JP3409285B2 - Manufacturing method of flue gas treatment agent - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flue gas treating agent, and more particularly to a method for producing a flue gas treating agent for removing acid gas in flue gas accompanying the incineration of general waste.

[0002]

2. Description of the Related Art Conventionally, as a relatively inexpensive flue gas treatment method, by spraying slaked lime into a flue through which flue gas passes,
In general, a method is used in which harmful acid gas in flue gas is adsorbed by slaked lime, the slaked lime adsorbed by the acid gas is collected by a dust collector, and the collected product is then treated as a managed waste such as landfill. Has been done.

The inventors of the present invention have been
A flue gas treatment agent for efficiently removing NO _x and SO _x contained in flue gas emitted by burning fossil fuels such as coal in a power plant is disclosed in, for example, Document 1 (Japanese Patent Laid-Open No. H11 (1999) -111945).
-76808). The flue gas treatment agent of Document 1 contains calcium oxide, silicon dioxide, aluminum oxide and gypsum as raw materials. Then, in the method for producing the flue gas treatment agent, a substance containing amorphous silicon dioxide in quicklime is added as 0.05 to 6 as silicon dioxide per 100 parts by weight of calcium oxide in quicklime.
Add 0 parts by weight, add water to carry out digestion reaction, and then mix and knead substances containing aluminum oxide, gypsum and, if necessary, silicon dioxide so as to obtain a predetermined flue gas treatment composition. Is characterized by. With the flue gas treatment agent produced in this way, high desulfurization (de-S
O _x) and denitrification (de NO _x) effect.

[0004]

Here, attention is paid to the toxic gas in the flue gas discharged from the refuse incinerator such as general refuse. During smoke emission from general waste incinerator,
It contains a large amount of HCl and SO _x as toxic gases. Conventionally used slaked lime is not so high in the adsorption performance of acid gas, especially SO ₂ gas. Therefore, in order to adsorb a large amount of acid gas, the amount of slaked lime sprayed becomes enormous. As a result, the amount of waste treated increases, and the cost for this treatment increases.

Further, the flue gas treating agent of Document 1 is manufactured for the purpose of removing SO _x and NO _x emitted along with the combustion of fossil fuel. Even if this flue gas treatment agent shows a high desalination (dechlorination) effect when it is used for flue gas treatment of a general waste incinerator, even if the waste treatment amount can be reduced, this flue gas treatment Due to the high manufacturing cost of the treatment agent, the cost of the entire flue gas treatment becomes expensive.

[0006] Therefore, the advent of a method for producing a flue gas treatment agent, which enables a flue gas treatment agent having a high desalting and desulfurizing effect to be produced more inexpensively and easily than ever before, has been desired. As such a flue gas treatment agent, the emergence of a flue gas treatment agent having a particularly high calcium content and capable of efficiently adsorbing SO ₂ has been desired.

[0007]

Therefore, according to the method for producing an flue gas treatment agent comprising slaked lime containing amorphous calcium silicate according to the present invention, quick lime 50-9 is used.
10 parts by weight of a mixture containing 9.9 parts by weight and 0.01 to 50 parts by weight of silicon dioxide, a stoichiometric amount of water for converting quicklime into slaked lime, and a solvent for dispersing the mixture 10. .About.200 parts by weight.

The above mixture contains 50 to 99.9 parts by weight of quicklime and 0.01 to 50 parts by weight of silicon dioxide based on 100 parts by weight of the mixture. Then, with respect to 100 parts by weight of this mixture, a stoichiometric amount of water for changing quicklime into slaked lime and a solvent 10 for dispersing this mixture 10
~ 200 parts by weight.

The mixture may be obtained by mixing quick lime and a silicon dioxide-containing material containing silicon dioxide, or may be a premixed mixture. In addition, the solvent as used herein refers to a liquid in which the mixture is dispersed, and is distinguished from the stoichiometric amount of water used in the digestion reaction for converting quicklime into slaked lime. Then, as the solvent, a mixed solution of water and an organic solvent, an additive aqueous solution in which an additive is dissolved, a solution in which an additive is dissolved in the mixed solution, or only water is used.

As a result, quick lime can be digested without fear of indigestion. Further, the heat of digestion generated during the digestion of quicklime can be used to react quicklime with silicon dioxide to produce amorphous calcium silicate, and the calcium silicate can be contained in the obtained slaked lime. As a result, a flue gas treatment agent having a high desalination and desulfurization effect can be obtained.
Further, the above-mentioned digestion reaction and reaction for producing calcium silicate can be carried out only by adding water necessary for digestion and a solvent for dispersion to a mixture of quicklime and a silicon dioxide-containing substance. Therefore, it is not necessary to heat the reaction system from the outside to cure the reaction system. Therefore, the cost and time required for manufacturing can be reduced more than ever before.

Further, in the method for producing a flue gas treatment agent of the present invention, preferably, the silicon dioxide-containing material is mixed such that silicon dioxide is contained in an amount of 1 to 20 parts by weight.

Since the flue gas treating agent produced by the method of the present invention uses a mixture of quicklime and silicon dioxide-containing material as a starting material, the calcium content of the treating agent is obtained by digesting quicklime only. Slightly lower than slaked lime. Therefore, in order to secure the content rate of calcium that reacts with the acidic gas, it is considered necessary to increase the spray amount of the flue gas treatment agent sprayed into the flue. When the content is within such a range, a high desalting effect and a higher desulfurization effect than before can be obtained without increasing the spray amount of the flue gas treatment agent.

In addition, in the method for producing a flue gas treating agent, it is preferable to add a solvent that decomposes the mixture in an amount that does not remain in the flue gas treating agent at the end of the reaction by evaporation due to the heat of digestion of quicklime.

As a result of reacting a mixture of quick lime and a substance containing silicon dioxide in a state of being dispersed in a solvent, slaked lime and calcium silicate having a relatively large pore size can be produced. Further, a higher effect of desulfurization can be obtained by the flue gas treatment agent having a large pore size. Further, since the solvent used for dispersion is added in an amount that evaporates due to the heat of digestion, it is not necessary to dry the treatment agent after the reaction is completed. Therefore, the cost and manufacturing time required for the manufacturing process of the smoke treatment agent can be further reduced.

A mixed solution of water and an organic solvent is preferably used as the dispersion solvent. The amount of this mixed solution is preferably 10 parts by weight or more and 100 parts by weight or less.

As a result, quicklime can be efficiently dispersed, and water and organic solvent can be evaporated by the heat of digestion during the digestion reaction. Therefore, a powdery flue gas treatment agent having a large pore size can be easily obtained at low cost without performing a drying treatment. As the organic solvent, for example, glycols such as ethylene glycol, diethylene glycol, propylene glycol and glycerin, amines such as monoethanolamine, diethanolamine and triethanolamine, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol may be used. You can

Regarding the effect of the organic solvent, evaporation of the organic solvent is prioritized during the digestion reaction, and as a result, the effect of improving the dispersibility of quicklime in water and the effect of the organic solvent directly delaying the evaporation of water. There are two possible effects, namely, the effect of improving dispersibility in water, and the latter effect is considered to have a large effect on glycols. The effect of amines is considered to be the latter. It is considered that the former effect has a large influence on alcohols.

Further, it is preferable that the amount of the organic solvent in the solvent is not more than twice the volume of water in the solvent. The water in the solvent is added for the purpose of preventing the water used for the digestion reaction from evaporating due to the heat of digestion and causing indigestion.

Further, as the dispersion solvent, an additive aqueous solution in which the additive is dissolved in water may be used. The amount of this aqueous solution is preferably 10 parts by weight or more and 100 parts by weight or less. Further, the additive in the aqueous solution is preferably dissolved in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the mixture.

This aqueous solution has the function of delaying the evaporation of the stoichiometric amount of water required for the digestion reaction. This allows the reaction to proceed smoothly. Therefore,
A powdery flue gas treatment agent having a large pore size can be easily obtained at low cost without performing a drying treatment. As the additive, for example, citric acid or sugars such as sucrose, glucose and sorbitol can be used.

A solvent selected from the above-mentioned organic solvents is used as a solvent for dispersing quicklime and delaying evaporation of water.
A solution in which one or more additives selected from the above additives are dissolved in a mixed solution of one or more organic solvents and water, or a mixed solution of the organic solvent and water and the additives. You may use the solution which mixed the dissolved additive aqueous solution. As a result, the same action and effect can be obtained as in the case where the solvent is the above-described mixed solution of the organic solvent and water and the case where the solvent is the additive aqueous solution.

Water may be used as the dispersing solvent. The amount of water is preferably 70 parts by weight or more and less than 200 parts by weight when the mixture is 100 parts by weight.

Thereby, quick lime can be dispersed in a sufficient amount of solvent. Therefore, there is no danger of indigestion,
Quicklime can be converted to slaked lime. However, in this case, it is necessary to carry out a drying treatment after the digestion reaction.

When water is used as the solvent for dispersion, the amount may be 10 to 70 parts by weight per 100 parts by weight of the mixture. At this time, for example, by making the particle size of quick lime used as a starting material smaller, it is possible to suppress the occurrence of an instantaneous digestion reaction. As a result, the timing of heat generation caused by the digestion reaction is adjusted, and the time required for water evaporation can be lengthened. Therefore, the occurrence of indigestion can be suppressed and the digestion reaction can be carried out with a sufficient amount of water. As a result,
A flue gas treatment agent having desired performance can be obtained. Further, when the amount of water is the above, it is not necessary to dry the obtained reaction product.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

Commercially available quick lime can be used as the starting material for producing the flue gas treatment agent of the present invention.

As the starting material containing silicon dioxide, a compound containing reactive silicon dioxide can be used. As such a compound, for example,
Examples include hydrous silicon, aluminum metasilicate, calcium silicate, and water glass. A natural product may be used as the silicon dioxide-containing material. Examples of natural products include cristobalite, tridymite, kaolin, bentonite, talc, perlite, zeolite, shirasu, diatomaceous earth, volcanic ash, and kira. A by-product may be used as the silicon dioxide-containing material. Examples of this by-product include blast furnace slag, coal ash, used flue gas treatment agent, and waste glass.

In the production of the flue gas treatment agent of this embodiment, first, quicklime and a silicon dioxide-containing substance are put in a reaction vessel and mixed. Next, a stoichiometric amount of water for converting quicklime into slaked lime and a solvent for dispersing the mixture are added to the mixture.

Since quick lime and water react at a molar ratio of 1: 1, the stoichiometric amount of water for converting quick lime into slaked lime is 32 when quick lime is 100 parts by weight. .1 part by weight. Further, the solvent for dispersion is added within the range of 10 to 200 parts by weight when the amount of the mixture is 100 parts by weight. As the solvent, water or a mixed liquid of water and alcohol can be used. In this embodiment, for example, the solvent for dispersion is 10 to 10
A mixed solution of water and an organic solvent in an amount within the range of 0 parts by weight is used.

In the reaction vessel, quick lime reacts with water and changes into slaked lime. Then, during this reaction, heat of digestion is generated. Further, the heat of digestion causes hydrothermal reaction between quicklime and silicon dioxide to produce calcium silicate. here,
Since the amount of the solvent for dispersion and the particle size of quick lime are set as described above, it is possible to allow the generated heat of digestion heat to remain to the extent that hydrothermal reaction is possible. Therefore, quick lime and silicon dioxide can be favorably reacted with each other to form calcium silicate without performing heat treatment for hydrothermal reaction from the outside. Moreover, the solvent for dispersion can be evaporated by this heat of digestion. As a result, slaked lime partially formed with amorphous calcium silicate is obtained in a dry powder state. This powder has a large pore size because the quicklime is digested with a dispersing solvent with good dispersibility. Further, since the obtained powder is in a state where it can be used as it is as a smoke exhaust treatment agent, it is not necessary to perform a drying treatment.

The flue gas treating agent thus obtained is used to remove harmful HC in the exhaust gas discharged by incineration of general waste.
It is used to remove 1 gas and SO ₂ gas. First, HCl
The gas adsorbs and reacts with slaked lime and calcium silicate to form CaCl ₂ . Therefore, in the flue gas treatment agent produced by the above-mentioned method, the specific surface area for adsorbing HCl gas is large, and therefore the desalination performance is higher than before. Further, SO ₂ gas is adsorbed via a complicated reaction mechanism. Briefly, SO ₂ is oxidized and fixed as CaSO ₄ . Then, this oxide immobilization required NO _x, NO _x is oxidized active species SO _2. Here, the flue gas treatment agent of this embodiment partially contains calcium silicate. This calcium silicate is particularly easy to absorb NO _x . For this reason,
This flue gas treating agent can have a significantly higher desulfurization effect than slaked lime containing no calcium silicate.

[0032]

EXAMPLES Some examples of a method for producing a flue gas treating agent according to the present invention will be described below with reference to the drawings together with comparative examples. It should be noted that each of the drawings merely schematically shows the shape, size, and arrangement relationship of each constituent component to the extent that the invention can be understood, and therefore the present invention is not limited to the illustrated examples. Further, it should be understood that the numerical conditions such as the materials used and the amounts of the respective materials mentioned in the following description are merely examples within the scope of these inventions.

In each of the following examples, about 400 g of a flue gas treating agent was experimentally produced using a mortar mixer, and the characteristics of the treating agent were investigated. In addition, its performance will be evaluated. The actual production of the flue gas treatment agent of the present invention is a continuous production using a conventional production apparatus for digesting quick lime to produce slaked lime and obtaining a large amount of the treatment agent. It is considered that there is almost no difference in characteristics or performance between the experimentally obtained treating agent and the treating agent produced using the conventional apparatus.

In Example 1, commercially available quicklime and coal ash as a silicon dioxide-containing material are used as starting materials. Then, water is used as a solvent, and a mixture of quicklime and coal ash 100
It is manufactured by preparing 192.3 parts by weight per part by weight.

In Example 2, as in Example 1, commercially available quicklime and coal ash were used as starting materials, and an aqueous citric acid solution was used as a solvent. Then, in Examples 2-1 to 2-3, the amount of the citric acid aqueous solution is changed and the treating agent is manufactured.

In Example 3, as in Example 1, commercially available quicklime and coal ash were used as starting materials, and an aqueous sucrose solution was used as a solvent. Then, in Examples 3-1 to 3-3, the concentration of sucrose and the amount of the sucrose aqueous solution are changed, and the respective treatment agents are manufactured.

In Example 4, as in Example 1, commercially available quicklime and coal ash are used as starting materials, and an aqueous glucose solution is used as a solvent. Then, in Examples 4-1 to 4-3, the concentration of glucose and the amount of the glucose aqueous solution are changed, and the treatment agents are manufactured.

In Example 5, as in Example 1, commercially available quicklime and coal ash were used as starting materials, and an aqueous sorbitol solution was used as a solvent. Then, in Examples 5-1 to 5-3, the treatment agent is manufactured by changing the concentration of sorbitol and the amount of the sorbitol aqueous solution.

In Example 6, as in Example 1, commercially available quicklime and coal ash are used as starting materials, and a mixed solution of water and EG (ethylene glycol) is used as a solvent. Then, in Examples 6-1 to 6-3, the treatment agent is manufactured by changing the amount of EG.

In Example 7, as in Example 1, commercially available quicklime and coal ash were used as starting materials, and a mixed solution of water and DEG (diethylene glycol) was used as a solvent. Then, in Examples 7-1 to 7-3, the amount of DEG is changed and the treatment agent is manufactured.

In Example 8, as in Example 1, commercially available quicklime and coal ash were used as starting materials, and a mixed solution of water and PG (propylene glycol) was used as a solvent.
Then, in Examples 8-1 to 8-3, the amount of PG is changed to produce the treatment agent.

In Example 9, as in Example 1, commercially available quicklime and coal ash are used as starting materials, and a mixed solution of water and MEA (monoethanolamine) is used as a solvent. Then, in Examples 9-1 to 9-3, the amount of MEA is changed and the treatment agent is manufactured.

In Example 10, as in Example 1, commercially available quicklime and coal ash were used as starting materials, and a mixed solution of water and DEA (diethanolamine) was used as a solvent. Then, in Examples 10-1 to 10-3, the amount of DEA was changed to produce the treatment agent.

In Example 11, as in Example 1, commercially available quicklime and coal ash were used as starting materials, and a mixed solution of water and TEA (triethanolamine) was used as a solvent. Then, in Examples 11-1 to 11-3, the treatment agent is manufactured by changing the amount of TEA.

In Example 12, as in Example 1, commercially available quicklime and coal ash were used as starting materials, and a mixed solution of water and MA (methyl alcohol) was used as a solvent. Then, in Examples 12-1 to 12-3, the amount of MA is changed and the treating agent is manufactured.

In Example 13, as in Example 1, commercially available quicklime and coal ash were used as starting materials, and a mixed solution of water and EA (ethyl alcohol) was used as a solvent. Then, in Examples 13-1 to 13-3, the amount of EA is changed and the treatment agent is manufactured.

In Example 14, as in Example 1, commercially available quicklime and coal ash were used as starting materials, and a mixed solution of water and IPA (isopropyl alcohol) was used as a solvent. And in Examples 14-1 to 14-3, IPA
The treatment agent is manufactured by changing the amount of each.

Example 15 starts with commercially available quicklime and zeolite as a silicon dioxide containing material. Water is prepared as the solvent.

In Example 16, as in Example 15, commercially available quicklime and zeolite are used as starting materials. Further, a mixed solution of water and IPA is used as a solvent. Then, in Examples 16-1 and 16-2, the IPA contents in the mixed solution are different from each other.

In Example 17, commercially available quicklime and glass powder containing silicon dioxide are used as the starting materials. In addition, water was prepared as a solvent, and Examples 17-1 to 17-
In No. 3, production is performed with different amounts of water.

In Example 18, as in Example 17, commercially available quicklime and glass powder are used as starting materials. Further, a mixed solution of water and IPA is used as a solvent. And in Examples 18-1 and 18-2, it manufactures so that the IPA content rate in a mixed solution may differ.

In Example 19, commercially available quicklime having a smaller particle size than in Example 1 and coal ash as a silicon dioxide-containing material are used as starting materials. Then, only water is prepared as the solvent. The amount of this water is between 10 and 70 parts by weight per 100 parts by weight of the mixture of quicklime and coal ash. In Examples 19-1 to 19-3, the treatment agent is manufactured by changing the amount of water as a solvent.

In Example 20, as in Example 1, commercially available quicklime and coal ash were used as starting materials, and a solution prepared by mixing an aqueous sorbitol solution and triethanolamine (TEA) was used as a solvent. Then, in Examples 20-1 and 20-2, the concentration of the sorbitol aqueous solution and T
The treatment agent is manufactured by changing the amount of EA.

As Comparative Example 1, a special slaked lime (manufactured by Hokkaido Kyodo Lime Co., Ltd.), which has been conventionally used as an exhaust gas treating agent, is prepared. As Comparative Example 2, highly reactive slaked lime is prepared.

Example 1 First, a commercially available quicklime (made by Ueda Lime Manufacturing Co., Ltd.) having a particle size of 2 to 4 mm, coal ash as a silicon dioxide-containing substance, and water are prepared.

272 g of the above quicklime (about 87.2 parts by weight)
And 40 g of ground coal ash (containing about 20 g (about 6.4 parts by weight) of silicon dioxide) are mixed in a mortar mixer. After the quicklime and the coal ash are mixed almost uniformly, 688 g of water at 70 ° C. is gradually added to the mortar mixer while stirring the mixture. Water is 88 g of water in a stoichiometric amount for digesting quicklime, and 600 g of water as a solvent for dispersing the mixture (about 192.3 parts by weight of the mixture).
And add together.

As a result, quicklime is digested to become slaked lime. During this digestion, digestive fever is generated. Further, the heat of digestion causes hydrothermal reaction between quick lime and coal ash on the surface of quick lime to form calcium silicate. In addition, part of the water added for dispersion evaporates due to this heat of digestion. In this example, since the reaction product contains a large amount of water, the reaction product is dried at a temperature of 160 ° C. for 3 hours using a hot air dryer as a drying means. As a result, about 400 g of the flue gas treatment agent of Example 1 is obtained.

<Example 2> As Example 2, an example in which the solvent in which the mixture is dispersed is different from Example 1 will be described. In Example 2, a citric acid aqueous solution in which citric acid as an additive is dissolved is used as a solvent. In addition, Example 1
The detailed description of the same points as the above is omitted.

(2-1) 272 g of quick lime (manufactured by Ueda Lime Manufacturing Co., Ltd.) as in Example 1 and crushed coal ash 40
g in a mortar mixer and then at 70 ° C. and a citric acid concentration of 0.25% by weight.
160 g of aqueous citric acid solution are slowly added while stirring the mixture. In addition to the citric acid aqueous solution, 88 g of water having a stoichiometric amount of water for digesting quicklime is also added to the mortar mixer.

As a result, about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate is produced by a hydrothermal reaction between quicklime and silicon dioxide in coal ash by utilizing the heat of digestion generated during the digestion of quicklime. The citric acid aqueous solution has a function of delaying the evaporation of the stoichiometric amount of water required for the digestion reaction by the heat of digestion of quicklime. Therefore, there is no fear that the digestion reaction will be insufficient. Finally, the citric acid aqueous solution evaporates due to the heat of digestion. Therefore, the obtained reaction product becomes powdery.

(2-2) Quicklime and coal ash are mixed in a mortar mixer, and then the solvent added to the mortar mixer is a citric acid aqueous solution having a citric acid concentration of 10% by weight.
The same as (2-1) above except that the weight is 80 g. As a result, a powdery reaction product is obtained.

(2-3) Quicklime and coal ash are mixed in a mortar mixer, and then the solvent added to the mortar mixer is a citric acid aqueous solution having a citric acid concentration of 20% by weight.
The procedure is the same as (2-1) above, except that the amount is set to 00 g. As a result, a powdery reaction product is obtained.

In the production of the flue gas treatment agent of this Example 2, the hydrothermal reaction for producing calcium silicate can be carried out without applying heat from the outside. In addition, since the solvent (citric acid aqueous solution) added to disperse the mixture of quick lime and coal ash also evaporates due to the heat of digestion, it is not necessary to dry the obtained slaked lime containing calcium silicate using a drying means. Absent. Therefore,
The flue gas treatment agent can be manufactured very inexpensively and easily.

<Example 3> As Example 3, an example in which the additive is different from that of Example 2 will be described. In this example, sucrose is used as an additive. Therefore, the solvent in which the mixture is dispersed is an aqueous sucrose solution in which sucrose is dissolved. Note that detailed description of the same points as those of the first and second embodiments will be omitted.

(3-1) 272 g of quick lime (manufactured by Ueda Lime Manufacturing Co., Ltd.) as in Example 1 and crushed coal ash 40
After mixing with g in a mortar mixer, 160 g of an aqueous sucrose solution having a sucrose concentration of 0.25% by weight at 70 ° C. is gradually added to the mortar mixer while stirring the mixture. In addition to this sucrose aqueous solution, 88 g of water having a stoichiometric amount of water for digesting quicklime is added to the mortar mixer.

As a result, about 400 g of slaked lime partially formed of calcium silicate is obtained. The sucrose aqueous solution has a function of delaying the evaporation of the stoichiometric amount of water required for the digestion reaction due to the heat of digestion of quicklime. Therefore, there is no fear that the digestion reaction will be insufficient. Finally, the sucrose aqueous solution evaporates due to the heat of digestion. Therefore, the obtained reaction product becomes powdery.

(3-2) Quicklime and coal ash are mixed in a mortar mixer, and then the solvent added to the mortar mixer is 180 g of a sucrose aqueous solution having a sucrose concentration of 10% by weight. Same as -1). As a result, a powdery reaction product is obtained.

(3-3) Quicklime and coal ash are mixed in a mortar mixer, and then the solvent added to this mortar mixer is 200 g of an aqueous sucrose solution having a sucrose concentration of 20% by weight. Same as -1). As a result, a powdery reaction product is obtained.

<Example 4> As Example 4, an example in which the additive used in the additive aqueous solution used as a solvent for dispersing the mixture is different from those in Examples 2 and 3 will be described. In this example, glucose is used as an additive. Note that detailed description of the same points as those of the first to third embodiments will be omitted.

(4-1) Instead of the sucrose aqueous solution of (3-1) of Example 3, 160 g of glucose aqueous solution having a glucose concentration of 0.25% by weight is used.

(4-2) Instead of the sucrose aqueous solution of (3-2) of Example 3, 180 g of glucose aqueous solution having a glucose concentration of 10% by weight is used.

(4-3) Instead of the sucrose aqueous solution of (3-3) of Example 3, 200 g of glucose aqueous solution having a glucose concentration of 20% by weight is used.

As a result, in the examples (4-1), (4-2) and (4-3), about 400 g of slaked lime partially formed of calcium silicate is obtained. The glucose aqueous solution has a function of delaying evaporation of the stoichiometric amount of water required for the digestion reaction due to the heat of digestion of quicklime. Therefore, there is no fear that the digestion reaction will be insufficient. Finally, the glucose aqueous solution evaporates due to the heat of digestion. Therefore, the obtained reaction product becomes powdery.

Example 5 As Example 5, an example in which the additive used in the additive aqueous solution used as the solvent for dispersing the mixture is different from those in Examples 2 to 4 will be described.
In this example, sorbitol is used as an additive. Note that detailed description of the same points as those of the first to fourth embodiments will be omitted.

(5-1) Instead of the sucrose aqueous solution of (3-1) of Example 3, the concentration of sorbitol was 0.25% by weight.
160 g of an aqueous sorbitol solution are used.

(5-2) Instead of the sucrose aqueous solution of (3-2) of Example 3, 180 g of an sorbitol aqueous solution having a sorbitol concentration of 10% by weight is used.

(5-3) Instead of the sucrose aqueous solution of (3-3) of Example 3, 200 g of sorbitol aqueous solution having a sorbitol concentration of 20% by weight is used.

As a result, in the examples (5-1), (5-2) and (5-3), about 400 g of slaked lime partially formed of calcium silicate is obtained. The sorbitol aqueous solution has the effect of delaying the evaporation of the stoichiometric amount of water required for the digestion reaction due to the heat of digestion of quicklime. Therefore, there is no fear that the digestion reaction will be insufficient. Finally, the sorbitol aqueous solution evaporates due to the heat of digestion. Therefore, the obtained reaction product becomes powdery.

Example 6 As Example 6, an example in which the solvent in which the mixture is dispersed is a mixed solution of water and an organic solvent will be described. In this example, EG (ethylene glycol) is used as the organic solvent. Note that detailed description of the same points as those of the first embodiment will be omitted.

(6-1) 272 g of quick lime (manufactured by Ueda Lime Manufacturing Co., Ltd.) as in Example 1 and crushed coal ash 40
After mixing with g in a mortar mixer, a mixed solution of water and EG at 70 ° C. is gradually added to the mortar mixer while stirring the mixture. The mixed solution is a mixture of 88 ml of water having a stoichiometric amount of water for digesting quicklime and 160.4 ml of the mixed solution as a solvent. The mixed solution as the solvent was 160 ml of water and EG0.
4 ml (water: EG = 1: 0.0025 (volume ratio)) was mixed.

As a result, about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate is produced by the hydrothermal reaction between quicklime and silicon dioxide in coal ash by utilizing the digestive heat generated during the digestion of quicklime. The mixed solution has a function of delaying the evaporation of the stoichiometric amount of water in the mixed solution due to the heat of digestion of quicklime. Therefore, the digestion reaction can be performed with a sufficient amount of water. Further, due to the heat of digestion, the mixed solution of water and EG added for dispersing the mixture evaporates. Therefore, the obtained reaction product becomes powdery.

(6-2) Quicklime and coal ash are mixed in a mortar mixer, and the solvent added to this mortar mixer is a mixed solution of 160 ml of water and 40 ml of EG (water:
EG = 1: 0.25 (volume ratio)), and the same as (6-1) above. As a result, a powdery reaction product is obtained.

(6-3) Quicklime and coal ash are mixed in a mortar mixer, and then the solvent added to the mortar mixer is a mixed solution of 160 ml of water and 80 ml of EG (water:
EG = 1: 0.5 (volume ratio)) except for the above (6
Same as -1). As a result, a powdery reaction product is obtained.

Example 7 As Example 7, an example in which the organic solvent used in the mixed solution used as the solvent for dispersing the mixture is a glycol different from that in Example 6 will be described. In this example, DEG (diethylene glycol) is used as the organic solvent. Note that detailed description of points similar to those of Examples 1 to 6 will be omitted.

(7-1) Instead of EG in the mixed solution of (6-1) of Example 6, 0.4 ml of DEG is used.

(7-2) 40 ml of DEG is used instead of EG in the mixed solution of (6-2) of Example 6.

(7-3) 80 ml of DEG is used instead of EG in the mixed solution of (6-3) of Example 6.

As a result, about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate is produced by the hydrothermal reaction between quicklime and silicon dioxide in coal ash by utilizing the digestive heat generated during the digestion of quicklime. The mixed solution has a function of delaying the evaporation of the stoichiometric amount of water in the mixed solution due to the heat of digestion of quicklime. Therefore, the digestion reaction can be performed with a sufficient amount of water. Further, due to the heat of digestion, the mixed solution of water and DEG added for dispersing the mixture evaporates. Therefore, the obtained reaction product becomes powdery.

<Example 8> As Example 8, an example in which the organic solvent used in the mixed solution used as the solvent for dispersing the mixture is a glycol different from those in Examples 6 and 7 will be described. In this example, PG is used as the organic solvent.
(Propylene glycol) is used. In addition, Example 1
The detailed description of the same points as those of No. 7 will be omitted.

(8-1) 0.4 ml of PG is used instead of EG in the mixed solution of (6-1) of Example 6.

(8-2) 40 ml of PG is used instead of EG in the mixed solution of (6-2) of Example 6.

(8-3) Instead of EG in the mixed solution of (6-3) of Example 6, 80 ml of PG is used.

As a result, about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate is produced by the hydrothermal reaction between quicklime and silicon dioxide in coal ash by utilizing the digestive heat generated during the digestion of quicklime. The mixed solution has a function of delaying the evaporation of the stoichiometric amount of water in the mixed solution due to the heat of digestion of quicklime. Therefore, the digestion reaction can be performed with a sufficient amount of water. Further, due to the heat of digestion, the mixed solution of water and PG added for dispersing the mixture evaporates. Therefore, the obtained reaction product becomes powdery.

<Example 9> As Example 9, an example in which the solvent in which the mixture is dispersed is a mixed solution of water and an organic solvent different from those in Examples 6 to 8 will be described. In this example, MEA (monoethanolamine) is used as the organic solvent. Note that detailed description of the same points as those of the first embodiment will be omitted.

(9-1) 272 g of quicklime (manufactured by Ueda Lime Manufacturing Co., Ltd.) as in Example 1 and 40 pieces of crushed coal ash
After mixing with g in a mortar mixer, a mixed solution of water and MEA at 70 ° C. is gradually added to the mortar mixer while stirring the mixture. The mixed solution is a mixture of 88 ml of water having a stoichiometric amount of water for digesting quicklime and 160.4 ml of the mixed solution as a solvent. The mixed solution as a solvent is 160 ml of water and MEA.
It is a mixture with 0.4 ml (water: MEA = 1: 0.0025 (volume ratio)).

As a result, about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate is produced by the hydrothermal reaction between quicklime and silicon dioxide in coal ash by utilizing the digestive heat generated during the digestion of quicklime. The mixed solution has a function of delaying the evaporation of the stoichiometric amount of water in the mixed solution due to the heat of digestion of quicklime. Therefore, the digestion reaction can be performed with a sufficient amount of water. Further, due to the heat of digestion, the mixed solution of water and MEA added for dispersing the mixture evaporates. Therefore, the obtained reaction product becomes powdery.

(9-2) Quicklime and coal ash are mixed in a mortar mixer, and then the solvent added to this mortar mixer is a mixed solution of 160 ml of water and 20 ml of MEA (water: MEA = 1: 0.125 ( The same as (9-1) above except that the volume ratio) is set. As a result, a powdery reaction product is obtained.

(9-3) Quicklime and coal ash are mixed in a mortar mixer, and then the solvent added to the mortar mixer is a mixed solution of 160 ml of water and 40 ml of MEA (water: MEA = 1: 0.25 ( The same as (9-1) above except that the volume ratio) is set. As a result, a powdery reaction product is obtained.

Example 10 As Example 10, an example in which the organic solvent used in the mixed solution used as the solvent for dispersing the mixture is ethanolamines different from that in Example 9 will be described. In this example, the organic solvent is DE
A (diethanolamine) is used. In addition, Example 1
The detailed description of the same points as those in 9 will be omitted.

(10-1) In place of MEA in the mixed solution of (9-1) of Example 9, 0.4 ml of DEA is used.

(10-2) 20 ml of DEA is used instead of MEA in the mixed solution of (9-2) of Example 9.

(10-3) In place of MEA in the mixed solution of (9-3) of Example 9, 40 ml of DEA is used.

As a result, about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate is produced by the hydrothermal reaction between quicklime and silicon dioxide in coal ash by utilizing the digestive heat generated during the digestion of quicklime. The mixed solution has a function of delaying the evaporation of the stoichiometric amount of water in the mixed solution due to the heat of digestion of quicklime. Therefore, the digestion reaction can be performed with a sufficient amount of water. Also, due to the heat of digestion, the mixed solution of water and DEA added for dispersing the mixture evaporates. Therefore, the obtained reaction product becomes powdery.

Example 11 As Example 11, an example in which the organic solvent used in the mixed solution used as the solvent for dispersing the mixture is ethanolamines different from those in Examples 9 and 10 will be described. In this example, TEA (triethanolamine) is used as the organic solvent. Note that detailed description of the same points as those in Examples 1 to 10 will be omitted.

(11-1) Instead of MEA in the mixed solution of (9-1) of Example 9, 0.4 ml of TEA is used.

(11-2) Instead of MEA in the mixed solution of (9-2) of Example 9, 20 ml of TEA is used.

(11-3) Instead of MEA in the mixed solution of (9-3) of Example 9, 40 ml of TEA is used.

As a result, about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate is produced by the hydrothermal reaction between quicklime and silicon dioxide in coal ash by utilizing the digestive heat generated during the digestion of quicklime. The mixed solution has a function of delaying the evaporation of the stoichiometric amount of water in the mixed solution due to the heat of digestion of quicklime. Therefore, the digestion reaction can be performed with a sufficient amount of water. Further, due to the heat of digestion, the mixed solution of water and TEA added for dispersing the mixture evaporates. Therefore, the obtained reaction product becomes powdery.

Example 12 As Example 12, an example in which the solvent in which the mixture is dispersed is a mixed solution of water and an organic solvent different from those of Examples 6 to 11 will be described. In this example, MA (methyl alcohol) is used as the organic solvent. Note that detailed description of the same points as those of the first embodiment will be omitted.

(12-1) 272 g of quicklime (manufactured by Ueda Lime Manufacturing Co., Ltd.) as in Example 1 and crushed coal ash 4
After mixing with 0 g in a mortar mixer, a mixed solution of water and MA at 70 ° C. is gradually added into the mortar mixer while stirring the mixture. The mixed solution is a mixture of 88 ml of stoichiometric water for digesting quicklime and 150 ml of the mixed solution as a solvent.
The mixed solution as solvent is 60 ml of water and 90 ml of MA.
(Water: MA = 1: 1.5 (volume ratio)).

As a result, about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate is produced by the hydrothermal reaction between quicklime and silicon dioxide in coal ash by utilizing the digestive heat generated during the digestion of quicklime. The organic solvent in the mixed solution is
Evaporates before water. This can delay the evaporation of water required for the digestion reaction. Therefore, quicklime can be dispersed in a sufficient amount of water, and by this,
The digestive reaction can be performed without causing indigestion. Further, due to the heat of digestion, the mixed solution of water and MA added for dispersing the mixture evaporates. Therefore, the obtained reaction product becomes powdery.

(12-2) Quicklime and coal ash are mixed in a mortar mixer, and the solvent added to this mortar mixer is a mixed solution of 80 ml of water and 120 ml of MA (water: MA = 1: 1.5 ( (12-1) except that the volume ratio)) is set. As a result, a powdery reaction product is obtained.

(12-3) Quicklime and coal ash are mixed in a mortar mixer, and then the solvent added to the mortar mixer is a mixed solution of 120 ml of water and 180 ml of MA (water: MA = 1: 1.5 ( (12-1) except that the volume ratio)) is set. As a result, a powdery reaction product is obtained.

Example 13 As Example 13, an example in which the organic solvent used in the mixed solution used as the solvent for dispersing the mixture is an alcohol different from that in Example 12 will be described. In this example, EA (ethyl alcohol) is used as the organic solvent. Note that detailed description of points similar to those of Examples 1 to 12 will be omitted.

(13-1) Instead of MA in the mixed solution of (12-1) of Example 12, 90 ml of EA is used.

(13-2) 120 ml of EA is used instead of MA in the mixed solution of (12-2) of Example 12.

(13-3) 180 ml of EA is used instead of MA in the mixed solution of (12-3) of Example 12.

As a result, about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate is produced by the hydrothermal reaction between quicklime and silicon dioxide in coal ash by utilizing the digestive heat generated during the digestion of quicklime. The organic solvent in the mixed solution is
Evaporates before water. This can delay the evaporation of water required for the digestion reaction. Therefore, quicklime can be dispersed in a sufficient amount of water, and by this,
The digestive reaction can be performed without causing indigestion. Further, due to the heat of digestion, the mixed solution of water and EA added for dispersing the mixture evaporates. Therefore, the obtained reaction product becomes powdery.

Example 14 As Example 14, an example in which the organic solvent used in the mixed solution used as the solvent for dispersing the mixture is an alcohol different from those in Examples 12 and 13 will be described. In this example, IPA (isopropyl alcohol) is used as the organic solvent. In addition,
Detailed description of the same points as those in Examples 1 to 13 will be omitted.

(14-1) Instead of MA in the mixed solution of (12-1) of Example 12, 90 ml of IPA is used.

(14-2) Instead of MA in the mixed solution of (12-2) of Example 12, 120 ml of IPA is used.

(14-3) Instead of MA in the mixed solution of (12-3) of Example 12, 180 ml of IPA is used.

(14-4) Quicklime and coal ash are mixed in a mortar mixer, and then the solvent added to the mortar mixer is a mixed solution of 140 ml of water and 210 ml of IPA (water: IPA = 1: 1.5 ( Volume ratio))
The same as (12-1) above.

As a result, in each of the above examples (14-1 to 4), about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate utilizes the digestive heat generated when quicklime is digested,
It is produced by a hydrothermal reaction between quicklime and silicon dioxide in coal ash. The organic solvent in the mixed solution evaporates before water. This can delay the evaporation of water required for the digestion reaction. Therefore, quicklime can be dispersed in a sufficient amount of water, whereby the digestion reaction can be performed without causing indigestion. Also, due to the heat of digestion, the water and IP added to disperse the mixture
The mixed solution with A evaporates. Therefore, the obtained reaction product becomes powdery.

<Embodiment 15> In Embodiment 15, Embodiment 1
14 to 14 describe examples in which the silicon dioxide-containing material that is a starting material for manufacturing is different.

First, 272 g of quick lime as in Example 1
(About 87.2 parts by weight) and 40 g of crushed zeolite
(Containing about 24 g of silicon dioxide (about 7.7 parts by weight)) in a mortar mixer. Quicklime and zeolite are mixed almost uniformly and then in a mortar mixer at 70 ° C.
688 g of water are slowly added while stirring the mixture.
Water is a stoichiometric amount of water to digest quicklime 8
8 g and 600 g of water as a solvent for dispersing the mixture
(About 192.3 parts by weight of the mixture) and are added together.

Next, the obtained reaction product is dried for 3 hours at a temperature of 160 ° C. using a hot air dryer. As a result, the flue gas treatment agent of Example 15 in powder form was about 4
00 g is obtained.

<Example 16> As Example 16, an example in which the solvent for dispersing the mixture is different from that in Example 15 will be described. In Example 16, a mixed solution of water and IPA is used as the solvent. Note that detailed description of the same points as in Example 15 will be omitted.

(16-1) Quicklime 2 as in Example 15
After mixing 72 g with 40 g of ground zeolite in a mortar mixer, 238 ml of a mixed solution of water and IPA at 70 ° C. is gradually added to this mortar mixer while stirring the mixture. This mixed solution contains 88 ml of stoichiometric amount of water for digesting quicklime, and 60 ml of water as a solvent and 90 ml of IPA (water: IPA = 1: 1.5 (volume ratio)). I'm out.

As a result, about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate is produced by hydrothermal reaction between quick lime and silicon dioxide in zeolite by utilizing the heat of digestion generated during quick lime digestion. The solvent composed of a mixed solution of water and IPA has a function of delaying evaporation of stoichiometric amount of water in the aqueous solution due to heat of digestion of quicklime and an effect of improving dispersibility of quicklime during the digestion reaction. Have As a result, the digestion reaction proceeds smoothly, and the solvent is finally evaporated by the heat of digestion. For this reason, the obtained reaction product becomes powdery even if it is not dried.

(16-2) Quicklime and zeolite are mixed in a mortar mixer, and then the solvent added to the mortar mixer is a mixed solution of 80 ml of water and 120 ml of IPA (water: IPA = 1: 1.5 (volume: The same as (16-1) above except that the ratio is set to (). As a result, a powdery reaction product is obtained.

(16-3) Quicklime and zeolite are mixed in a mortar mixer, and then the solvent added to this mortar mixer is a mixed solution of 120 ml of water and 180 ml of IPA (water: IPA = 1: 1.5 (volume: The same as (16-1) above except that the ratio is set to (). As a result, a powdery reaction product is obtained.

In the production of the flue gas treating agent of Example 16, the hydrothermal reaction for producing calcium silicate can be carried out without applying heat from the outside. In addition, since the solvent (mixed solution of water and IPA) added to disperse the mixture of quick lime and coal ash also evaporates by the heat of digestion, the obtained slaked lime containing calcium silicate is dried using a drying means. No need to dry.
Therefore, the flue gas treatment agent can be manufactured very inexpensively and easily.

<Embodiment 17> In Embodiment 17, Embodiment 1
The description will be made of an example in which the silicon dioxide-containing material, which is a starting material for production, is different from ˜16.

(17-1) First, 272 g of quicklime (about 87.2 parts by weight) as in Example 1 and 40 g of crushed glass powder (including about 30 g of silicon dioxide (about 9.6 parts by weight)). Are mixed in a mortar mixer. After the quicklime and the glass powder are mixed almost uniformly, 7 in a mortar mixer
408 g of water at 0 ° C. are added slowly with stirring the mixture. The water is 88 g of stoichiometric amount of water for digesting quicklime, and 320 of water as a solvent for dispersing the mixture.
g (about 102.5 parts by weight of the mixture) are added together.

Then, the obtained reaction product is dried for 3 hours at a temperature of 160 ° C. using a hot air dryer. As a result, about 400 g of the flue gas treatment agent of Example (17-1) in powder form is obtained.

(17-2) Smoke exhaust was performed in the same manner as in (17-1) above, except that quick lime and glass powder were mixed in a mortar mixer, and then the amount of water added to this mortar mixer was 488 g. A treating agent is manufactured. Amount of water above (488
g) is the combined amount of 88 g of water for digesting quicklime and 400 g of water as a solvent (about 128.2 parts by weight of the mixture). As a result, a powdery reaction product is obtained.

(17-3) Quick lime and glass powder are mixed in a mortar mixer, and the amount of water added to this mortar mixer is 688 g, except that the amount of water added is 688 g. A treating agent is manufactured. Amount of water (688)
g) is the combined amount of 88 g of water for digesting quicklime and 600 g of water as a solvent (about 192.3 parts by weight of the mixture). As a result, a powdery reaction product is obtained.

<Embodiment 18> In Embodiment 18, Embodiment 1
Similarly to 7, glass powder is used as the silicon dioxide-containing material that is the starting material for production, and a mixed solution of water and IPA is used as a solvent for dispersing the mixture of the glass powder and quicklime.

(18-1) Quicklime 27 similar to that in Example 1
2 g and 40 g of crushed glass powder were mixed in a mortar mixer, and then water and I at 70 ° C. were mixed in the mortar mixer.
The mixed solution with PA is gradually added while stirring the mixture. The mixed solution is a mixture of 88 ml of water, which is the amount of water necessary for digesting quicklime, and a mixed solution of water as a solvent and IPA. The mixed solution as a solvent is a mixture of 80 ml of water and 120 ml of IPA (water: IPA = 1: 1.5 (volume ratio)). As a result, the powdery flue gas treatment agent of Example 18-1 was about 400
g obtained.

(18-2) Quicklime and glass powder are mixed in a mortar mixer, and the solvent added to this mortar mixer is a mixed solution of 120 ml of water and 120 ml of IPA (water: IPA = 1: 1 (volume ratio). )) Except that the same as (18-1) above. As a result, a powdery reaction product is obtained.

As a result, (18-1) and (18-
In the example of 2), about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate is produced by the hydrothermal reaction between quicklime and silicon dioxide in glass powder by utilizing the heat of digestion generated during quicklime digestion. The solvent composed of a mixed solution of water and IPA has a function of delaying evaporation of stoichiometric amount of water in the aqueous solution due to heat of digestion of quicklime and an effect of improving dispersibility of quicklime during the digestion reaction. Have As a result, the digestion reaction proceeds smoothly, and the solvent is finally evaporated by the heat of digestion. For this reason, the obtained reaction product becomes powdery even if it is not dried.

<Example 19> As Example 19, commercially available quick lime having a particle size of 0.25 mm or less (manufactured by Ueda Lime Manufacturing Co., Ltd.), coal ash as a silicon dioxide-containing substance, and water were used. prepare. An example in which the amount of water is smaller than that in Example 1 and the drying process is not necessary will be described.

(19-1) 272 g of the above-mentioned quick lime (about 8
(7.2 parts by weight) and 40 g of ground coal ash (containing about 20 g of silicon dioxide (about 6.4 parts by weight)) are mixed in a mortar mixer. Then, 208 g of water at 70 ° C. is gradually added to the mortar mixer while stirring the mixture. Water is a stoichiometric amount of water to digest quicklime 8
8g and 120g of water as a solvent for dispersing the mixture
(About 38.5 parts by weight per 100 parts by weight of the mixture) are added together. After sufficiently stirring, the reaction product obtained by radiating heat in the air atmosphere at room temperature is used as the treating agent of Example 19-1. As a result, about 400 g of powdered slaked lime partially formed of calcium silicate is obtained.

(19-2) Same as (19-1) above except that quick lime and coal ash are mixed in a mortar mixer and then the amount of water added to this mortar mixer is 248 g. The amount of water (248 g) is a total amount of 88 g of water for digesting quicklime and 160 g of water as a solvent (51.3 parts by weight per 100 parts by weight of the mixture). As a result, a powdery reaction product is obtained.

(19-3) The same as (19-1) above except that quick lime and coal ash are mixed in a mortar mixer and then the amount of water added to this mortar mixer is 288 g. The amount of water (288 g) is a total amount of 88 g of water for digesting quicklime and 200 g of water as a solvent (64.1 parts by weight per 100 parts by weight of the mixture). As a result, a powdery reaction product is obtained.

<Example 20> As Example 20, an example in which the solvent in which the mixture is dispersed is a solution in which a mixed solution of an organic solvent and water and an aqueous solution of an additive are mixed will be described. In this example, triethanolamine (TEA) is used as the organic solvent and sorbitol is used as the additive. Note that detailed description of the same points as those of the first embodiment will be omitted.

(20-1) 272 g of quicklime (manufactured by Ueda Lime Manufacturing Co., Ltd.) as in Example 1 and crushed coal ash 4
After mixing with 0 g in a mortar mixer, in this mortar mixer at 70 ° C. and a sorbitol concentration of 0.
160 g of 25 wt% sorbitol aqueous solution and TEA20
The solution mixed with ml is gradually added while stirring the mixture. In addition to this solution, 88 g of a stoichiometric amount of water for digesting quicklime is added to the mortar mixer.

As a result, about 400 g of slaked lime partially formed of calcium silicate is obtained. Calcium silicate is produced by a hydrothermal reaction between quicklime and silicon dioxide in coal ash by utilizing the heat of digestion generated during the digestion of quicklime. The solution used as a solvent has the effect of delaying the evaporation of the stoichiometric amount of water in this solution by the heat of digestion of quicklime. Therefore, there is no fear that the digestion reaction will be insufficient. Finally, the solution evaporates due to the heat of digestion. Therefore, the obtained reaction product becomes powdery.

(20-2) Quicklime and coal ash are mixed in a mortar mixer, and the solvent added to the mortar mixer is 180 g of an aqueous sorbitol solution having a sorbitol concentration of 10% by weight, and the amount of TEA is 0.1. The procedure is the same as (20-1) above, except that the volume is 4 ml. This allows
A powdery reaction product is obtained.

<Comparative Example 1> As Comparative Example 1, a special slaked lime (trade name: manufactured by Hokkaido Kyodo Lime Co., Ltd.) is prepared.

<Comparative Example 2> As Comparative Example 2, a highly reactive slaked lime is prepared.

(Performance Test of Smoke Treatment Agent) Next, the performance test is performed on each of the smoke treatment agents obtained in Examples 1 to 20. Here, the desulfurization performance of the flue gas treatment agent is tested using the test apparatus shown in FIG. 1 by a powder-dispersed filling gas flow system using absorbent cotton.

The test apparatus 10 comprises an electric furnace 12 and an electric furnace 1.
2, a reaction tube 14 installed in the reaction tube 14, absorbent cotton 16 packed in the reaction tube 14, a gas concentration measuring device 18 for measuring the concentration of each gas in the exhaust gas from the reaction tube 14, and a flow meter, respectively. Multiple gas cylinders 2 with 20a-20e
2a to 22e, a humidifier 24, a mixer 26 that mixes the steam from the humidifier 24 with the gas from the gas cylinders 22a to 22e, and a gas supply that supplies the mixed gas from the mixer 26 to the reaction tube 14. And a tube 28 (FIG. 1).

Here, as the gas cylinders 22a to 22e, there are prepared a gas cylinder 22a of SO ₂ gas, a gas cylinder 22b of NO gas, a gas cylinder 22c of CO ₂ gas, a gas cylinder 22d of O ₂ gas and a gas cylinder 22e of N ₂ gas. Then, the concentration of each gas in the mixed gas supplied to the reaction tube 14 is set to the following concentration.

SO ₂ : 2250 ppm, NO: 700 p
_{pm, CO 2: 13%,} O 2: 6%, H 2 O: 10%. Then, the concentration of these gases is adjusted by using N ₂ gas.

The gas flow rate of this mixed gas was set to 1 l (liter) / min, and the gas passage time to the reaction tube 14 was set to 4
0 hours. Further, the electric furnace 12 heats the inside of the reaction tube 14 to 130 ° C. In addition, 25 g of the flue gas treating agent is dispersed in the absorbent cotton 16 packed in the reaction tube 14.

Under the conditions as described above, the mixed gas is supplied to the reaction tube 1.
After passing through No. 4 for 40 hours, the treating agent dispersed in the absorbent cotton is taken out. After that, the content of S (sulfur) in the treating agent is measured by the CS method by using a CS meter. As the CS meter, for example, EMIA2000 (trade name: manufactured by Horiba Ltd.) is used. SO ₂ in the mixed gas reacts with the Ca (calcium) content in the flue gas treatment agent to produce CaSO ₄ (calcium sulfate). This calcium sulfate is cotton wool 1
Since adhering to 6, S in the treatment agent which has absorbed SO ₂
By measuring the minutes, the calcium utilization rate (%) of the flue gas treatment agent can be obtained. This calcium utilization rate shows desulfurization performance. Therefore, it can be said that the higher the calcium utilization rate is, the higher the desulfurization performance is.

Further, the specific surface areas of the flue gas treating agents of Examples 1 to 20 are measured, and the pore volume and the average pore diameter of several treating agents are measured. here,
The specific surface area is measured by the BET method, and the pore volume and average pore diameter are measured by the BJH method.

As a result of the desulfurization performance test, the values of specific surface area, pore volume and average pore diameter are shown in Tables 1 to 7 below together with the production conditions (starting material and solvent) of each Example.

[0161]

[Table 1]

[0162]

[Table 2]

[0163]

[Table 3]

[0164]

[Table 4]

[0165]

[Table 5]

[0166]

[Table 6]

[0167]

[Table 7]

Table 1 shows Example 1 using only water as a solvent and Example 2 using an aqueous citric acid solution as a solvent.
The result of is shown.

According to Table 1, the treating agent of Example 1 has a calcium utilization rate of 66%, a specific surface area of 25 m ² / g, a pore volume of 0.163 cm ³ / g and an average pore diameter of 13.5 nm.
Met.

In Example 2 using an aqueous citric acid solution as a solvent, Table 1 shows that the treating agent of Example 2-1 had a calcium utilization rate of 37% and a specific surface area of 29 m ^2.
/ G, the pore volume was 0.113 cm ³ / g, and the average pore diameter was 11.3 nm. The calcium utilization factor of the treating agent of Example 2-2 was 38%, and the specific surface area was 28 m ² / g. The calcium utilization of the treating agent of Example 2-3 is 36.
%, Specific surface area 28 m ² / g, pore volume 0.124 c
m ³ / g, average pore diameter was 11.5 nm.

Table 2 shows the results of Examples 3, 4 and 5 in which an aqueous solution of an additive was used as a solvent and a saccharide was used as an additive.

In Example 3 using an aqueous sucrose solution as the solvent, referring to Table 2, the treating agent of Example 3-1 had a calcium utilization rate of 34% and a specific surface area of 26 m ² / g.
The pore volume is 0.075 cm ³ / g, and the average pore diameter is 10.
It was 2 nm. The calcium utilization factor of the treating agent of Example 3-2 was 30%, and the specific surface area was 23 m ² / g. The calcium utilization rate of the treatment agent of Example 3-3 was 27%, and the specific surface area was 20 m ² / g.

In Example 4 using an aqueous glucose solution as the solvent, Table 2 shows that the treating agent of Example 4-1 has a calcium utilization rate of 33% and a specific surface area of 24 m.
² / g, the pore volume was 0.069 cm ³ / g, and the average pore diameter was 10.5 nm. The calcium utilization factor of the treating agent of Example 4-2 was 32%, and the specific surface area was 19 m ² / g. The calcium utilization rate of the treatment agent of Example 4-3 is 29%.
The specific surface area was 18 m ² / g.

In addition, in Example 5 using the sorbitol aqueous solution as the solvent, Table 2 shows that Example 5-1
The treating agent has a calcium utilization rate of 34% and a specific surface area of 29.
m ² / g, pore volume was 0.079 cm ³ / g, and average pore diameter was 10.8 nm. The calcium utilization factor of the treating agent of Example 5-2 was 30%, and the specific surface area was 20 m ² / g. The calcium utilization rate of the treatment agent of Example 5-3 is 29%.
The specific surface area was 19 m ² / g.

Table 3 is an example using a mixed solution of water and an organic solvent as the solvent, and shows the results of Examples 6, 7 and 8 in which glycols were used as the organic solvent.

In Example 6 using EG as the organic solvent, referring to Table 3, the calcium utilization rate of the treating agent of Example 6-1 was 47%, the specific surface area was 26 m ² / g, and the pore volume was 0.155 cm ³ / g, average pore size is 11.0
was nm. The calcium utilization factor of the treating agent of Example 6-2 was 50%, the specific surface area was 26 m ² / g, and the pore volume was 0.
The average pore diameter was 157 cm ³ / g and 11.2 nm. The calcium utilization rate of the treating agent of Example 6-3 is 57%.
And has a specific surface area of 26 m ² / g and a pore volume of 0.175 c
m ³ / g, average pore diameter was 11.4 nm.

In Example 7 using DEG as the organic solvent, Table 3 shows that the treating agent of Example 7-1 had a calcium utilization rate of 40% and a specific surface area of 24 m ² / g.
Met. The calcium utilization factor of the treating agent of Example 7-2 was 44%, the specific surface area was 23 m ² / g, and the pore volume was 0.15.
It was 1 cm ³ / g and the average pore diameter was 11.8 nm. The calcium utilization factor of the treating agent of Example 7-3 was 51%, and the specific surface area was 23 m ² / g.

According to Table 3, in Example 8 using PG as the organic solvent, the treating agent of Example 8-1 had a calcium utilization rate of 38% and a specific surface area of 23 m ² / g. . The calcium utilization rate of the treating agent of Example 8-2 was 4
0%, specific surface area 23 m ² / g, pore volume 0.144
cm ³ / g, average pore diameter was 10.9 nm. The calcium utilization factor of the treating agent of Example 8-3 was 46%, and the specific surface area was 23 m ² / g.

Table 4 is an example using a mixed solution of water and an organic solvent as the solvent, and shows the results of Examples 9, 10 and 11 using ethanolamines as the organic solvent.

In Example 9 using MEA as the organic solvent, referring to Table 4, the treating agent of Example 9-1 had a calcium utilization rate of 43% and a specific surface area of 35 m ² / g. The calcium utilization rate of the treating agent of Example 9-2 is 4
7%, specific surface area 30 m ² / g, pore volume 0.180
cm ³ / g, average pore size was 10.0 nm. The calcium utilization factor of the treating agent of Example 9-3 was 50%, and the specific surface area was 28 m ² / g.

In Example 10 using DEA as the organic solvent, the calcium utilization factor of the treating agent of Example 10-1 was 41%, and the specific surface area was 44 m ² / g.
The calcium utilization rate of the treatment agent of Example 10-2 is 45%,
Specific surface area is 40 m ² / g, pore volume is 0.172 cm ³ /
g, and the average pore diameter was 9.6 nm. Example 10-3
The treatment agent has a calcium utilization rate of 49% and a specific surface area of 3
It was 7 m ² / g.

In Example 11 using TEA as the organic solvent, the treating agent of Example 11-1 had a calcium utilization rate of 40%, a specific surface area of 40 m ² / g and a pore volume of 0.155 cm ^3. / G, and the average pore diameter was 8.2 nm. The calcium utilization rate of the treating agent of Example 11-2 is 4
1%, specific surface area 42 m ² / g, pore volume 0.151
cm ³ / g, average pore size was 8.2 nm. The calcium utilization factor of the treating agent of Example 11-3 was 48%, and the specific surface area was 48 m ² / g.

Table 5 is an example using a mixed solution of water and an organic solvent as a solvent, and shows the results of Examples 12, 13 and 14 using alcohols as the organic solvent.

Example 12 using MA as the organic solvent
In reference to Table 5, the treating agent of Example 12-1
Has a calcium utilization rate of 59% and a specific surface area of 31m²/ G
Met. Calcium utilization rate of treatment agent of Example 12-2
Is 61%, specific surface area is 30m ²/ G, pore volume is 0.1
61 cm³/ G, and the average pore diameter was 13.9 nm.
The calcium utilization rate of the treatment agent of Example 12-3 is 63%.
And the specific surface area is 32m²/ G.

In Example 13 using EA as the organic solvent, the calcium utilization factor of the treating agent of Example 13-1 was 61% and the specific surface area was 31 m ² / g. The calcium utilization rate of the treatment agent of Example 13-2 was 62%, the specific surface area was 30 m ² / g, and the pore volume was 0.175 cm ³ /
g, the average pore diameter was 14.2 nm. Example 13-
The calcium utilization rate of the treating agent of No. 3 was 62%, and the specific surface area was 30 m ² / g.

In Example 14 using IPA as the organic solvent, the treating agent of Example 14-1 had a calcium utilization rate of 52%, a specific surface area of 24 m ² / g and a pore volume of 0.114 cm ^3. / G, the average pore diameter was 12.6 nm. The calcium utilization factor of the treating agent of Example 14-2 was 62%, and the specific surface area was 35 m ² / g. Example 14
The calcium utilization rate of the treating agent of No. -3 was 66%, and the specific surface area was 34 m ² / g. The calcium utilization factor of the treating agent of Example 14-4 was 63%, and the specific surface area was 32 cm ² /
g, pore volume is 0.172 cm ³ / g, average pore diameter is 1
It was 4.0 nm.

In Table 6, as a result of Example 15 in which the silicon dioxide-containing material which is one of the starting materials is a zeolite, the silicon dioxide-containing material is a zeolite and a mixed solution of water and an organic solvent is used as a solvent. , This organic solvent is IPA
As a result of Example 16, the result of Example 17 in which the silicon dioxide-containing material is glass powder and the result in Example 17 in which the silicon dioxide-containing material is glass powder, and a mixed solution of water and an organic solvent is used as a solvent. Example 18 in which is IPA
The results of are shown.

According to Table 6, the calcium utilization factor of the treating agent of Example 15 is 62%, the specific surface area is 24 m ² / g, the pore volume is 0.152 cm ³ / g, and the average pore diameter is 13.1 n.
It was m.

Example 1 using zeolite as the silicon dioxide-containing material and IPA as the organic solvent
In Example 6, the calcium utilization factor of the treating agent of Example 16-1 was 56%, and the specific surface area was 30 m ² / g. The calcium utilization rate of the treatment agent of Example 16-2 was 59%, the specific surface area was 33 m ² / g, the pore volume was 0.163 cm ³ / g,
The average pore diameter was 14.2 nm. The calcium utilization factor of the treating agent of Example 16-3 was 62%, and the specific surface area was 32.
It was m ² / g.

In Example 17 using glass powder as the silicon dioxide-containing material, the treating agent of Example 17-1 had a calcium utilization ratio of 37% and a specific surface area of 15 m ² /
It was g. The calcium utilization factor of the treating agent of Example 17-2 was 42%, and the specific surface area was 17 m ² / g. The calcium utilization factor of the treating agent of Example 17-3 was 48%, and the specific surface area was 26 m ² / g.

Example 18 using glass powder as the silicon dioxide-containing material and IPA as the organic solvent
In Example 18, the calcium utilization factor of the treatment agent of Example 18-1 was 57%, and the specific surface area was 27 m ² / g. The calcium utilization factor of the treating agent of Example 18-2 was 46%, and the specific surface area was 20 m ² / g.

Table 7 shows that, as a result of Example 19 in which only water was used as a solvent and the amount of water was smaller than that in Example 1, a mixed solution of an organic solvent and water as a solvent and an additive aqueous solution was mixed. The results of Example 20 in which is used and the performance test results of the treatment agent of the comparative example are shown.

According to Table 7, the treating agent of Example 19-1 had a calcium utilization rate of 37% and a specific surface area of 27 m ² / g.
The pore volume is 0.115 cm ³ / g, the average pore diameter is 9.2.
was nm. The calcium utilization factor of the treatment agent of Example 19-2 was 54%, the specific surface area was 30 m ² / g, the pore volume was 0.148 cm ³ / g, and the average pore diameter was 9.9 nm. The calcium utilization rate of the treating agent of Example 19-3 is 57.
%, Specific surface area 31 m ² / g, pore volume 0.158 c
m ³ / g, average pore diameter was 11.0 nm.

The calcium utilization factor of the treating agent of Example 20-1 was 41%, the specific surface area was 32 m ² / g, the pore volume was 0.119 cm ³ / g, and the average pore diameter was 11.3 nm. . The calcium utilization factor of the treating agent of Example 20-2 was 45%, and the specific surface area was 33 m ² / g.

Further, the same test was carried out for the special feature slaked lime and the highly reactive slaked lime of Comparative Example, and Comparative Example 1
The calcium utilization rate of slaked lime was 20%, and the specific surface area was 10 m ² / g. The calcium utilization of the highly reactive slaked lime of Comparative Example 2 was 25%, and the specific surface area was 37 m ² /
g, the pore volume was 0.119 cm ³ / g, and the average pore diameter was 5.8 nm (Table 7).

Comparing Example 1 with Example 19, it can be seen that the larger the amount of water as the solvent, the higher the values of pore volume and average pore diameter, and the higher the desulfurization performance. However, from the results of Example 19, the amount of water as the solvent was
It was confirmed that even if the amount was less than 70 parts by weight with respect to 100 parts by weight of the mixture, by reducing the particle size of quick lime used as the starting material, the performance that could be used as a flue gas treatment agent could be achieved. . In addition, Example 1
In No. 9, since the reaction product is powder after the digestion reaction, it is not necessary to perform the drying treatment. Therefore, there are advantages over the first embodiment in terms of manufacturing time and cost.

Further, by adding citric acid, sucrose, glucose, sorbitol or the like as an additive to the solvent in which the quick lime is dispersed, even if the amount of the solvent is reduced, the specific surface area, the pore volume and the average are larger than those in Comparative Example 2. A treatment agent with a large pore size can be obtained and desulfurization performance is also high. The additive is not limited to citric acid and sugar used in the examples, and other sugars having similar properties can be used.

In addition, according to the results of Examples 6 to 8 in which glycols were used as the organic solvent among the examples in which the mixed solution of water and the organic solvent was used as the solvent in which the quicklime was dispersed, both were compared. The specific surface area can be increased and the desulfurization performance is higher than in Example 2. Further, according to the results of Examples 9 to 11 in which ethanolamines were used as the organic solvent, those having an extremely large pore volume were obtained. Further, a product having a large specific surface area and high desulfurization performance can be obtained. Further, according to the results of Examples 12 to 14 in which alcohols were used as the organic solvent, those having a large specific surface area, a large pore volume and a large average pore diameter, and a high desulfurization performance were obtained.

The organic solvent is not limited to the ethanolamines and alcohols used in the examples, but other amines and alcohols having similar properties can be used.

Further, looking at the results of Example 20, even when a solution obtained by mixing a mixed solution of an organic solvent and water with an aqueous additive solution was used as a solvent, the desulfurization performance was high, the specific surface area was large, and the pores were A large volume and a large average pore diameter can be obtained. As the organic solvent, the organic solvent used in the other examples described above can be used. Further, not only these organic solvents but also other organic solvents having similar properties may be used. As for the additive, not only the additive used in the other examples described above but also other additives having the same properties may be used. Further, in Example 20, an example in which the content of triethanolamine in the solvent was 20 ml (Example 20-1) and an amount in which the amount of TEA was 0.4 ml (Example 20-2) was mentioned. However, with respect to this content, if the content is within the range of 0.4 to 20 ml, the same characteristics as the characteristics of the treating agent of the example of Example 20 shown in Table 7 can be obtained. It has been confirmed by the inventors. Similarly, regarding the sorbitol aqueous solution, it has been confirmed that a treating agent having characteristics similar to those of the treating agent of Example 20 can be obtained when used at a concentration within the range of 0.25 to 10% by weight.

Further, according to the results of Examples 15 and 16 produced using zeolite as the starting material, it can be seen that a treating agent having a performance almost equivalent to that of the case of using coal ash can be obtained. Further, when only water is used as the solvent, the larger the amount of water, the higher the performance as the treating agent.
In addition, since the alcohol (IPA) is contained as the solvent, the specific surface area of the obtained treating agent is increased,
It can be seen that the desulfurization performance is also improved.

Further, the treating agents (Examples 17 and 18) produced by using glass powder as the starting material have obtained desulfurization performance to the extent that they can be used as smoke treating agents.
It was found that the treating agent manufactured using coal ash as the starting material has higher desulfurization performance. Further, the desulfurization performance is higher as the amount of water as the solvent is larger. Further, it has been found that the inclusion of alcohol in the solvent increases the specific surface area of the resulting treating agent and improves the desulfurization performance.

Comparing the results of Examples 1 to 20 with the results of Comparative Example 1 and Comparative Example 2, the flue gas treating agent produced by the method of the present invention shows that the special slaked lime and the highly reactive slaked lime. Higher desulfurization performance can be obtained.

Further, the treating agents of Examples 1 to 9 and 12 to 20 having a smaller specific surface area than the highly reactive slaked lime have a higher desulfurization performance than the highly reactive slaked lime. Further, in the examples in which the pore volume and the average pore diameter were measured, the value of either or both of the pore volume and the average pore diameter was higher than that of the highly reactive slaked lime. There is.
Therefore, it is suggested that the desulfurization performance is a value that depends on the pore volume and / or the pore diameter rather than the specific surface area.

Next, Example 17-3 of the above Examples.
An evaluation experiment of the desalination and desulfurization performance of the flue gas treatment agent will be conducted.
In this evaluation experiment, the bag filter test apparatus shown in FIG. 2 is used to examine the desalination and desulfurization performance of the flue gas treatment agent in a state where the atmosphere of the municipal waste incinerator is reproduced (FIG. 2).

The bag filter testing device 30 has a vertical length of 1350.
mm, width 600 mm, and internal volume 0.486 m³
The housing 32 and the heat insulating material wound on the outer wall of the housing 32 (see FIG.
(Not shown). 150m in diameter in the housing 32
m, length 1050 mm, surface area 0.945 m²The ba
G-filter CN5555 (Product name: Teijin Limited) 3
Two 4 are installed. In addition, from the outside of the housing 32 to the inside
The sample introduction pipe 36 and the steam introduction pipe 38 are respectively pipes.
Has been done. The sample introduction pipe 36 and the steam introduction pipe 3
8 is an iron pipe having an inner diameter of 35 mm. In addition, the sample introduction pipe 36
The sample input port 40 is provided in the
The distance from 40 to the bag filter 34 is 1000 mm
is there. Also, the water vapor introduced into the housing 32 is
Humidifier 42 which is a modification of the bread type humidifier manufactured by Hako Electric Co., Ltd.
Generated by using. In addition, the sample introduction pipe 36
HCl gas, SO with treatment agent₂Gas and NO gas
To introduce. Then, the sample introduction pipe 36 and the water vapor introduction
The hot air heated by the burner 44 blows on the pipe 38.
It is set to be impressed. This makes this sample
The introduction pipe 36 reproduces the flue of the refuse incinerator. Also,
The housing 32 has a gas discharge passage through which the bag filter 34 passes.
46 is provided, and the gas discharged from this discharge path 46 is
It passes through the discharge pipe 48. The discharge pipe 48 has a discharge gas
HCl gas concentration measuring device 50 in the gas and SO₂Gas concentration
Each measuring device 52 is installed. HCl gas concentration
In this example, the STACK PROBE CONT is used as the degree measuring device 50.
ROLLERMODEL200SPC (Product name: Nippon Thermo Electron
Co., Ltd. and HCl ANALYZER MODEL15 (trade name: Nippon Service)
-Manufactured by Mo Electron Co., Ltd.). Also, SO
₂As the gas concentration measuring device 52, in this example, SO₂Automatic
Analyzer MODEL711P (trade name: Nippon Thermo Electron Co., Ltd.
Shiki company) is used (Fig. 2).

Next, in this performance test, the flue gas treating agent produced in the above Example 17-3 is used as a sample. Then, as a comparative sample, the special slaked lime of Comparative Example 1 and the highly reactive slaked lime of Comparative Example 2 are used.

The test conditions are shown in Table 8 below.

[0209]

[Table 8]

According to Table 8, the equivalent weight of the sample charged from the sample charging port 40 of the test apparatus is 3 equivalents. Here, 1 equivalent means that the sample is all Ca (OH) ₂ and reacts stoichiometrically with all of the HCl gas and SO ₂ gas introduced into the sample introduction pipe 36 to form CaCl ₂ It is the amount of Ca (OH) ₂ that becomes CaSO ₄ . Therefore, 1
When an equivalent amount of flue gas treatment agent (sample) is introduced, HCl gas concentration measuring device 50 and SO ₂ gas concentration measuring device 52
If the concentrations of the HCl gas and the SO ₂ gas detected in 1 are 0 (ppm), the desalination and desulfurization efficiency of the sample is 100%. When flue gas treatment is performed using slaked lime in the flue where the flue gas of a conventional general garbage incinerator passes, if the concentration of HCl gas in the flue gas is about 1000 ppm, about 3 equivalents of slaked lime are obtained. 90% by adding
A degree of desalination effect is obtained.

As other test conditions, the filtration rate was 0.8 m / min, the HCl gas concentration in the sample introducing pipe 36 was 1000 ppm, and the SO ₂ gas concentration was 200 pp.
m and the NO gas concentration is 100 ppm. Further, the water concentration introduced into the casing 32 as water vapor is 18% by volume. The temperature inside the device is maintained at a temperature between 160 and 170 ° C.

The results of the test are shown in FIGS. 3 and 4.

3 and 4 are characteristic diagrams of desalination efficiency and desulfurization efficiency, in which the efficiency (%) is plotted on the vertical axis and the time (minutes) is plotted on the horizontal axis. In each figure, the solid line is the characteristic curve of the smoke control agent produced in Example 13, the dashed line is the characteristic curve of the special slaked lime of Comparative Example 1, and the dotted line is the characteristic curve of the highly reactive slaked lime of Comparative Example 2. Shown respectively.

Three equivalents of the sample were introduced and the filtration rate was 0.8 m.
As shown in FIG. 3, the desalination efficiency at 80 / min is 80%.
After the lapse of minutes, the efficiency of the treating agent of Example 13 exceeds the efficiencies of the special slaked lime and the highly reactive slaked lime. Moreover, the desulfurization efficiency of the treating agent of Example 13 was much higher than that of the special slaked lime and the highly reactive slaked lime before 30 minutes had passed (FIG. 4).

As a result, with the smoke control agent of Example 17-3, when 3.0 equivalents of the sample was introduced and the filtration rate was 0.8 m / min, both the desalination efficiency and the desulfurization efficiency were comparative examples. It has been found that it shows significantly superior properties to the special slaked lime and highly reactive slaked lime. In addition, comparing the calcium content per unit amount of the flue gas treatment agent of Example 17-3 with the calcium content per unit amount of special slaked lime and highly reactive slaked lime, it was found to be contained as the starting material of the treatment agent. The calcium content in the treating agent of Example 17-3 is small by the amount of the silicon dioxide-containing material. Therefore, Example 17
Desalination and desulfurization efficiency of calcium contained in the treating agent of No. 3 per unit weight, that is, the calcium utilization rate is higher than that estimated from the results shown in the figure. It is thought that it exceeds the utilization rate.

Further, it is empirically known that the desalting efficiency becomes higher as the specific surface area of the sample increases. And from the results of this evaluation experiment and the above-mentioned performance test,
It is assumed that the desulfurization efficiency is a performance that depends on the pore volume and / or the pore diameter.

The flue gas treating agent produced by the method of the present invention has a desalination effect equivalent to or higher than that of the highly reactive slaked lime, and has a desulfurization effect higher than that of the special slaked lime and the highly reactive slaked lime. Is obtained. Therefore, it is possible to efficiently remove the harmful gases HCl gas and SO ₂ gas in the flue gas discharged from the incinerator of general garbage. Then, such a flue gas treating agent can be manufactured easily and at low cost.

Although the flue gas treating agent of the present invention was experimentally produced by using the mortar mixer in the above-mentioned embodiment, when the flue gas treating agent which is the actual product is produced,
An apparatus conventionally used for producing slaked lime can be used.

[0219]

As is apparent from the above description, according to the method for producing a flue gas treating agent of the present invention, quicklime 50 to 9
10 parts by weight of a mixture containing 9.9 parts by weight and 0.01 to 50 parts by weight of silicon dioxide, a stoichiometric amount of water for converting quicklime into slaked lime, and a solvent for dispersing the mixture 10 .About.200 parts by weight. This allows quicklime to be digested without fear of indigestion. Further, the heat of digestion generated during the digestion of quicklime can be used to react quicklime with silicon dioxide to produce amorphous calcium silicate, and the calcium silicate can be contained in the obtained slaked lime. As a result, a flue gas treatment agent having a high desalination and desulfurization effect can be obtained. Further, the above-mentioned digestion reaction and reaction for producing calcium silicate can be carried out only by adding water necessary for digestion and a solvent for dispersion to a mixture of quicklime and a silicon dioxide-containing substance. Therefore, it is not necessary to heat the reaction system from the outside to cure the reaction system. Therefore, the cost and time required for producing the flue gas treatment agent can be reduced as compared with the conventional case.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a test apparatus used for explaining a performance test of a flue gas treatment agent.

FIG. 2 is a schematic configuration diagram of a bag filter test apparatus used for investigating desalination and desulfurization performance of a flue gas treatment agent.

FIG. 3 is a characteristic diagram of desalination efficiency in an evaluation experiment using a bag filter.

FIG. 4 is a desulfurization efficiency characteristic diagram in an evaluation experiment using a bag filter.

[Explanation of symbols]

10: Test device 12: Electric furnace 14: Reaction tube 16: Absorbent cotton 18: Gas concentration measuring devices 20a, 20b, 20c, 20d, 20e: Flowmeter 22a: SO ₂ gas gas cylinder 22b: NO gas gas cylinder 22c: CO ₂ Gas cylinder 22d of gas: Gas cylinder 22e of O ₂ gas: Gas cylinder 24 of N ₂ gas: Humidifier 26: Mixer 28: Gas supply pipe 30: Bag filter test device 32: Case 34: Bag filter 36: Sample introduction pipe 38 : Water vapor introducing pipe 40: Sample inlet 42: Humidifier 44: Burner 46: Exhaust passage 48: Exhaust pipe 50: HCl gas concentration measuring device 52: SO ₂ gas concentration measuring device

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI B01J 20/30 (72) Inventor Atsushi Sugimura 2-1 Gobetsu, Ebetsu City, Hokkaido 2-1 Hokkaido Electric Power Company Research Institute (72) Inventor Tatsuo Murakami, 3751 Akasaka-cho, Ogaki-shi, Gifu Ueda Lime Manufacturing Co., Ltd. (72) Inventor Tsutomu Imai 3751, Akasaka-cho, Ogaki-shi, Gifu Ueda Lime Manufacturing Co., Ltd. (56) Reference JP-A-58-166933 (JP) , A)

Claims (15)

(57) [Claims] 1. A mixture 1 containing quicklime and silicon dioxide.
A stoichiometry for converting the quicklime into slaked lime, based on 100 parts by weight of the mixture, and 50 to 99.9 parts by weight of the quicklime and 0.01 to 50 parts by weight of the silicon dioxide. A method for producing a flue gas treatment agent comprising slaked lime containing amorphous calcium silicate, which comprises the step of adding 10 to 200 parts by weight of a solvent for dispersing the mixture and a specific amount of water. 2. The method for producing a flue gas treatment agent according to claim 1, wherein the mixture is 50 to 99.9 parts by weight of quick lime and a silicon dioxide-containing material containing 0.01 to 50 parts by weight of silicon dioxide. A method for producing a flue gas treatment agent, which is obtained by mixing 3. The method for producing a flue gas treatment agent according to claim 2, wherein the silicon dioxide-containing material is replaced with the silicon dioxides 1 to 20.
A method for producing a flue gas treatment agent, which comprises mixing so as to be part by weight. 4. The method for producing a flue gas treatment agent according to claim 1 or 2, wherein the solvent is vaporized by the heat of digestion of the quicklime and does not remain in the flue gas treatment agent at the end of the reaction. A method for producing a flue gas treatment agent, which is characterized by being added. 5. The method for producing a flue gas treatment agent according to claim 1, 2 or 4, wherein the solvent is a mixed solution of water and an organic solvent. Production method. 6. The method for producing a flue gas treatment agent according to claim 5, wherein the organic solvent is one or more organic solvents selected from the group of organic solvents consisting of glycols, amines and alcohols. A method for producing a flue gas treatment agent, comprising: 7. The method for producing a smoke treatment agent according to claim 5 or 6, wherein the amount of the solvent is 10 parts by weight or more and 100 parts by weight or less. Manufacturing method. 8. The method for producing a flue gas treatment agent according to claim 5, wherein the volume of the organic solvent is not more than twice the volume of water in the solvent. A method for producing a flue gas treatment agent, comprising: 9. The method for producing a flue gas treatment agent according to claim 1 or 2, wherein the solvent is one or more additives selected from the group of additives consisting of citric acid and saccharides in water. A method for producing a flue gas treatment agent, which comprises using an aqueous solution of an additive in which is dissolved. 10. The method for producing a flue gas treatment agent according to claim 9, wherein the additive is 0.1 to 100 parts by weight of the mixture.
To 20 parts by weight of the flue gas is dissolved in the flue gas treatment agent. 11. The method for producing a flue gas treatment agent according to claim 9 or 10, wherein the amount of the solvent is 10 parts by weight or more and 100 parts by weight or less. Method. 12. The method for producing a flue gas treatment agent according to claim 1 or 2, wherein the solvent is a solution in which an additive is dissolved in a mixed solution of water and an organic solvent. Manufacturing method of flue gas treatment agent. 13. The method for producing a flue gas treating agent according to claim 1 or 2, wherein the solvent is water. 14. The method for producing a flue gas treatment agent according to claim 13, wherein the amount of water is 70 parts by weight or more and less than 200 parts by weight. 15. The method for producing a flue gas treatment agent according to claim 13, wherein the amount of water is 10 parts by weight or more and less than 70 parts by weight.