreased by stirring for 5 minutes or more, and the viscosity was not increased thereafter. Therefore, it is important to stir the Bord slurry for 5 minutes or more.

In the present invention, when the Bordeaux solution is produced,
Lime milk and copper sulphate solution are used. In addition to these, various additives are used as necessary. For example, a surfactant is used. Examples of such surfactants include "Surfactant Handbook" (edited by Nishi Ichiro, Industrial Books) and "Elucidation of the functional action of new surfactants and development of applied products and practical technical reference materials" (Management Development Center publication department) etc. can be used. Further, a dispersion stabilizer such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose or starch can be used. Also, alkali agents such as sodium silicate and sodium phosphate, chelating agents,
Preservatives, spreading agents and the like can be used. Quick lime or slaked lime can be used as the lime milk source.

As the wet pulverizing means in the present invention, for example, a ball mill, a tube mill, a tower mill, a pearl mill, a universal mill, a homogenizer, an ultrasonic emulsifier, etc. are used.

[0020]

EXAMPLE FIG. 7 is a schematic view showing an example of an apparatus for producing Bordeaux liquid according to the present invention. In the figure, 1 is a lime milk tank with stirring blades, 2 is a copper sulfate tank having a temperature control device, 3 is a reaction tank with stirring blades, 4 is an intermediate tank with stirring blades, and 5 is a temperature control device. Wet grinder, 6 is an intermediate tank with stirring blades, 7 is a storage tank with stirring blades, 8 is a pump, 9 is a slaked lime tank, 10 is a water tank having a temperature control device, 11 is various additive tanks, 12
Is a transportation pipe that connects various tanks.

In the apparatus constructed as described above, after confirming that the water temperature in the water tank 10 is 20 ° C., this is introduced into the lime milk tank 1. Also, lime milk tank 1
Then, a predetermined amount of slaked lime is transported from the slaked lime tank 9. or,
A predetermined amount of various additives are transported from the additive tank 11.
Then, in the lime milk tank 1, it is sufficiently stirred to produce lime milk having a predetermined concentration. Then, a predetermined amount of lime milk is transported to the reaction tank 3.

Further, a predetermined amount of aqueous copper sulfate solution is transported from the copper sulfate tank 2 kept at 20 ° C. to the reaction tank 3. The rate of supplying this copper sulfate aqueous solution into the reaction tank 3 is as follows. That is, the addition rate of the copper sulfate solution to lime milk is controlled so that the copper in the copper sulfate solution is 0.01 to 0.03 mol / min to 1 mol of calcium in lime milk. After the lime milk and the copper sulfate solution are mixed in the reaction tank 3, the mixed solution is transported to the intermediate tank 4. Then, the intermediate tank 4 is continuously stirred for 30 minutes or more.

After sufficiently stirring, the mixed liquid is transported to the wet pulverizer 5. Then, the wet crusher 5
The 0% passage diameter is 10 μm or less, preferably 6 μm or less. The temperature of the slurries at the outlet of the wet crusher 5 is controlled to be 35 ° C. Then, the balde slurry (temperature 35
(° C.) is transported to the intermediate tank 6 and stirred there for 5 minutes or more.

After sufficient stirring, the Bord slurry is transported to the storage tank 7 for storage. And prepare for shipping. When the Bord slurry (Bordeaux liquid) is manufactured as described above, the Bord slurry can be obtained with high productivity without clogging in the transportation pipe. That is,
The manufacturing cost of the boron slurry is low.

In particular, it becomes possible to mass-produce the Bord slurry that could not be made and stored on an industrial scale, and the required amount of Bordeaux liquid having stable performance can be supplied. Furthermore, a bald slurry can be obtained in which the nozzle is not clogged during spraying and the effect as a pesticide does not decrease even when diluted with water.

[0026]

[Effect] At the time of production, the bould slurry can be obtained with high productivity without being clogged in the transportation pipe. That is,
The manufacturing cost of the boron slurry is low. In particular, it becomes possible to mass-produce the Bord slurry that could not be made and stored on an industrial scale, and to supply the required amount of Bordeaux liquid with stable performance.

Further, it is possible to obtain a bold slurry in which the nozzle is not clogged during spraying and the effect as a pesticide is not deteriorated even when diluted with water.

[Brief description of drawings]

FIG. 1 is a graph showing the viscosity when lime milk and a copper sulfate aqueous solution are mixed.

FIG. 2 is a graph showing the viscosity when lime milk and a copper sulfate aqueous solution are mixed.

FIG. 3 is a graph showing the relationship between water temperature and Bordeaux slurry temperature.

FIG. 4 is a graph showing the relationship between stirring time and Bordeaux slurry viscosity.

FIG. 5 is a graph showing the relationship between crushing temperature and Bordeaux slurry viscosity.

FIG. 6 is a graph showing the relationship between re-stirring time and Bordeaux slurry viscosity.

FIG. 7 is a schematic view of an apparatus for producing Bordeaux liquid.

[Explanation of symbols]

 1 Lime milk tank 2 Copper sulfate tank 3 Reaction tank 4 Intermediate tank 5 Wet grinder 6 Intermediate tank 7 Storage tank 12 Transport pipe

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yu Sakashita 3-14-1, Kuzushima, Kochi City, Kochi Prefecture

Claims (6)

[Claims] 1. A method for producing a Bordeaux solution in which a stock solution of Bordeaux solution obtained by mixing and reacting lime milk and a copper sulfate solution is wet-milled, wherein the addition rate of the copper sulfate solution to the lime milk is The method for producing a Bordeaux liquid, wherein the copper (Cu) of the copper sulfate solution is controlled to be 0.001 to 0.03 mol / min with respect to 1 mol of calcium (Ca). 2. A method for producing a Bordeaux liquid by wet pulverizing an undiluted solution of Bordeaux liquid obtained by mixing and reacting lime milk and a copper sulfate solution, wherein the water used for producing the lime milk and the copper sulfate solution is: A method for producing a Bordeaux liquid, characterized in that water having a temperature of 15 ° C to 35 ° C is used. 3. A method for producing a Bordeaux liquid by wet crushing an undiluted solution of Bordeaux liquid obtained by mixing and reacting lime milk and a copper sulfate solution, which comprises mixing the lime milk and the copper sulfate solution and then ending the mixing. A method for producing a Bordeaux liquid, which is characterized by continuously stirring for 30 minutes or more. 4. A method for producing a Bordeaux liquid by wet pulverizing a stock solution of Bordeaux liquid obtained by mixing and reacting lime milk with a copper sulfate solution, wherein the temperature of the Bord slurry at the outlet of the pulverizer for wet pulverization is 15 ° C. or higher. A method for producing a Bordeaux liquid, which comprises controlling the temperature to be 40 ° C. 5. A method for producing a Bordeaux liquid by wet pulverizing an undiluted Bordeaux liquid obtained by mixing and reacting lime milk and a copper sulfate solution, wherein the Bord slurry from the outlet of the wet pulverizer is stirred for 5 minutes or more. A method for producing a Bordeaux liquid, comprising: 6. A device for producing a Bordeaux liquid, which wet pulverizes an undiluted solution of Bordeaux liquid obtained by mixing and reacting lime milk and a copper sulfate solution, and a reaction tank for mixing and reacting the lime milk and the copper sulfate solution. An intermediate tank provided with a stirring means provided in a subsequent step of this reaction tank, a wet crushing means provided in a subsequent step of the intermediate tank, and a stirring means provided in a subsequent step of the wet crushing means An apparatus for producing a Bordeaux liquid, comprising: