JP4606238B2 - Method for producing calcium hydroxide slurry - Google Patents

Description

  The present invention relates to a method for producing a novel calcium hydroxide slurry. Specifically, it is a method for producing a slurry in which fine calcium hydroxide is dispersed by pulverization, and provides a method for producing a calcium hydroxide slurry capable of suppressing changes over time in the viscosity of the resulting slurry. is there.

  Calcium hydroxide slurry is widely used as a wastewater treatment agent, exhaust gas treatment agent, neutralizing agent, additive for cementitious compositions, and the like. High reactivity is required for calcium hydroxide used in these applications. Therefore, in order to use it more efficiently, it is necessary to increase the reactivity by reducing the diameter and making it finer.

  As a method for obtaining a fine calcium hydroxide slurry, a method in which high-concentration calcium hydroxide slurry is digested under pressure using calcium oxide (quick lime) as a raw material and then stirred at high speed (see Patent Document 1), calcium hydroxide slurry In this digestion step, a method of obtaining a fine calcium hydroxide slurry by separating a coarse slurry (see Patent Document 2) has been proposed.

  By these methods, a calcium hydroxide slurry that is fine to some extent can be obtained. However, since this method only separates the coarse portion of the slurry after digestion and does not involve a pulverization step, the average particle size is about 5 μm at most. It was. Therefore, further refinement by pulverization has been required in applications where a fine slurry is more effective, particularly when added as a hardening accelerator for cementitious compositions.

  In general, the slurry viscosity of an inorganic powder rapidly increases with the refinement by pulverization, and the pulverization efficiency decreases. Therefore, in order to increase the grinding efficiency, it is essential to reduce the viscosity of the slurry by adding a polymer dispersant. In the pulverization step of the calcium hydroxide slurry, it is considered necessary to add a polymer dispersant having an effect of dispersing the calcium hydroxide particles in order to increase the pulverization efficiency. At present, a detailed study on the pulverization technology of the added calcium hydroxide slurry has not yet been made.

JP 2001-220185 A JP 2004-345915 A

  The present inventors tried to pulverize a fine calcium hydroxide slurry having an average particle size of 3 μm or less by adding a polymer dispersant with a normal addition amount and addition method, but sufficiently reduced the viscosity. In order to achieve this, not only a large amount of dispersant was required, but the resulting slurry had a large change in viscosity and was unstable.

  Therefore, the object of the present invention is to reduce the amount of the polymeric dispersant used to obtain the fine calcium hydroxide slurry, and to change the viscosity of the pulverized slurry over time. It is providing the manufacturing method of the calcium hydroxide slurry which can be suppressed.

  The present inventors have conducted intensive research to solve the above problems. As a result, in the production of fine calcium hydroxide slurry having an average particle size of 3 μm or less, the amount of the polymer dispersant present in the liquid phase at the time of pulverization is limited to a specific amount, so that the finally required polymer system It was found that a good pulverizing effect could be obtained while reducing the amount of the dispersant, and that the obtained calcium hydroxide slurry showed extremely stable viscosity, and the present invention was completed.

That is, the present invention relates to a method for producing a calcium hydroxide slurry by pulverizing calcium hydroxide and / or calcium oxide in an aqueous medium in the presence of the polymer dispersant. includes a compound having a polyalkylene glycol chain, and, as the amount of said polymeric dispersing agent present in the liquid phase, the following calcium hydroxide 1g per 20 mg, and the total amount of the amount of the polymer dispersant The average particle diameter of calcium hydroxide is 0.55 μm or less while adjusting the addition amount of the polymer-based dispersant so that the amount is 2.4 to 6.0% by mass with respect to calcium hydroxide. It is a manufacturing method of the calcium hydroxide slurry characterized by grind | pulverizing.

According to the present invention, in the pulverization step of a slurry comprising calcium hydroxide having an average particle size of 0.55 μm or less, water and a polymeric dispersant, the polymer dispersion for maintaining the viscosity necessary for pulverization It is possible to significantly reduce the amount of agent used. Moreover, it is also possible to suppress the change with time of the slurry viscosity after pulverization, and it can be used stably in the above applications.

  Hereinafter, the present invention will be described in more detail.

  In the present invention, the raw material of the calcium hydroxide slurry may use calcium hydroxide from the beginning, or may use calcium oxide (quick lime) that reacts with water in an aqueous medium to form calcium hydroxide. . Specifically, examples of calcium hydroxide include industrial slaked lime, agricultural slaked lime, and calcium hydroxide reagents. Further, as calcium oxide, hard calcined lime that can suppress aggregation due to digestion reaction is preferably used because of its low hydration reactivity.

  Moreover, the particle size and particle size distribution of calcium hydroxide and / or calcium oxide used as a raw material are not particularly limited.

  In the present invention, tap water, ion exchange water, distilled water, industrial water and the like can be used without particular limitation as the aqueous medium.

  In the present invention, the polymer dispersant can be used without particular limitation as long as it has an effect of dispersing calcium hydroxide. Specifically, polymer dispersants mainly composed of lignin sulfonate, melamine sulfonate, naphthalene sulfonate, polycarboxylate and the like are preferable examples.

  Among these, a polymer dispersant characterized by containing a compound having a polyalkylene glycol chain as a component can be more suitably used. Specifically, cement dispersants called polycarboxylic acid type, polyether type and the like can be mentioned. These exhibit a high dispersion effect due to the action of the polyethylene glycol chain in the compound. Such a polymeric dispersant can be used in a solid form or a solution form.

  In the present invention, the amount of calcium hydroxide and / or calcium oxide with respect to the aqueous medium is desirably such that the solid content concentration of the obtained calcium hydroxide slurry is 20 to 60% by mass. That is, when the solid content concentration is less than 20% by mass, the tendency of the slurry to separate is not preferable. Moreover, when it exceeds 60 mass%, since slurry viscosity will increase and a grinding | pulverization efficiency will fall, it is unpreferable.

  The greatest feature of the present invention is that in the method for producing the calcium hydroxide slurry, the amount of the polymer dispersant present in the liquid phase is 20 mg or less per gram of calcium hydroxide. The purpose is to pulverize while adjusting the addition amount.

  That is, when the amount of the polymeric dispersant in the liquid phase exceeds 20 mg per gram of calcium hydroxide, it is preferable because the required amount of dispersant used increases and the change in slurry viscosity with time after pulverization increases. Absent.

  Such a phenomenon is presumed to be caused by part of the dispersant adsorbed on the particles during pulverization being temporarily taken into the particles during the pulverization process or taken into the aggregated particles. That is, the dispersant adsorbed or taken in in such a state does not exhibit the dispersion effect at the end of pulverization, but gradually exhibits the dispersion effect as time elapses. It is thought that a change will occur. When the amount of the dispersant present in the liquid phase of the slurry is large in the pulverization step, the amount of the dispersant that is adsorbed or incorporated in the unfavorable state as described above increases.

Therefore, in the present invention, it is necessary to adjust the amount of the polymeric dispersant in the liquid phase to 20 mg or less per 1 g of calcium hydroxide. In particular, it is estimated that the dispersant adsorbed at the initial stage of pulverization is likely to be temporarily incorporated into the particles or aggregated particles in the subsequent pulverization process. It is important to control the amount of the polymeric dispersant in the liquid phase so as to suppress the adsorption amount to a small amount.
The amount of the polymeric dispersant in the liquid phase of the calcium hydroxide slurry is desirably adjusted to 0.5 mg or more per 1 g of calcium hydroxide. When the amount is less than 0.5 mg, the grinding efficiency is lowered due to an increase in slurry viscosity, and the required grinding time becomes long, which is not preferable.
In the present invention, the amount of the polymeric dispersant in the liquid phase of the calcium hydroxide slurry indicates a value measured by a total organic carbon analyzer after separating the liquid phase of the calcium hydroxide slurry by filtration. A detailed measurement method will be described in Examples described later.
The management method of the amount of the polymeric dispersant present in the liquid phase is not particularly limited. Although it seems suitable to measure and manage the amount of the polymeric dispersant by the above method, it can be managed by any index having a correlation with the amount measured by the above method. In that case, it is necessary to confirm the correlation with the measured value of the above method in advance. Specific examples include management using a COD meter, an infrared spectrophotometer, an ultraviolet spectrophotometer, and the like.

By the above operation, the total amount of the polymeric dispersant used can be greatly reduced. In general, the amount used can be suppressed to 10.0 mass% or less, usually 2.4 to 6.0 mass% with respect to calcium hydroxide.

  In addition, the usage-amount of a polymeric dispersing agent is the value converted into the solid content of a dispersing agent.

  In the present invention, it is preferable to adjust the concentration of the calcium hydroxide slurry so that the viscosity of the calcium hydroxide slurry at the end of pulverization is 10000 cps or less, particularly 5000 cps or less.

That is, if it exceeds 10,000 cps, it is not preferable because it causes a decrease in pumpability during storage or use.
In the present invention, the pulverizer used for pulverizing the slurry is not particularly limited. A known pulverizer capable of wet pulverization, such as a ball mill, a planetary mill, a stirring tank mill, and a slurry circulation mill, can be preferably used. Two or more of these pulverizers can be used in appropriate combination. Among these, a stirring tank mill and a slurry circulation mill that can easily add the polymer dispersant in the pulverization step can be suitably used.
Regardless of which type of pulverizer is used, it is important to adjust the amount of dispersant added so that the amount of dispersant present in the liquid phase of the slurry is 20 mg or less per gram of calcium hydroxide.
As a specific example, in a ball mill which is a batch type pulverizer, the pulverizer is stopped at an arbitrary time, the amount of the polymer dispersant in the liquid phase is confirmed, and within 20 mg or less per 1 g of calcium hydroxide. Dispersant is added and the process is continued until the target average particle size is reached. In the continuous slurry circulation mill, the amount of the dispersant in the liquid phase is confirmed at an arbitrary time, and the dispersant may be added in a range where the amount of the dispersant in the liquid phase is 20 mg or less per gram of calcium hydroxide. Then, a method of adjusting the addition amount so that the amount of the dispersing agent in the liquid phase is 20 mg or less per 1 g of calcium hydroxide with a constant supply device and continuously adding a certain amount may be adopted.

  In the present invention, the order in which calcium hydroxide and / or calcium oxide, water, and the polymer dispersant are added to the pulverizer is not particularly limited.

  Specifically, a method in which all the materials are simultaneously charged and pulverized, a method in which calcium hydroxide, water and a part of the dispersant are added in advance, and the remainder of the dispersant is added in the process of pulverization, calcium hydroxide and water A method in which a dispersant is added in the course of pulverization, a method in which calcium hydroxide is dry pulverized, a method in which water and a dispersant are added and wet pulverized, and a calcium hydroxide slurry obtained by a quick lime digestion reaction is dispersed. And a method of adding an agent and pulverizing, a method of adding water and a part of the dispersant in advance, simultaneously starting digestion reaction and pulverization of quicklime, and adding the remainder of the dispersant in the pulverization step.

  The slurry of the present invention may contain substances other than calcium hydroxide, water, and polymer dispersant constituting the slurry as long as the effects of the present invention are not significantly impaired. Specifically, grinding aids, antifoaming agents, air amount adjusting agents, separation reducing agents, setting accelerators, setting retarders, thickeners, rust preventives, shrinkage reducing agents, gypsum, blast furnace slag, fly ash, Examples thereof include silica fume, limestone fine powder, and fine mineral powder.

  Hereinafter, although an example explains composition and an effect of the present invention, the present invention is not limited to these examples.

(1) Method for measuring the amount of the polymeric dispersant remaining in the liquid phase of the slurry The liquid phase of the calcium hydroxide slurry is extracted by centrifugation (7000 rpm), and the total organic carbon analyzer (TOC-650, manufactured by Toray Engineering) ) Was used to measure the residual amount of the polymeric dispersant, and the residual amount per gram of calcium hydroxide in the slurry was calculated.

(2) Evaluation method of average particle diameter Using ethanol as a dispersion medium, the particle size distribution of calcium hydroxide is measured using a laser diffraction particle size analyzer, and the volume average diameter is calculated from the measurement results. The diameter. The measurement was performed at the end of grinding.

(3) Evaluation method of slurry viscosity The viscosity of the slurry was measured with a B-type rotational viscometer.

Example 1
The calcium hydroxide slurry was pulverized by a planetary mill. Industrial slaked lime (JIS special name, average particle size: 19.0 μm) as calcium hydroxide, polycarboxylic acid-based high-performance AE water reducing agent (solution, solid content concentration: 30%) as a polymeric dispersant, Water used was ion exchange water. The solid content concentration of slaked lime was 34% by mass. As shown in Table 1, the polymer dispersant was added as needed at the start of pulverization and after a lapse of a certain time. In addition, the addition amount of the dispersing agent was represented by the mass% of the dispersing agent solid content with respect to the slaked lime solid content. The residual amount of the dispersant was measured by extracting the liquid phase from the slurry when pulverized for 2 minutes after the addition of the dispersant. After pulverization, the viscosity of the slurry was measured until 30 days had elapsed. The results are shown in Tables 1 and 2.

Example 2
The calcium hydroxide slurry was ground and measured in the same manner as in Example 1 except that the solid content concentration of slaked lime was 41% by mass and the dispersant was added at the time shown in Table 1. The results are shown in Tables 1 and 2.

Comparative Example 1
The calcium hydroxide slurry was pulverized and measured in the same manner as in Example 2 except that the polymer dispersant was added at the time of pulverization at the start, 45 minutes, 180 minutes, and 240 minutes. The results are shown in Tables 1 and 2.

Comparative Example 2
The calcium hydroxide slurry was pulverized and measured in the same manner as in Example 2 except that the polymer dispersant was added at the time of pulverization at the start, 45 minutes, 180 minutes, and 240 minutes. The results are shown in Tables 1 and 2.

Example 3
The calcium hydroxide slurry was pulverized using quick lime as a raw material by a slurry circulation type pulverizer. Soft calcined quick lime for industrial use (maximum particle size: 150 μm) as quick lime, polycarboxylic acid-based high-performance AE water reducing agent (solution, solid content concentration: 31%) as polymer dispersant, and ion-exchanged water as water used. The compounding quantity of quicklime was determined so that the solid content density | concentration of slaked lime might be 40 mass%. Grinding started simultaneously with the start of the quicklime digestion reaction. The polymer dispersant was added as needed at the start of pulverization and after a lapse of a certain time.

  In addition, the addition amount of the dispersing agent was represented by the mass% of the dispersing agent solid content with respect to the slaked lime solid content. The residual amount of the dispersant was measured by extracting the liquid phase from the slurry at the time of pulverization for 2 minutes after the addition of the dispersant. After pulverization, the viscosity of the slurry was measured until 30 days had elapsed. The results are shown in Tables 3 and 4.

Example 4
The calcium hydroxide slurry was pulverized and measured in the same manner as in Example 3 except that industrial hardened quicklime (maximum particle size: 75 μm) was used as quicklime. The results are shown in Table 3 and Table 4.

Comparative Example 3
The calcium hydroxide slurry was ground and measured in the same manner as in Example 3 except that the polymer dispersant was added at the start, 60 minutes and 120 minutes. The results are shown in Table 3 and Table 4.

Claims (3)

In a method for producing a calcium hydroxide slurry by pulverizing calcium hydroxide and / or calcium oxide in an aqueous medium in the presence of a polymer dispersant , the polymer dispersant has a polyalkylene glycol chain. They comprise a compound, and the amount of said polymeric dispersing agent present in the liquid phase, so as to be less of calcium hydroxide per 1g 20 mg, and, with respect to the total amount of calcium hydroxide used amount of the polymer dispersant Pulverizing so that the average particle size of calcium hydroxide is 0.55 μm or less while adjusting the amount of the polymeric dispersant to be 2.4 to 6.0% by mass. A method for producing a calcium hydroxide slurry. The process according to claim 1 Symbol placement of calcium hydroxide slurry using quick lime as raw materials. The method for producing a calcium hydroxide slurry according to claim 2 , wherein the quicklime is hard-burned quicklime .