JP2022044571A - Manufacturing method of cement, cement manufacturing system, manufacturing method of cement hardened material - Google Patents

Abstract

To provide a cement manufacturing method capable of effectively utilizing a biomass ash, while suppressing an increase of a chlorine content rate of a generated cement hardened material, a cement manufacturing method and a cement manufacturing system.SOLUTION: A cement manufacturing method of the present invention comprises: a step (a) of classifying a biomass ash into coarse powder and fine powder; and a step of charging the coarse powder obtained in the step (a) to at least any one of a cement clinker raw material charged into a cement kiln, a cement clinker obtained from the cement kiln, or a cement after pulverization treatment to the cement clinker.SELECTED DRAWING: Figure 2

Description

The present invention relates to a cement manufacturing method and a cement manufacturing system, and more particularly to a cement manufacturing method and a cement manufacturing system using biomass ash as a cement raw material or the like. The present invention also relates to a method for producing a hardened cement product using biomass ash.

Incinerator ash generated by incineration of municipal waste is desired to be recycled as a raw material for cement, etc. against the background of the tightness of disposal sites in recent years. In addition, the construction and operation of biomass power generation facilities are progressing due to various efforts toward the spread of renewable energy, and the amount of incineration ash (biomass ash) generated by biomass power generation is also increasing. Therefore, it is expected that biomass ash will be recycled as a raw material for cement as well as incinerated ash such as municipal waste.

In relation to such a problem, for example, in Non-Patent Document 1 below, it is considered to apply biomass ash to a cement admixture.

Takahiro Sagawa et al., "Application of Woody Biomass Incinerator Ash to Cement Admixtures", Abstract of the 70th Cement Technology Conference, 2016 [1307]

In Non-Patent Document 1, biomass ash is used as it is as a cement admixture. However, according to this method, since the biomass ash contains a large amount of chlorine, the chlorine content of the concrete using the obtained cement exceeds the regulation value, and in some cases, rebar corrosion may occur. ..

An object of the present invention is to provide a cement manufacturing method and a cement manufacturing system capable of effectively utilizing biomass ash while suppressing an increase in the chlorine content of the produced hardened cement product.

The cement manufacturing method according to the present invention is
Step (a) of classifying biomass ash into coarse powder and fine powder,
The coarse powder obtained in the step (a) is applied to at least one of a cement clinker raw material to be charged into a cement kiln, a cement clinker obtained from the cement clinker, or a cement after crushing the cement clinker. It is characterized by having a step (b) of charging.

As described above, since the biomass ash has a high chlorine content, it is directly added to a cement clinker raw material, a cement clinker (hereinafter, both may be collectively referred to as “cement raw material”) or cement. In addition, the chlorine regulation value in cement may be exceeded, leading to reinforcement corrosion.

Of the biomass ash, the coarse powder having a relatively large particle size has a lower content of calcium, sulfur, chlorine, and carbon than the fine powder having a relatively small particle size, and has a composition close to that of coal ash. Therefore, when used as a clinker raw material, homogeneity with that of a conventional clinker raw material can be ensured. In particular, since the content of sulfur and chlorine is low, it is difficult to generate coaching in the cement kiln, and it is difficult to increase the load on the chlorine bypass. Further, even when it is used as a mixed material of cement, it has an effect that the quality of cement can be homogenized because the content of calcium, sulfur, chlorine and carbon is low.

As a specific method of the above step (b), it is put into the raw material mixing system equipment such as a mixer and a crusher for preparing the raw material of the cement cleaner, and to the preheater top and the calcination furnace before the cement kiln (rotary kiln). , Put into the cement kiln kiln butt, Put into the front of the cement kiln kiln, Put into the cleaner cooler to cool the cement clinker obtained by firing, Crushing device (mill) to crush the cement cleaner. It can be put into a mixing machine, put into a mixer for producing mixed cement, put into a concrete mixer, and the like. That is, the coarse powder of biomass ash obtained in the step (a) can be added to various stages during cement production, and can be suitably used as a raw material for cement clinker or a cement mixture.

In the following, when the term "mixed material" is used in the present specification, it means a material to be added to cement clinker or cement regardless of the cement manufacturing stage.

Therefore, by utilizing the difference in characteristics such as the chemical composition of the classified biomass ash (that is, coarse powder and fine powder) obtained through the step (a), the influence on the clinker characteristics and the clinker manufacturing process and the cement characteristics can be obtained. All or part of the coarse powder or fine powder can be added to the raw material or mixture of cement clinker while considering the effect. As a result, the composition and characteristics of the cement clinker and cement are different from those in which the raw biomass ash powder is added as it is.

It should be noted that at least a part of the coarse powder obtained in the step (a) may be added to the cement raw material or cement, and it is not always necessary that all the coarse powder is added to the cement raw material or cement. The residual coarse powder can also be used, for example, as a fine aggregate.

This step (a) is preferably carried out on biomass ash (preferably dry ash) in a state where water has not been added and the hydrate formation reaction has not progressed. For example, when the biomass ash is wet ash and aggregates or hydrates are formed, there is a possibility that a large amount of chlorine is contained on the coarse powder side even when the classification is performed. ..

As used herein, the term "dry ash" refers to biomass ash that has been recovered in a dry state, has not been watered by the time it is classified, and has not aggregated or formed hydrates. Point to. Further, the dry ash is in a state where a large amount of water is added and dispersed even if water is added before the classification treatment, and a case where hydrate is not formed by long-term storage is also included. Further, in the present specification, "wet ash" is, for example, water-cooled or sprinkled with water-cooled or sprinkled with main ash which is an incineration residue discharged from the bottom of an incinerator or fly ash collected by a dust collector or the like. Refers to those collected in a state containing ash and those that have been dried. Generally, the wet ash has a water content of 15% by mass or more.

The cement manufacturing method includes a step (c) of charging the fine powder obtained in the step (a) into at least one of the cement clinker and the cement after the crushing treatment for the cement clinker. death,
The step (b) may be a step of putting the coarse powder obtained in the step (a) into a cement clinker raw material to be put into a cement kiln.

Further, the cement manufacturing method includes a step (c) of feeding the fine powder obtained in the step (a) into the cement clinker raw material.
The step (b) may be a step of putting the coarse powder obtained in the step (a) into a cement clinker raw material to be put into a cement kiln.

Biomass ash has low activity, but finer powder with smaller particle size has higher activity and higher alkali metal content. Therefore, as in the above method, the fine powder obtained after classifying the biomass ash is mixed with the cement raw material or cement to activate the pozzolan reaction. Therefore, the strength of the hardened cement product is higher than that in the case where the biomass ash before classification (hereinafter, may be referred to as “raw ash”) is added to the cement raw material or cement.

If all of the fine powder and coarse powder obtained in the step (a) are simply added to the cement clinker raw material without performing the washing step (d) described later, it is the same as adding the raw ash. Therefore, it is excluded from the present invention.

The cement manufacturing method includes a step (d) of washing the biomass ash with water.
The step (c) may be a step of adding the fine powder after being washed with water by the step (d).

According to the studies by the present inventors, biomass ash contains harmful components in cement and concrete, and the quality is not stable due to the presence of easily reactive calcium components. Therefore, cement raw materials and the like are used. There was a concern that it would be restricted by the recycling of resources. On the other hand, according to the above method, the biomass ash that has undergone the washing step (d) is charged into the cement raw material (cement clinker raw material, cement clinker) or cement, so that the charged biomass ash is chlorine, which is a cement repellent component. Is efficiently removed, and the corrosion of the reinforcing bars of concrete as a hardened cement product can be suppressed. In addition, heavy metals such as selenium and chromium, which may pollute the environment, and easily reactive calcium oxide and calcium hydroxide are reduced, and the quality of cement can be homogenized. When the biomass ash that has undergone the water washing step (d) is used as a cleanser raw material, clogging due to adhesion of a low melting point substance to the preheater, the kiln bottom, and the kiln is suppressed.

The water washing step (d) includes a step (d1) of adding water to biomass ash to form a slurry, a step of supplying water washing water to the slurry and washing it with water (d2), and dehydration of the slurry after washing with water. It is preferable to have the step (d3). Chlorine and heavy metals can be removed because the dehydrated product is obtained by washing the slurry with water and then dehydrating it.

The step (b) can also be a step in which the coarse powder obtained by classifying the biomass ash after the washing treatment in the step (d) is added to the cement raw material or cement. I do not care.

In the step (d), only the fine powder obtained in the step (a) may be washed with water.

According to the study by the present inventors, it was confirmed that most of the chlorine content contained in the biomass ash is contained in the fine powder when the coarse powder obtained after classifying the biomass ash and the fine powder are compared. Therefore, according to the above method, chlorine contained in the biomass ash can be efficiently removed while suppressing the amount of water used for washing with water.

The cement manufacturing method includes a step (e) of pulverizing at least a part of the coarse powder obtained in the step (a).
The step (b) is a step of putting the coarse powder after being crushed by the step (e) into a cement clinker obtained from the cement kiln or a cement after crushing the cement clinker. It doesn't matter.

According to this method, the coarse powder is crushed and put into a cement clinker or cement in a state where the particle size is made fine, so that the strength of the cement can be increased. The crushing of the coarse powder may be performed at the same time as the crushing of the cement clinker.

The cement manufacturing method may include a step (f) of oxidizing the biomass ash during or after the execution of the step (d).

According to the above method, since the pH at the time of washing with water is adjusted to the acidic side, chlorine can be removed more efficiently. In addition, even if the biomass ash contains a large amount of easily reactive calcium oxide or calcium hydroxide, it can be replaced without omission in the form of calcium carbonate or calcium sulfate, so that the quality such as the fluidity of cement is uniform. Can be transformed into.

In the step (f), an acid solution may be added during washing of the biomass ash, or a carbon dioxide (CO ₂ ) -containing gas may be blown into the biomass ash, or the CO ₂ -containing gas may be added to the biomass ash after the washing treatment. It does not matter if it is blown into it. In particular, by using the combustion exhaust gas of cement kiln, the bleed gas of chlorine bypass, and the combustion exhaust gas of biomass incineration equipment and biomass power plant as CO ₂ containing gas, CO ₂ contained in these gases can be changed to calcium carbonate. Since it can be fixed to biomass ash, it can be expected to reduce CO ₂ emissions. In addition, harmful gases such as sulfur acid substances (SO _x ) contained in the exhaust gas can be converted into calcium sulfate and immobilized on biomass ash.

Further, especially in the step (f), by carbonating the biomass ash during the washing with water according to the step (d), the calcium content contained in a large amount in the waste liquid after washing with water can be precipitated as calcium carbonate, so that scale is generated. It is suppressed. As a result, it is possible to prevent the piping for wastewater treatment from being blocked.

The cement manufacturing method may include a step (g) of removing unburned carbon contained in the biomass ash during the execution of the step (d).

Biomass ash (raw ash) can contain a lot of unburned carbon. For this reason, when biomass ash containing a large amount of carbon is used as a raw material for cement clinker, the temperature of the preheater may rise, and when used as a mixed material, darkening of concrete and a water reducing agent may be adsorbed on carbon. May cause a decrease in liquidity.

On the other hand, according to the above method, unburned carbon can be removed during washing with water, so that the above-mentioned problems can be suppressed. Specifically, the amount of unburned carbon contained may be reduced by performing flotation by mixing a decombustible carbon agent such as oil or a surfactant.

The step (c) may be a step of mixing at least one of a latent hydraulic substance and pozzolan in addition to the fine powder.

When fine powder after classification of biomass ash is added during cement production, cement having a high alkali metal content can be produced. When this cement and aggregate are mixed to form concrete, the alkali-reactive minerals (amorphous silica, etc.) in the aggregate react with the alkali metal to generate water-absorbent alkaline silica gel, which causes cracks in the concrete. (Alkaline aggregate reaction).

On the other hand, according to the above method, latent hydraulic substances such as blast furnace slag and pozzolan (including natural pozzolan such as silica stone powder and stone powder and artificial pozzolan such as fly ash and calcined clay) are combined with fine powder. Since it is added, the reaction of alkaline aggregate can be suppressed.

However, by using an aggregate that does not easily cause an alkaline aggregate reaction as the aggregate that is mixed during the production of concrete, it is possible to suppress the alkaline aggregate reaction without mixing latent hydraulic substances or pozzolan. Is possible.

The step (a) is preferably a step of classifying with a classification point of 20 μm or more and 100 μm or less. This is particularly efficient because chlorine and sulfur are predominantly distributed to the fine powder side.

The cement manufacturing system according to the present invention is
A classification facility that classifies biomass ash into coarse powder and fine powder,
Cement clinker A cement kiln that fires raw materials to produce cement clinker,
It is equipped with a first crushing facility that crushes the cement clinker obtained from the cement kiln to produce cement.
The coarse powder obtained by the classification device is charged into at least one of the cement clinker raw material, the cement clinker obtained from the cement kiln, or the cement obtained from the first crushing facility. It is characterized by that.

According to the above system, the coarse powder obtained after classifying the biomass ash is added to the cement raw material or cement, so that the chlorine content is lower than when the raw ash is mixed with the cement raw material or cement, and the reinforcing bar is reinforced. Invitation of corrosion can be suppressed.

At this time, the coarse powder obtained by the classification device may be charged into the first crushing equipment.

According to this, the step of crushing the coarse powder can be performed in parallel with the step of crushing the cement clinker. As a result, the strength of the cement can be increased without providing a separate crushing facility.

Further, the cement manufacturing system includes a second crushing facility for crushing the coarse powder classified by the classifying facility.
The coarse powder after being crushed by the second crushing facility is charged into at least one of the cement clinker obtained from the cement kiln or the cement obtained from the first crushing facility. It doesn't matter.

Further, the method for producing a hardened cement product according to the present invention is as follows.
Step (a) of classifying biomass ash into coarse powder and fine powder,
In the step (e) of crushing the coarse powder obtained in the step (a),
It is characterized by having the step (b) of adding the coarse powder after pulverization obtained in the step (e), the cement after the pulverization treatment, and water.

Also by this method, for the same reason as described above, it is possible to obtain a hardened cement product having a lower chlorine content and higher strength than the case where the raw ash before classification is added. Examples of the hardened cement product include concrete and mortar. In either case, in addition to the pulverized coarse powder, cement, and water, an appropriate aggregate may be appropriately added. After these are added, they may be mixed as a concrete admixture in a concrete mixer, for example.

According to the present invention, it is possible to effectively utilize biomass ash in cement production while suppressing an increase in the chlorine content of the produced hardened cement product.

It is a figure which shows typically the processing flow of the cement manufacturing method in 1st Embodiment. It is a block diagram which shows typically the structure of the cement manufacturing system in 1st Embodiment. It is a graph which shows the particle size distribution of the incinerator fly ash from the biomass power generation facility P1 of Example 1. It is a block diagram schematically showing another structure of the cement manufacturing system in 1st Embodiment. It is a figure which shows typically the processing flow of the cement manufacturing method in 2nd Embodiment. It is a figure which shows typically an example of the detailed processing flow of a water washing process. It is a block diagram which shows typically the structure of the cement manufacturing system in 2nd Embodiment. It is a block diagram schematically showing an example of the structure of the washing equipment provided in the cement manufacturing system of FIG. 7. It is a drawing which shows another example of the processing flow of the cement manufacturing method in 2nd Embodiment schematically. It is a block diagram schematically showing an example of the structure of a water washing facility. It is a figure which shows typically the processing flow of the cement manufacturing method in 3rd Embodiment. It is a block diagram which shows typically the structure of the cement manufacturing system in 3rd Embodiment. It is a block diagram schematically showing another structure of the cement manufacturing system in 3rd Embodiment. It is a block diagram which shows typically the structure of the cement manufacturing system in another embodiment.

[Biomass ash]
The present invention relates to a technique for using biomass ash in the production of cement. First, the biomass ash to which the present invention is applied will be described.

The biomass ash to which the present invention is applied generally includes incinerator ash of biomass, and includes, for example, incinerator ash of plants and bamboo and incinerator ash of food residue. The biomass ash contains water-soluble alkali metal chloride, alkali metal sulfate, and alkali metal carbonate. Compared to municipal waste incineration ash and chlorine bypass dust, biomass ash has the advantage that the proportion of alkali metal sulfate and alkali metal carbonate is large and the concentration of alkaline chlorine is low.

Since the biomass ash is an incinerator ash, it contains a glass component having pozzolan reactivity like coal ash. Among the biomass ash, the incinerated ash of vegetation and bamboo has a relatively high content of K ₂ O, and some of them contain potassium (K ₂ O) embedded in the glass phase. Therefore, since biomass ash has high activity when used as a mixed material, it is preferable to use it at the time of cement production.

The content of K ₂ O in the biomass ash is preferably 2% by mass to 10% by mass, more preferably 3% by mass to 8% by mass, and further preferably 3% by mass to 5% by mass. More preferred. If the K ₂ O content of the biomass ash is less than 2% by mass, the strength of the cement when used as a mixed material may be low, and the required amount as a material to be added to the cement is secured in the first place. It may not be possible. On the other hand, when the K ₂ O content of biomass ash exceeds 10% by mass, the amount used as a raw material for cement clinker is limited, and the occurrence of alkaline aggregate reaction when used as a mixed material increases. There is a risk.

The total alkali concentration contained in the biomass ash is preferably 2% by mass to 11% by mass, more preferably 3% by mass to 6% by mass in terms of R ₂ O (R ₂ O = Na ₂ O + 0.658 × K ₂ O). .. The sulfur oxide (SO ₃ ) concentration contained in the biomass ash is preferably 0.5% by mass to 6% by mass, more preferably 1% by mass to 5% by mass.

In a biomass power plant, co-firing of biomass and coal may be carried out, and the biomass ash to which the present invention is applied includes ash generated when such co-firing is carried out. However, since coal ash obtained by burning coal generally has a low K ₂ O content, the activity of biomass ash differs depending on the amount of coal used during co-firing. Therefore, from the viewpoint of recycling as a mixed material at the time of cement production, in the case of co-firing with coal, it is preferable that the ash is obtained from a fuel having a biomass ratio of 50% by mass or more.

As the biomass ash to which the present invention is applied, palm coconut ash (PKS ash) obtained by using palm coconut husk as a fuel is also preferably exemplified among the incinerated ash of vegetation and bamboo. Palm palm husks are a by-product of palm oil production and are primarily used in the natural biomass energy industry. Palm coconut shell is a yellowish brown fibrous substance with low ash content, its particle size is about 5 mm to 40 mm, and its calorific value is about 4000 Kcal / kg. Therefore, in energy production using renewable resources, palm coconut husks. In recent years, shells have been increasingly used as fuel for biomass power generation.

Generally, there are stoker type and fluidized bed type combustion furnaces for biomass power generation, but in fluidized bed type and pressurized fluidized bed type combustion furnaces, limestone is added to perform desulfurization in the furnace. Will be done. Therefore, the biomass ash from such a combustion furnace contains a large amount of calcium component and sulfur component, and for example, the CaO content is generally 5% by mass to 45% by mass. The morphology of the Ca compound derived from the added limestone includes forms such as CaO (quick lime), Ca (OH) ₂ (slaked lime), CaCO ₃ (limestone), and CaSO ₄ (plaster).

The CaO content of the biomass ash to which the present invention is applied is preferably 10% by mass to 40% by mass, preferably 15% by mass to 30% by mass, from the viewpoint of the strength of cement when recycled as a mixed material. It is more preferable to have.

The ash type of the biomass ash to which the present invention is applied may be the main ash that remains unburned at the bottom of the combustion furnace of biomass power generation, or soot dust that is contained in the combustion exhaust gas and floats as a gas is collected by a dust collector. It does not matter if it is the fly ash obtained by the above. Of these, fly ash is preferable because it has a higher concentration of alkali metal and chlorine, and chlorine is easily separated by classification or washing with water, which is efficient.

Further, the biomass ash is preferably dry ash. Biomass ash that has been sprayed with water once may become granular, or chlorine may be incorporated into the produced hydrate, making it difficult to separate chlorine by classification or washing with water. As the dry ash, for example, it is preferable that Friedel's salt or ettringite, which is a hydrate, is not detected by powder X-ray diffraction. Alternatively, the water content is preferably 10% by mass or less, and more preferably 5% by mass or less. Alternatively, the ignition loss is preferably 10% or less. The water content can be determined as the mass reduction rate when dried at 105 ° C. The ignition loss can be determined as the mass loss rate when the object dried at 105 ° C. is heated at 975 ° C.

Further, the structural water amount of the hydrate in the biomass ash may be obtained as the hydrate production amount by subtracting the decarbonation amount by calcium carbonate from the ignition loss. The amount of hydrate produced is preferably 5% or less, more preferably 3% or less.

The particle size of the biomass ash is, for example, preferably 200 μm or less, more preferably 150 μm or less, and further preferably ₉₀ μm or less, which increases the strength of the cement. The particle size can be measured by using a laser diffraction / scattering type particle size distribution measuring device, for example, by using ethanol as a dispersion medium with MW3300EXII manufactured by Microtrac Bell, and measuring after ultrasonic dispersion for 1 minute. can. The D ₅₀ value means the particle size at a cumulative 50% in the volume-based particle size distribution.

[First Embodiment]
The cement manufacturing method and the first embodiment of the cement manufacturing system will be described. FIG. 1 is a drawing schematically showing a processing flow of the cement manufacturing method in the present embodiment. FIG. 2 is a block diagram schematically showing the structure of the cement manufacturing system according to the present embodiment.

The cement manufacturing system 1 shown in FIG. 2 includes a raw material tank 3 in which the cement clinker raw material Y1 is stored, a powder storage tank 5 in which the biomass ash B1 is stored, a clinker manufacturing facility 10, a classification facility 20, and first crushing. It is equipped with equipment 30. The clinker manufacturing facility 10 is a facility for firing the cement clinker raw material Y1 to generate the cement clinker Cn1, and is a preheater that preheats the cement clinker 12 for firing and the cement clinker raw material Y1 before being charged into the cement kiln 12. 11 and a clinker cooler 13 for cooling the cement clinker Cn1 after firing.

As shown in FIG. 1, the cement manufacturing method of the present embodiment includes a step S10 for classifying the biomass ash B1 and a step S20 for adding or adding the classified biomass ash B1 to a cement raw material or the like. In the following, the charging or adding process is collectively referred to as a “loading” process.

(Classification step S10)
The biomass ash B1 stored in the powder storage tank 5 is classified into coarse powder B1C having a coarse particle size and fine powder B1F having a fine particle size based on a predetermined classification point by the classification equipment 20. The classification point defined in the classification step S10 is preferably 20 μm or more and 100 μm or less, more preferably 30 μm or more and 90 μm or less, and particularly preferably 38 μm or more and 75 μm or less.

The classification equipment 20 is not particularly limited as long as it is a device capable of classifying the biomass ash B1 at the classification points on the order of μm as described above. Etc. can be preferably used, and particularly from the viewpoint of classification accuracy, it is preferable to use a cyclone type air separator, a vortex type centrifugal classification device, a sieving device and the like. When washing with water, it is efficient to perform it in a wet manner.

In the fluidized bed type incinerator, sand containing quartz as a main component as a fluidized medium and limestone for desulfurization are put into the incinerator. Therefore, the fly ash of biomass ash from such an incinerator includes relatively coarse-grained melt-solidified and aggregated glass and sand-derived substances, and relatively fine-grained volatile alkali metal salts and the above-mentioned limestone-derived substances. And are included. Therefore, when the particle size distribution of biomass ash is expressed by frequency, if the classification point is set between the peaks on the fine grain side and the peaks on the coarse grain side, chlorine, sulfur, and calcium can be efficiently separated. ..

FIG. 3 is a graph showing the particle size distribution of incinerated fly ash from the biomass power generation facility P1 of Example 1 described later. According to the graph of FIG. 3, it is confirmed that peaks appear on the fine grain side and the coarse grain side, respectively. It is considered that the fine grain side is derived from limes and alkali metal salts, and the coarse grain side is derived from quartz or glass. Therefore, it can be seen that chlorine, sulfur, and calcium can be efficiently separated by classifying the particle size of the region between these mountains (the region of the valley) as the classification point. The fluidized bed incinerator is equipped with a boiler, an air preheater, equipment to recover incinerated ash settled in a high-temperature gas flow path, incinerator ash recovery equipment using a cyclone, and incinerator ash recovery equipment using a bag filter. It may be incinerated. Since the particle size of the incinerator ash collected by these collection facilities is different, it is possible to replace them with a classification device by separately collecting them.

The classification facility 20 may be provided with a storage tank for biomass ash B1. Further, a supply device for quantitatively supplying the biomass ash B1 from the storage tank to the classification facility 20 may be attached. These storage tanks and supply devices may be appropriately used depending on the state of the received biomass ash B1.

Examples of the classification in the classification step S10 include the activity index of the fine powder B1F, the yield of the fine powder B1F, the chlorine concentration, the sulfur oxide concentration, and the calcium oxide concentration of the fine powder B1F and the coarse powder B1C.

The activity index of the fine powder B1F obtained in the classification step S10 is higher than that of biomass ash (raw ash) B1, typically 70% or more in 7 days, 65% or more in 28 days, and more typically. Will be 75% or more in 7 days and 70% or more in 28 days.

The activity index contained in the biomass ash B1 (B1C, B1F, etc.) can be measured by a well-known method, and for example, a method based on JIS A 6201: 2015 “Fly ash for concrete” is preferably exemplified.

The yield of the fine powder B1F is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, and further preferably 30% by mass to 60% by mass. The yield of the fine powder B1F may be the ratio of the total mass of the obtained fine powder B1F to the total mass of the biomass ash B1 before the execution of the classification step S10. On the other hand, the yield of the crude powder B1C is preferably 20% by mass to 90% by mass, more preferably 30% by mass to 80% by mass, and further preferably 40% by mass to 70% by mass. ..

The chlorine concentration ratio of the fine powder B1F to the coarse powder B1C is preferably 4 or more, more preferably 8 or more, and further preferably 12 or more. The chlorine concentration of the fine powder B1F is, for example, typically 0.2% by mass to 2% by mass, and more typically 0.3% by mass to 1.5% by mass. On the other hand, the chlorine concentration of the crude powder B1C is typically reduced to 0.01% by mass to 0.2% by mass, and more typically reduced to 0.02% by mass to 0.1% by mass. To.

The chlorine concentration contained in the biomass ash B1 (B1C, B1F, etc.) can be measured by a well-known method, and for example, a method of measuring by a potentiometric titration method after acid decomposition treatment is preferably exemplified.

The total alkali concentration ratio of the fine powder B1F to the coarse powder B1C is preferably 1.05 or more, preferably 1.1 or more in terms of R ₂ O (R ₂ O = Na ₂ O + 0.658 × K ₂ O). More preferably, it is more preferably 1.2 or more. The total alkali concentration of the fine powder B1F is, for example, typically 2% by mass to 10% by mass, and more typically 3% by mass to 8% by mass. On the other hand, the total alkali concentration of the crude powder B1C is typically reduced to 0.5% by mass to 6% by mass, and more typically to 2% by mass to 5% by mass.

The total alkali concentration contained in the biomass ash B1 (B1C, B1F, etc.) can be measured by a well-known method, and for example, a method based on JISR 5204 "Fluorescent X-ray analysis method of cement" is preferably exemplified. To.

The sulfur oxide concentration ratio of the fine powder B1F to the coarse powder B1C is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more. The sulfur oxide concentration of the fine powder B1F is, for example, typically 1% by mass to 6% by mass, and more typically 2% by mass to 5% by mass. On the other hand, the sulfur oxide concentration of the crude powder B1C is typically reduced to 0.01% by mass to 2% by mass, and more typically to 0.05% by mass to 1% by mass.

The sulfur oxide concentration contained in the biomass ash B1 (B1C, B1F, etc.) can be measured by a well-known method, and for example, a calibration curve method using a fluorescent X-ray apparatus is preferably exemplified.

The calcium oxide concentration ratio of the fine powder B1F to the coarse powder B1C is preferably 1.5 or more, more preferably 2 or more, and further preferably 3 or more. The calcium oxide concentration of the fine powder B1F is, for example, typically 8% by mass to 40% by mass, and more typically 15% by mass to 35% by mass. On the other hand, the calcium oxide concentration of the crude powder B1C is typically reduced to 3% by mass to 15% by mass, and more typically reduced to 5% by mass to 10% by mass.

The calcium oxide concentration contained in the biomass ash B1 (B1C, B1F, etc.) can be measured by a well-known method, and for example, a calibration curve method using a fluorescent X-ray apparatus is preferably exemplified.

This classification step S10 corresponds to the step (a).

(Injection step S20)
The crude powder B1C obtained in the classification step S10 is added (added) as a raw material for cement clinker or as a mixed material to cement clinker or cement. In the example of FIG. 2, the coarse powder B1C is charged into the clinker manufacturing facility 10, and the cement clinker Cn1 obtained from the clinker manufacturing facility 10 is mixed with gypsum as needed and crushed into the first crushing facility 30. The case of being thrown in is illustrated. In the latter case, the coarse powder B1C is pulverized together with the cement clinker Cn1 to produce mixed cement. At that time, watering and crushing aids are added as needed. However, the coarse powder B1C may be charged into either the clinker production facility 10 or the first crushing facility 30.

As the first crushing equipment 30, a general mill used in a finishing process such as a tube mill can be used. The mill is also called a finish crusher, and in a cylindrical drum, a steel ball, cement clinker Cn1, and gypsum added as needed are crushed while colliding with each other by the rotation of the drum. When gypsum is used, the gypsum is not particularly limited, and examples thereof include natural dihydrate gypsum, flue gas desulfurized gypsum, phosphoric acid gypsum, titanium gypsum, and phosphoric acid gypsum. These may be used alone or in combination of two or more.

The crude powder B1C replaces a part of the cement raw material, and it is preferable to add 0.5% by mass to 30% by mass with respect to the mass of the cement raw material. Further, it is preferable to add gypsum in an SO ₃ equivalent of 1.5% by mass to 5.0% by mass in order to improve the strength development and fluidity of the cement.

As another method, the crude powder B1C obtained in the classification step S10 may be directly charged into the clinker cooler 13. Examples of the charging method include a method of dropping from the upper part of the clinker cooler 13 at a position of a desired temperature in the clinker cooler 13. The input amount is preferably set to be about 0.5% by mass to 20% by mass with respect to the mass of the cement. If an air-quenching cooler is used as the clinker cooler 13, the coarse powder B1C can be charged at a predetermined position in the clinker cooler 13, which is preferable.

When the crude powder B1C is washed with water and then put into the clinker cooler 13, it is convenient because the water can be evaporated and removed by using heat energy which is not directly related to the production of the cement clinker Cn1. Further, in order to prevent a large amount of dust from being generated in the clinker cooler 13, the coarse powder B1C preferably has a water content of 50% by mass or less, and is preferably added in the form of lumps or granules.

The crude powder B1C obtained after the classification step S10 is also reduced in alkali metal concentration, calcium concentration, chlorine concentration, and sulfur concentration as compared with the fine powder B1F. Therefore, as shown in FIG. 2, it can be used in the clinker manufacturing facility 10 together with the cement clinker raw material Y1. For example, in the clinker manufacturing facility 10, it is possible to put the cement clinker raw material Y1 into a mixer for preparation, put it into a preheater 11 or a calcination furnace, put the cement kiln 12 into a kiln butt or a kiln front, and the like. It can be suitably used as a raw material for cement clinker Cn1 that can be put into various cement manufacturing stages.

As another example, as shown in FIG. 4, assuming that the cement manufacturing system 1 is provided with a crushing facility (second crushing facility 35) different from the first crushing facility 30 for crushing the cement clinker Cn1. It doesn't matter. The coarse powder B1C classified in the classification facility 20 may be crushed in the second crushing facility 35 and then charged into the clinker cooler 13 or the first crushing facility 30. The second crushing equipment 35 can be realized by the same equipment as the first crushing equipment 30.

Further, the coarse powder B1C after crushing may be mixed with the cement obtained after the cement clinker Cn1 is crushed in the first crushing facility 30. The timing of this mixing may be on the route to the cement silo in which the cement is stored in the subsequent stage of the first crushing facility 30, may be in the cement silo, and further, when the cement is used. It does not matter even during the cement mixing process. Since the crude powder B1C has a low chlorine content, the effect of suppressing an increase in the chlorine content of the hardened cement product can be obtained while using the biomass ash B1 regardless of the timing of mixing the crude powder B1C.

The crude powder ^{B1C is preferably pulverized so that the specific surface area of the brain is 4000 cm 2 /} g or more in order to activate the pozzolan reaction and increase the strength of the hardened cement product. It is particularly preferable to do so. The activity index of the coarse powder B1C after pulverization is higher than that of biomass ash (raw ash) B1, typically 65% or more in 7 days, 70% or more in 28 days, and more typically. It will be 68% or more in 7 days and 70% or more in 28 days.

Further, as described above, the chlorine concentration of the crude powder B1C is greatly reduced by the classification step S10, and the sulfur content is also greatly reduced, so that clogging due to the adhesion of the low melting point substance to the preheater, the kiln bottom, and the kiln is suppressed. To. Further, the coarse powder B1C in a state where the reactivity is enhanced by being crushed by the second crushing equipment 35 may be used as a cement mixture.

This charging step S20 corresponds to the step (b).

In the cement manufacturing system 1 of the present embodiment, the use of the fine powder B1F classified in the classification facility 20 is not restricted. For example, as will be described later, like the coarse powder B1C, it may be used as a raw material for cement clinker, or may be added (added) to cement clinker or cement as a mixed material, and may be used as fertilizer or fine aggregate. It doesn't matter if it is a thing. In particular, the fine powder B1F has a finer particle size and exhibits higher reactivity than the coarse powder B1C. Therefore, by recovering the fine powder B1F and using it as a cement mixture, the pozzolan reaction is activated and the cement cured product is obtained. The effect of increasing the strength is expected.

[Second Embodiment]
The cement manufacturing method and the second embodiment of the cement manufacturing system will be described focusing on the parts different from the first embodiment. FIG. 5 is a drawing schematically showing a processing flow of the cement manufacturing method in the present embodiment. FIG. 6 is a drawing schematically showing an example of a detailed processing flow of the water washing step S30 described later. FIG. 7 is a block diagram schematically showing the structure of the cement manufacturing system according to the present embodiment.

The cement manufacturing system 1 of the present embodiment shown in FIG. 7 is different from the first embodiment in that it is provided with a water washing facility 40. The water washing facility 40 is a facility for washing the biomass ash B1 with water, and is provided for the purpose of reducing the concentration of cement repellent components such as chlorine contained in the biomass ash B1. An example of the detailed structure of the water washing facility 40 will be described later with reference to FIG.

In the cement manufacturing system 1 of the present embodiment shown in FIG. 7, the coarse powder B2C obtained after classifying the biomass ash (modified biomass ash B2) after washing with water in the classification facility 20 is cement. An example is shown in which the fine powder B2F is charged into the production facility 10 and is charged into the first crushing facility 30 together with the cement cleaner Cn1. However, as described above in the first embodiment, the coarse powder B2C may be charged into the first crushing equipment 30, and the cement clinker Cn1 may be charged into the cement obtained after being crushed in the first crushing equipment 30. It does not matter if it is thrown in. In particular, in the latter case, as described above with reference to FIG. 4, the coarse powder B2C is crushed in the second crushing equipment 35 to make the cement in a state where the reactivity is enhanced. It is preferable to mix.

(Water washing step S30)
The biomass ash B1 is washed with water by the water washing facility 40. More specifically, as shown in FIG. 6, a step S31 for slurrying the biomass ash B1, a step S32 for washing the slurry with water, and a step S33 for dehydrating the biomass ash B1 are executed.

As an example, in the water washing facility 40 shown in FIG. 8, water W1 is added to the contained biomass ash B1 to form a slurry Lr1 for washing with water, and the water is discharged from the powder dissolving tank 43 after washing with water. It is provided with a solid-liquid separation device 46 for dehydrating the slurry Lr2 and a transfer device 47 for transporting the dehydrated product Ck1 separated by the solid-liquid separation device 46.

Further, in the example of the water washing facility 40 shown in FIG. 8, the powder dissolving tank 43 is provided with a powder supply device 41 for supplying the biomass ash B1 and a liquid supply device 42 for supplying the water W1. ing. Further, a slurry stirring device 44 equipped with a stirring blade is attached for mixing the biomass ash B1 and water W1 and stirring the slurry Lr1 generated by the mixing.

In the powder dissolution tank 43, a slurrying step S31 for mixing and stirring biomass ash B1 and water W1 to generate a slurry Lr1 and a water washing step S32 for eluting a cement repellent component such as chlorine into the liquid phase in the slurry Lr1 are performed. Will be done. As the slurry agitator 44 for that purpose, for example, a paddle type or screw type general agitator can be used.

The mass ratio (W1 / B1) of the biomass ash B1 and the water W1 in the slurrying step S31 is preferably 2 to 10, more preferably 3 to 7, and particularly preferably 4 to 5. If the mass ratio (W1 / B1) is smaller than 2, the reforming effect may be insufficient, such as insufficient elution of water-soluble components such as chlorine from the biomass ash B1. Further, if the mass ratio (W1 / B1) is larger than 10, the amount of wastewater W3 will increase.

The water washing step S32 is performed by allowing the slurry Lr1 to stand for a predetermined time or stirring it. As a result, the slurry Lr2 in which the soluble component of the biomass ash B1 is eluted in the liquid phase of the slurry can be obtained.

The time required for the water washing step S32 is preferably 30 minutes or more, more preferably 45 minutes or more, because the biomass ash B1 is sufficiently reformed with water W1. Further, the higher the temperature condition, the better the elution efficiency of water-soluble components such as chlorine from the biomass ash B1, but from the viewpoint of the cost of treatment, it is preferably 5 ° C to 50 ° C, and 25 ° C to 25 ° C. 50 ° C. is more preferable.

After the washing step S32, the slurry Lr2 in which the cement repellent component such as chlorine is eluted in the liquid phase in the slurry is discharged from the powder dissolution tank 43 and transferred to the solid-liquid separation device 46. For the transfer of the slurry Lr2, a normal slurry liquid transport device (not shown) such as a centrifugal pump for slurry, a piston pump, and a mono pump may be used.

In the solid-liquid separation device 46, the slurry Lr2 is solid-liquid separated to obtain a dehydrated product Ck1 (dehydration step S33). As the solid-liquid separation device 46, a filter press, a pressurized leaf filter device, a screw press, a belt press, a belt filter, a normal filtration device such as sedimentation separation, or the like can be used.

In the dehydration step S33, in order to prevent water-soluble components such as chlorine contained in the slurry Lr2 from remaining together with the liquid phase, the water content of the dehydrated product is preferably 20% by mass to 90% by mass, preferably 30% by mass. It is more preferably to be about 70% by mass.

Since the components eluted in the liquid phase of the slurry Lr2 are removed to the waste water W3, the amount of the cement repellent component such as chlorine is reduced in the obtained dehydrated product Ck1 as compared with the raw ash (biomass ash B1). On the other hand, since heavy metals and the like contained in the raw ash are also eluted in the wastewater W3, they may be discharged into the environment after being appropriately treated for water quality.

As shown in FIG. 8, a water cleaning device 49 may be attached to the solid-liquid separation device 46, and water W2 may be added to the dehydrated product Ck1 and then dehydrated again. According to this, since the liquid phase of the slurry Lr2 is almost replaced with water, the eluted components can be removed more reliably.

This water washing step S30 corresponds to the step (d).

The dehydrated product Ck1 obtained through the washing step S30 is in a state where the biomass ash B1 is modified (modified biomass ash B2), the cement repellent component such as chlorine is reduced, and the strength development of the cement is increased. The content of easily reactive calcium oxide and calcium hydroxide that affect fluidity is sufficiently reduced. Therefore, by using the modified biomass ash B2 to perform each step of classification and mixing as in the first embodiment, it becomes easy to keep the quality as a cement mixed material homogeneous. In particular, the above effect can be remarkably realized by using the biomass ash B1 discharged from the fluidized bed type combustion furnace into which the limestone containing the calcium component is charged.

The wastewater W3 obtained in the dehydration step S33 may be mixed with cement clinker Cn1 in a state where the contained chlorine ions are reduced by a well-known method such as an ion exchange resin, membrane separation, and precipitation formation by silver or lead ions. do not have. This makes it possible to effectively utilize the alkali metal contained in the wastewater W3, which has a strength-enhancing effect, while removing chlorine that causes corrosion of the reinforcing bars. As in the present embodiment, the modified biomass ash B2 obtained by executing the water washing step S30 has low activity by washing with water. Therefore, by adding the waste water W3 after washing with water as a cement additive, the modified biomass ash B2 It is possible to make up for the weakness of reduced activity.

In particular, since the biomass ash B1 has a lower chlorine concentration than the municipal waste incineration ash, the chlorine contained in the wastewater W3 can be easily separated, and a large amount of alkali metal sulfates and carbonates can be obtained in the wastewater W3. Therefore, by charging the wastewater W3 on the route from the clinker cooler 13 to the first crushing facility 30, more alkali metals can be utilized as the cement additive.

By throwing the drainage W3 between the clinker cooler 13 and the first crushing equipment 30, the cement can be used for cooling the cement clinker Cn1 and for controlling the temperature in the crushing equipment 30 without drying or solidifying. Can be used as an additive. More specific charging points include a clinker cooler 13 at 400 ° C. or lower in a cement manufacturing facility, a subsequent transport aircraft, and a first crushing facility 30. If the temperature exceeds 400 ° C., it evaporates instantly, so that it is difficult to be contained in the cement. If the temperature is higher than the first crushing facility 30, water remains in the cement and the quality may deteriorate due to the influence of weathering and hydration.

The drainage W3 may be charged between the clinker cooler 13 and the first crushing facility 30 in a state where the water content has been reduced by drying or the like. According to this, more alkali metals can be utilized as a cement additive without weathering the cement. In particular, if the wastewater W3 is dried and solidified, it can be added even when crushed cement or concrete is kneaded, and an arbitrary amount can be easily added.

As a means for reducing the contained chlorine ions, an amphoteric ion exchange resin or a nanofiltration membrane is particularly preferable. According to this, sulfate ion / carbonate ion and chlorine ion can be selectively separated, and water having a high sulfate ion / carbonate ion concentration and a low chlorine ion concentration and water having a low sulfate ion / carbonate ion concentration and a chlorine ion can be separated. Highly concentrated water can be obtained.

The wastewater W3 obtained after washing the biomass ash B1 with water often contains selenium and hexavalent chromium. By using the above-mentioned amphoteric ion exchange resin and nanofiltration membrane, selenium and hexavalent chromium, which have the same morphology as sulfate ions, are separated on the water side with a low chlorine concentration. Water with a high chlorine concentration is disposed of, but the water has a low concentration of selenium and hexavalent chromium, which facilitates wastewater treatment. In addition, the amount of water can be reduced (increasing the concentration of alkali metal) without drying, and when charged between the clinker cooler 13 and the first crushing facility 30, more alkali metal can be used as a cement additive with the same amount of water sprinkled. Can be utilized.

As described above, since the wastewater W3 (cement additive) obtained from the washed water and the reformed biomass ash B2 washed with water can be used at the same time as the cement mixture, the biomass ash B1 can be fully used. As a result, the effect of reducing the amount of wastewater to be disposed of and the load of wastewater treatment can be expected.

In this embodiment, it is also possible to carry out the oxidation step S41 and the unburned carbon removing step S42 together with the water washing step S30 (see FIGS. 9A and 9B). These steps may be performed in parallel with the execution of the water washing step S30, or may be performed after the execution of the water washing step S30. In addition, only one of the oxidation step S41 and the unburned carbon removal step S42 may be performed.

FIG. 9A is a drawing schematically showing a treatment flow when both the oxidation step S41 and the unburned carbon removal step S42 are executed in the present embodiment, and FIG. 9B shows the structure of the water washing facility 40 in this case. It is a drawing which shows typically by following FIG. Note that FIG. 9B shows the gas supply device 51 and the flotation device 53 as well as the water washing facility 40.

(Oxidation step S41)
The oxidation step S41 is a step of oxidizing the biomass ash B1. As an example, in the washing step S30, it can be carried out by adding a pH adjuster to the powder dissolving tank 43 and washing with water. As a result, the washing step S30 and the oxidizing step S41 are performed in parallel.

By adjusting the pH at the time of washing with water to the acidic side, chlorine contained in the biomass ash B1 can be more efficiently water-soluble as compared with the case where the pH is not adjusted. Further, the calcium component contained in the biomass ash B1 can be easily reacted with the form of slow-reactive calcium carbonate or calcium sulfate added to the cement cleaner Cn1 at the time of cement production, and the modified biomass obtained after the washing step S30 can be easily reacted. Ash B2 is suitable as a cement mixture material with small quality fluctuation.

The pH condition of the slurry Lr1 in the oxidation step S41 is preferably pH 4 to 13, and more preferably pH 5 to 12.

The pH adjuster is not particularly limited as long as the pH of the slurry Lr1 can be adjusted to the acidic side, and examples thereof include an acid solution such as sulfuric acid and a CO2 _- containing gas. As the CO2 _- containing gas, the combustion exhaust gas of the cement kiln 12 and the combustion exhaust gas of a biomass incineration facility or a biomass power plant can be used. Since these exhaust gases contain carbon dioxide ( _CO2 ), the pH can be adjusted to the acidic side by blowing the combustion exhaust gas into the slurry Lr1. According to this, the calcium component contained in the biomass ash B1 is carbonated, and it becomes easier to react with the form of calcium carbonate.

In FIG. 9B, as an example, a case where the _CO2 -containing gas G1 is supplied from the gas supply device 51 to the slurry Lr1 in the powder dissolution tank 43 is shown. In this case, the gas supply device 51 corresponds to the above-mentioned device for supplying the combustion exhaust gas of the cement kiln 12, the combustion exhaust gas of the biomass incineration facility, the biomass power plant, and the like to the powder melting tank 43.

The CO2 _- containing gas G1 may contain carbon dioxide, but in order to promote efficient carbonation, the carbon dioxide concentration is preferably 10% or more, more preferably 20% or more. In addition, among the combustion exhaust gas, the gas after collecting the chlorine bypass dust of the clinker manufacturing facility 10 contains harmful gas such as sulfur oxide (SO _x ), so by blowing this gas into the slurry Lr1. , The effect of immobilizing sulfur oxides can also be expected.

By using the combustion exhaust gas of the clinker production facility 10 in this way, the combustion exhaust gas containing carbon dioxide can be obtained on the spot and used for reforming the biomass ash B1, and the reformed biomass ash B2 can be used as a cement mixture. can. Further, if the biomass incineration facility or the combustion exhaust gas of the biomass power plant is used, the biomass ash B1 can be reformed by using the combustion exhaust gas containing carbon dioxide obtained on the spot, which can be used in the clinker production facility 10 or the crushing facility 30. If it is transported to a cement manufacturing facility such as, it can be immediately used as a cement mixture.

Further, in the water washing step S30, the waste liquid obtained from the amine-based carbon dioxide recovery device may be added to the powder dissolution tank 43 and washed with water. In an amine carbon dioxide recovery device for recovering carbon dioxide from exhaust gas of a factory or the like, a liquid containing deteriorated amines is usually discarded, but according to this method, the waste liquid can be effectively utilized.

It is known that amines have an action of promoting the production of carbonic acid ions by reacting with carbon dioxide, and can efficiently promote the carbonation of calcium components. It is also known that amines function as a pulverizing aid when pulverizing cement clinker Cn1 in the first pulverizing equipment 30. The amines have an amino group and a hydroxyl group in the molecule, and in particular, the amines used as a grinding aid include, for example, monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine. (TEA), diglycolamine (DGA), diisopropanolamine (DIPA), methyldiethanolamine (MDEA) and the like can be mentioned. Therefore, the modified biomass ash B2 incorporating amines brought in from the added waste liquid can be expected to impart functionality as a pulverizing aid in a subsequent step, and is therefore suitable as a cement mixture.

The dehydrated product Ck1 obtained through the dehydration step S33 may be blown with the _CO2 -containing gas G1. According to this, the easily reactive calcium component remaining in the dehydrated product Ck1 is carbonated, and the obtained modified biomass ash B2 can be further homogenized in quality, which makes it suitable as a cement mixture. It also helps to dry the water contained in the dehydrated product Ck1.

As the gas blowing means (gas supply device 51), any method may be used as long as the dehydrated anhydride Ck1 can be brought into contact with the _CO2 -containing gas. For example, means such as circulating the _CO2 -containing gas in a container filled with the dehydrated product Ck1 or passing the dehydrated product Ck1 through the exhaust gas flue can be used. Further, similarly to the above-mentioned blowing into the slurry Lr1, the combustion exhaust gas of the cement kiln 12 or the combustion exhaust gas of the biomass incineration facility or the biomass power plant may be blown into the dehydrated product Ck1.

This oxidation step S41 corresponds to the step (f).

(Unburned carbon removal step S42)
The unburned carbon removing step S42 is a step of removing the unburned carbon contained in the biomass ash B1. Since the biomass ash B1 contains a large amount of unburned carbon, it may cause the temperature of the preheater 11 to rise when used as a raw material for cement clinker Cn1, and when used as a mixed material, darkening of concrete may occur. And may lead to a decrease in liquidity.

Specifically, at the time of executing the washing step S30, stirring or the like is performed with the deburned carbon agent D1 such as oil or a surfactant added from the deburned carbon agent supply device 52 into the powder dissolution tank 43. A method of processing can be adopted. The obtained slurry Lr2a is subjected to a flotation treatment by adding a predetermined foaming agent, for example, in a flotation apparatus 53 to form a floss containing unburned carbon and a tail from which unburned carbon has been removed or reduced. Be separated. Then, the slurry Lr2b as a tail is sent to the solid-liquid separation device 46 for solid-liquid separation.

As a result, the washing step S30 and the unburned carbon removing step S42 are performed in parallel and continuously.

This unburned carbon removing step S42 corresponds to the step (g).

The above-mentioned oxidation step S41 and unburned carbon removing step S42 may be performed only on the fine powder B2F containing a larger amount of calcium component and unburned carbon, respectively.

(Classification step S10)
By adopting the same method as the above-mentioned method in the first embodiment, the modified biomass ash B2 is classified into coarse powder B2C and fine powder B2F.

The water washing step S30 and the classification step S10 may be performed simultaneously by the wet classifier. Specific examples thereof include methods such as water sieving, liquid cyclone, and centrifugation.

The activity index of the fine powder B2F obtained through the water washing step S30 and the classification step S10 is higher than that of the biomass ash (raw ash) B1, and is typically 70% or more in 7 days and 65% or more in 28 days. More typically, it is 73% or more in 7 days and 68% or more in 28 days.

The chlorine concentration of the fine powder B2F is typically reduced to, for example, 0.01% by mass to 0.2% by mass, and more typically 0.02% by mass to 0.1% by mass.

The total alkali metal concentration of the fine powder B2F is typically reduced to, for example, 1% by mass to 8% by mass, and more typically 3% by mass to 6% by mass.

The sulfur oxide concentration of the fine powder B2F is typically reduced to, for example, 0.5% by mass to 4% by mass, and more typically 1% by mass to 3% by mass.

The elution amount of selenium in the fine powder B2F is typically reduced to, for example, 0.002 mg / L to 0.02 mg / L, and more typically 0.005 mg / L to 0.01 mg / L.

The amount of hexavalent chromium eluted from this fine powder B2F is typically reduced to, for example, 0.01 mg / L to 0.1 mg / L, and more typically 0.02 mg / L to 0.05 mg / L. ..

The above-mentioned elution amounts of selenium (Se) and hexavalent chromium (Cr ⁶⁺ ) can be measured by a well-known method. As a suitable example of the measurement method, after preparing a test solution in accordance with JISK 0058-1 "Test method for chemical substances of slag-Part 1: Dissolution test method 5. Test by appearance", selenium (Se) ) Is measured by the ICP mass analysis method, and hexavalent chromium (Cr ⁶⁺ ) is measured by the diphenylcarbazide absorptiometry.

Further, as shown in Examples described later, the water washing step S30 sufficiently reduces the content of easily reactive calcium oxide and calcium hydroxide that affect the strength development and fluidity of the cement, and the calcium component is reduced. It is stabilized in the form of calcium carbonate and can suppress quality fluctuations.

For example, the content of calcium hydroxide in the modified biomass ash B2 after the washing step S30 is typically 0.5% by mass or less, and more typically 0.1% by mass or less.

Further, for example, the content of calcium sulfate (gypsum) in the modified biomass ash B2 is typically 0.5% by mass or more in terms of SO ₃ , and more typically 3% by mass or more.

The chlorine concentration described above can be measured by a well-known method, and for example, a method of measuring by a potentiometric titration method after acid decomposition treatment is preferably exemplified.

Further, the above-mentioned calcium hydroxide content can be measured by a well-known method, and for example, a method of obtaining dehydration at around 400 ° C. by a DSC (differential operating calorimeter) by measuring the calorific value is preferably exemplified.

Further, the above-mentioned calcium sulfate (gypsum) content can be measured by a well-known method, and for example, a method of quantifying by the Rietveld method from the pattern of X-ray powder diffraction is preferably exemplified.

(Injection step S20)
A method similar to the method described above can be adopted in the first embodiment. That is, as for the charging procedure, the coarse powder B1C in the first embodiment may be replaced with the coarse powder B2C obtained by executing the washing step S30. In the present embodiment, in the charging step S20, the fine powder B2F obtained through the water washing step S30 is also charged into the first crushing facility 30.

In particular, in the present embodiment, since the washing step S30 is executed before the charging step S20, the fine powder B2F obtained after the classification can contain water as compared with the fine powder B1F obtained in the first embodiment. There is sex. Therefore, the water contained in the fine powder B2F can be used for temperature control in the first crushing equipment 30 for preventing deterioration of gypsum and the like. If the water content in the fine powder B2F is excessive, dehydration can be easily performed by sedimentation separation or the like, and conversely, if the water content is insufficient, an appropriate amount can be sprinkled on the crushing equipment 30. good. The same applies to the coarse powder B2C.

As described above in the first embodiment, the crude powder B2C obtained after classification can also be directly charged into the clinker cooler 13. The temperature inside the clinker cooler 13 is usually 200 to 1200 ° C., and the heating temperature can be selected according to the charging position. However, when the above oxidation step S41 is executed, the modified biomass ash B2 contains a large amount of CaCO ₃ obtained by immobilizing CO ₂ . In this case, from 200 ° C. in the clinker cooler 13 so that CaCO ₃ contained in the modified biomass ash B2 does not decompose to generate quicklime (CaO) or release carbon dioxide. It is preferable to put it in a low temperature portion of 800 ° C. As described above with reference to FIG. 4, the coarse powder B2C may be crushed in the second crushing facility 35 and then charged into the clinker cooler 13.

Although the alkali metal content of the modified biomass ash B2 obtained by the method of the present embodiment is reduced by executing the washing step S30, the alkali metal content may still be higher than that of coal ash. is assumed. Therefore, when this modified biomass ash B2 is used as a raw material for cement clinker Cn1, cement having a high alkali metal content may be produced. The main component of the cement additive obtained from the wastewater W3 is an alkali metal salt. Therefore, if these are contained in a large amount in concrete, an alkaline aggregate reaction may occur depending on the aggregate.

Therefore, in order to reduce the possibility of alkaline aggregate reaction, latent hydrohard substances such as blast furnace slag and pozzolan substances such as fly ash, volcanic ash, volcanic rock, and calcined clay are added (added) together with modified biomass ash B2. It doesn't matter. It should be noted that such addition (addition) of the latent hydraulic substance or the pozzolan substance can also be applied to the case of using the coarse powder B1C in the case where the washing step S30 is not performed as in the first embodiment. However, since the coarse powder B1C has a lower alkali metal content than the fine powder B1F, a latent water-hardening substance or a pozzolan substance is added, especially when the fine powder B1F (B2F) is mixed with a cement raw material or cement. A high effect can be obtained by doing so.

Further, the modified biomass ash B2 and a chlorine-containing substance are mixed, and the mixture is heated to form an alkali metal chloride, which is further heated at a high temperature to volatilize and remove the chloride, or to add water. By removing the dissolved alkali metal chloride by solid-liquid separation, the alkali metal concentration when used as a cement raw material may be reduced.

[Third Embodiment]
The cement manufacturing method and the third embodiment of the cement manufacturing system will be described focusing on the parts different from the first embodiment and the second embodiment. FIG. 10 is a drawing schematically showing a processing flow of the cement manufacturing method in the present embodiment. FIG. 11A is a block diagram schematically showing the structure of the cement manufacturing system according to the present embodiment.

The present embodiment is different from the second embodiment in that the washing step S30 is performed after the classification step S10. In the present embodiment, the washing step S30 is performed only on the fine powder B1F classified by the classification step S10. In addition, in the example of FIG. 11A, the case where the fine powder B2F after the washing treatment is put into the cement manufacturing facility 10 is shown. Further, in the example of FIG. 11A, the coarse powder B1C obtained after the classification treatment is put into the cement manufacturing equipment 10 and the first crushing equipment 30 without being washed with water.

Comparing the coarse powder B1C obtained by classifying the biomass ash B1 in the classification step S10 with the fine powder B1F, more of the chlorine content is contained in the fine powder B1F than in the coarse powder B1C. Therefore, according to the present embodiment, the cement repellent component such as chlorine contained in the biomass ash B1 can be efficiently reduced while reducing the amount of water required for carrying out the water washing step S30.

As a specific method for charging the fine powder B2F after washing with water into the cement manufacturing facility 10, as in the case of the coarse powder B1C, raw material preparation such as a mixer or a crusher for preparation of the raw material of the cement clinker is performed. It can be put into the system equipment, put into the preheater top or calcination furnace before the cement kiln, put into the cement kiln kiln butt, and put into the high temperature part in front of the cement kiln (rotary kiln) kiln. Although the fine powder B1F contains chlorine and sulfur at a higher concentration than the coarse powder B1C, the concentration of chlorine and sulfur contained in the biomass ash B1 is reduced by washing with water, so that the cement clinker is used. It can be used as a raw material for Cn1.

As a result, clogging due to adhesion of the low melting point substance to the preheater, the kiln bottom, and the kiln is suppressed as compared with the case of not washing with water, and the chlorine content of the cement clinker Cn1 is also reduced. In addition, the alkali metal content of the cement clinker Cn1 is high, and high-strength cement can be obtained. In particular, when coarse powder B1C is added as a cement mixture, or when latent hydrohard substances such as blast furnace slag and pozzolan substances such as fly ash, volcanic ash, volcanic rocks, and calcined clay are added, alkali metals supplied from cement clinker. Activates the reaction of these mixtures.

In the present embodiment as well, the oxidation step S41 and the unburned carbon removal step S42 may be executed as in the second embodiment. Since the others are common to each of the above embodiments, the description is omitted.

As shown in FIG. 11B, the fine powder B2F after the washing treatment may be charged into the first crushing equipment 30 and crushed and mixed together with the cement clinker Cn1.

[Another Embodiment]
Hereinafter, another embodiment will be described.

<1> As shown in FIG. 12, of the coarse powder B1C and the fine powder B1F obtained by classifying the biomass ash B1 in the classification equipment 20, the coarse powder B1C is to be washed with water by the water washing equipment 40. It doesn't matter. The content concentrations of chlorine and sulfur in the crude powder B1C are reduced by the classification step S10, but these concentrations are further reduced by performing the washing step S30. Therefore, it can be used as a raw material for cement clinker Cn1. As shown in FIG. 12, the coarse powder B2C after the washing treatment may be added to the cement manufacturing facility 10 and charged into the first crushing facility 30. Further, as in the example shown in FIG. 4, the coarse powder B2C after the washing treatment may be crushed by the second crushing facility 35 and then charged into the cement manufacturing facility 10.

The wastewater W3 obtained in the water washing step S30 is originally obtained after washing with water for the crude powder B1C having a small amount of chlorine, and therefore has a low chlorine content. Therefore, the waste water W3 may be mixed with the cement clinker Cn1 without taking measures for reducing the contained chlorine ions as described above in the second embodiment.

On the other hand, the fine powder B1F may be mixed with cement clinker Cn1 or cement after being separately washed with water as necessary, or may be used as fertilizer or fine aggregate. do not have.

<2> In each of the above embodiments, the process of producing cement by crushing the cement clinker Cn1 in the crushing equipment 30 has been described. However, as the charging step S20, the coarse powder (B1C, B2C) of the biomass ash obtained in each embodiment is charged into cement and water and kneaded to produce a hardened cement product such as concrete or mortar. You may use it for the method.

[Example 1]
Incinerator fly ash BA-1 (grain size D ₅₀ (frequency) 47.2 μm, ignition loss at 975 ° C. (ig. Loss) was 4.17%), and the effect of classifying it on the composition of biomass ash was investigated. The content of coal in the mixed fuel of palm coconut shell and coal was 10% by mass. The particle size distribution of this incinerated fly ash (laser diffraction type particle size distribution measuring device: using MT3300EX II manufactured by Microtrac Bell) is as shown in FIG.

"Test method"
The test method will be described below.

<1. Classification>
Sift using a sieve with a mesh opening (spin air sheave: SAR-75 / 200 manufactured by Seishin Enterprise Co., Ltd.) set to be the classification point shown in Table 1, and use fine powder B1F as the sieve passage residue. Crude powder B1C was obtained. This process corresponds to the classification step S10. The classification point is set based on the particle size distribution shown in FIG. .. In the test, biomass ash B1 was classified at three classification points of 32 μm, 45 μm, and 90 μm, respectively. In the following, in order to clarify that the biomass ash B1 is before classification, it may be referred to as "raw ash B1".

Table 1 shows the particle size distribution of the biomass ash after classification. Table 1 also shows the crude powder B1C obtained after classifying the incinerated fly ash BA-2 obtained from the biomass power generation facility P2, which is different from the biomass power generation facility P1, with a classification point of 45 μm. It is shown. The particle size distribution was measured by a laser diffraction type particle size distribution measuring device (MT3300EX II manufactured by Microtrac Bell).

<2. Chemical composition analysis>
Wet the raw ash B1 (# 1) derived from the incinerated fly ash BA-1, each coarse powder B1C (# 2, # 4), each fine powder B1F (# 3, # 5), and the raw ash B1 by the following method. The chemical composition was measured for each of the incinerated product (# 1W) and the crude powder B1C (# 2W) obtained by classifying the wet ashed raw ash B1 (# 1W) at 45 μm. Further, coarse powder B1C (# 9) and fine powder B1F (# 10), which were classified by classifying the raw ash B1 with 20 μm as a classification point, were obtained, and the chemical components of these were also measured in the same manner. Further, for the raw ash B1 (# 1) and the fine powder B1F (# 3) classified by 45 μm, those which have been washed with water by the following method are prepared (# 1Wp, # 3Wp) and similarly chemicalized. The components were measured.

The method of wet ashing is as follows. Wet ash by adding 20% by mass (water content 16.7% by mass) of water to the raw ash B1 (reference numeral # 1), storing at 20 ° C for 3 days, and drying at 105 ° C. And said. The raw ash B1 moistened by this method corresponds to "reference numeral # 1W", and the crude powder B1C obtained by classifying the wet ashed raw ash # 1W corresponds to "reference numeral # 2W". .. When classifying the wet ash raw ash B1 (# 1W), an air jet sheave (manufactured by Hosokawa Micron Corporation, e200LS) was used.

The method of washing with water is as follows. This treatment corresponds to the washing step S30.
(Procedure 1) 100 g of biomass ash (B1, B1F) and 400 g of tap water were put into a beaker to make a slurry, which was stirred with a stirrer at 400 rpm for 30 minutes. At this time, when adjusting the pH by inflowing CO ₂ gas during washing with water, the flow rate was adjusted while monitoring the pH in the liquid with a pH meter.
(Procedure 2) After stopping stirring, filtration was performed using a Büchner funnel, and 400 g of tap water was further added to the obtained cake on the filter paper to wash the slurry and then recovered.
(Procedure 3) After the collected cake was naturally dried, the mass was measured and various analyzes were performed.

Further, the obtained coarse powder was pulverized using a ball mill.

"analysis"
The measurement of the chemical composition was carried out by the following method.
For each prepared sample (# 1 to # 5, # 9 to # 10, # 1W, # 2W, # 1Wp, # 3Wp), a fluorescent X-ray apparatus (Rigaku, ZSX Primus II) was used. The chemical composition was measured by the calibration curve (coal ash) method. The results are shown in Table 2. Each ignition loss was measured by a method according to JIS R5202 "Cement Chemical Analysis Method". The amount of incinerated fly ash and the amount of calcium carbonate in the obtained sample is about 600 ° C to 700 ° C when the temperature of the sample is about 50 mg in a nitrogen atmosphere and the temperature is raised to 1000 ° C at a heating rate of 20 ° C / min. The amount of reduction was calculated and calculated by the ratio of the weight reduction with the reagent (using TG-DTA 2000SR manufactured by NETZSCH). As for the amount of calcium hydroxide in the incinerated fly ash and the obtained sample, the amount of heat absorption around 400 ° C. when the temperature of the sample is about 50 mg in a nitrogen atmosphere and the temperature is raised to 1000 ° C. at a heating rate of 10 ° C./min is obtained. , Determined by the ratio of weight loss with the reagent (using DSC404F3 manufactured by NETZSCH).

The amount of hydrate produced was defined as the amount of calcium carbonate minus the decarboxylated content that volatilized from the loss on ignition. The amount of hydrate produced from the raw ash B1 was 1.8%, and that of the wet ash (# 1W) was 6.0%.

According to Table 2, when the raw ash B1 which is a dry ash is classified by the division point between the mountain on the fine grain side and the mountain on the coarse grain side when the particle size distribution is expressed by frequency, the fine powder (B1F) side is obtained. Contained most of the chlorine and sulfur components (SO ₃ ). In addition, it was confirmed that the chlorine component could be efficiently removed by washing this with water (B2F). Therefore, it can be seen that the fine powder after washing with water is particularly suitable as a cement mixture.

On the other hand, although the amount of decrease in alkali metal on the crude powder (B1C) side obtained by classifying raw ash is small, it contains almost no chlorine component and sulfur component, CaO decreases and SiO ₂ increases compared to raw ash. There is. Therefore, it can be seen that the crude powder has a chemical composition close to that of coal ash and is suitable as a raw material for cement clinker.

Further, when the raw ash B1 that has been moistened (# 1W) is compared with the crude powder B1C (# 2W) that has been classified by 45 μm, it is confirmed that the degree of decrease in chlorine concentration due to the classification is low. .. This is because the raw ash B1 was moistened to cause agglutination and hydration reaction, and chlorine (Cl) was incorporated into the produced hydrate, resulting in a decrease in the removal rate by classification. It is estimated to be. The wet ash of the raw ash B1 (# 1W) had a hydration reaction, and the ignition loss was increased as compared with the dry ash B1.

<3. Physical test>
For the raw ash B1 (# 1) derived from incinerated fly ash BA-1, the coarse powder B1C (# 2) and the fine powder B1F (# 3) obtained with a classification point of 45 μm, the brain specific surface area, flow value ratio, and The activity index was measured by a method according to Annex C of JIS A 6201 "Fly Ash for Concrete". Further, the coarse powder B1C (# 2) was pulverized with a mill so as to have a particle size equivalent to that of the fine powder B1F, and the brain specific surface area, flow value ratio, and activity index were measured in the same manner. The pulverized product (# 2C) obtained by pulverizing the crude powder B1C is, for example, in FIG. 12, the crude powder B1C after classification is pulverized by the pulverization equipment 30 (for convenience, it is referred to as “B1Cp”. .) Is simulated. The measurement results are shown in Table 3.

According to Table 3, it was confirmed that when the fine powder B1F obtained by classifying the raw ash B1 was used as a mixed material, the activity index was higher than that of the raw ash B1. It was clarified that the crude powder B1C does not contain chlorine and can be used as a pozzolan mixture having higher reactivity than the raw ash if it is pulverized until the brain specific surface area becomes 4000 cm ² / g or more (B1Cp). ..

[Example 2]
Fly ash (grain size D ₅₀ (frequency) is 45.3 μm, ignition loss at 750 ° C (ig.loss) from biomass power generation facility P2 that uses woody biomass (thinned wood) as fuel to generate electricity with a circulating flow bed furnace. ) Obtained 2.3%), and the effect of washing it with water and the presence or absence of an oxidation step (particularly a carbonation step) at the time of washing with water was examined.

"Test method"
The test was conducted according to the following procedure.
(Procedure 1) 100 g of biomass ash and 400 g of tap water were put into a beaker to make a slurry, which was stirred with a stirrer at 400 rpm for 30 minutes. At this time, when adjusting the pH by inflowing CO ₂ gas during washing with water, the flow rate was adjusted while monitoring the pH in the liquid with a pH meter.
(Procedure 2) After stopping stirring, filtration was performed using a Büchner funnel, and 400 g of tap water was further added to the obtained cake on the filter paper to wash the slurry and then recovered.
(Procedure 3) After the collected cake was naturally dried, the mass was measured and various analyzes were performed.

Table 4 below shows the level of each washing condition.

"analysis"
The obtained samples were analyzed by the following methods.
Quantification of Cl: After the sample was subjected to nitric acid decomposition treatment, it was measured by a potentiometric titration method.
Quantification of K and Na: After the sample was acid-decomposed, it was measured by ICP emission spectroscopy.
Dissolution test of Se, Cr ⁶⁺ : After preparing the test solution by the method based on JIS K 0058-1 "Test method for chemical substances of slag-Part 1: Dissolution test method 5. Test by appearance" Se was measured by the ICP mass analysis method, and Cr ⁶⁺ was measured by the diphenylcarbazide absorptiometry.
Quantification of C, Mg, Al, Si, P, S, Ca, Fe: The sample subjected to the drying treatment at 40 ° C. was measured by a fluorescent X-ray apparatus (FP method: fundamental parameter method). The measurement results are shown in Tables 5 and 6.

According to Table 5, most of the chlorine is effectively removed by washing the raw ash with water, and it is evaluated that there is no risk of corrosive action on the reinforcing bars, etc. after the cement is water-hardened when used as a mixed material. It was confirmed that the allowable standard of 0.035% by mass or less was satisfied. That is, it can be seen that when the biomass ash after washing with water is classified, chlorine is hardly contained on both the fine powder side and the coarse powder side.

In addition, according to Table 5, it is clear that water-soluble selenium and hexavalent chromium contained in the raw ash are also effectively removed by washing with water, and the risk of elution of heavy metals when used as a mixed material is reduced. became.

As shown in Table 6, it was clarified that this biomass ash contains SiO ₂ and CaO as main constituents and is useful as a highly reactive pozzolan mixture.

According to the results of Level 2-2, it was clarified that the CO ₂ content of the biomass ash after washing with water was increased by washing with water while blowing CO ₂ gas. Therefore, it is considered that at least a part of the component for pH adjustment was immobilized in the ash after the operation of washing with water to generate calcium carbonate. In addition, calcium hydroxide disappeared by washing with water while blowing CO ₂ gas. In Table 5, a calcium hydroxide content of less than 0.01% means below the detection limit.

Table 7 below shows the results of examining the existence form of the calcium component in the ash by the XRD method (X-ray diffraction method).

According to Tables 6 and 7, the presence of each Ca compound of CaO (quicklime), Ca (OH) ₂ (slaked lime), CaCO ₃ (limestone), and CaSO ₄ (plaster) as the form of calcium component in raw ash. confirmed. On the other hand, at level 2-1 washed with water without adjusting the pH, the presence of CaO (quick lime) disappeared, and the presence of Ca (OH) ₂ (slaked lime) was confirmed to decrease. It was also confirmed that the presence of CaO (quick lime) and Ca (OH) ₂ (slaked lime) disappeared and calcium carbonate increased at level 2-2, which was washed with water under the condition of pH 9 while injecting CO ₂ gas. ..

[Example 3]
Incinerator fly ash (grain size D ₅₀ (frequency) 20.0 μm, ignition loss at 750 ° C (ig.loss) from biomass power generation facility P3 that uses wood pellets and palm coconut shells as fuel to generate electricity with a stoker furnace. 6.1%) was obtained and the same test as in Example 2 was performed. The results are shown in Tables 8 and 9. At level 3-2, sulfuric acid for pH adjustment is added at the time of washing with water.

According to Table 8, most of the chlorine is effectively removed by washing the raw ash with water, and it is evaluated that there is no risk of corrosive action on the reinforcing bars, etc. after the cement is hydrohardened when used as a mixed material. It was confirmed that the allowable standard of 0.035% by mass or less was satisfied. That is, it can be seen that when the biomass ash after washing with water is classified, chlorine is hardly contained on both the fine powder side and the coarse powder side.

Further, according to Table 8, it is clear that water-soluble selenium and hexavalent chromium contained in the raw ash are also effectively removed by washing with water, and the risk of elution of heavy metals when used as a mixed material is reduced. became.

As shown in Table 9, it was clarified that this biomass ash contains SiO ₂ and CaO as main constituents and is useful as a highly reactive pozzolan mixture.

1: Cement manufacturing system 3: Raw material tank 5: Powder storage tank 10: Cleaner manufacturing equipment 11: Preheater 12: Cement kiln 13: Cleaner cooler 20: Classification equipment 30: First crushing equipment 35: Second crushing equipment 40: Washing equipment 41: Powder supply device 42: Liquid supply device 43: Powder dissolution tank 44: Slurry stirrer 46: Solid-liquid separation device 47: Transfer device 49: Water cleaning device 51: Gas supply device 52: Decombustible carbon agent supply Equipment 53: Floating beneficiation equipment B1: Biomass ash B1C: Coarse powder B1F: Fine powder B2: (Modified) Biomass ash B2C: (Modified) Coarse powder B2F: (Modified) Fine powder Ck1: Dehydrated product Cn1: Cement clinker D1: Decombustible carbon agent G1: _CO2 -containing gas Lr1: Slurry Lr2 (Lr2a, Lr2b): Slurry W1, W2: Water W3: Drainage Y1: Cement cleaner raw material

Claims (13)

Step (a) of classifying biomass ash into coarse powder and fine powder,
The coarse powder obtained in the step (a) is applied to at least one of a cement clinker raw material to be charged into a cement kiln, a cement clinker obtained from the cement clinker, or cement after a pulverization treatment for the cement clinker. A cement manufacturing method, which comprises a step (b) of charging. It has a step (c) of putting the fine powder obtained in the step (a) into at least one of the cement clinker or the cement after the pulverization treatment for the cement clinker.
The cement production according to claim 1, wherein the step (b) is a step of putting the coarse powder obtained in the step (a) into a cement clinker raw material to be put into a cement kiln. Method. It has a step (c) in which the fine powder obtained in the step (a) is charged into the cement clinker raw material.
The cement production according to claim 1, wherein the step (b) is a step of putting the coarse powder obtained in the step (a) into a cement clinker raw material to be put into a cement kiln. Method. It has a step (d) of washing the biomass ash with water, and has a step (d).
The cement manufacturing method according to claim 2 or 3, wherein the step (c) is a step of adding the fine powder after being washed with water by the step (d). The cement manufacturing method according to claim 4, wherein the step (d) is a step of washing only the fine powder obtained in the step (a) with water. The cement manufacturing method according to claim 4 or 5, further comprising a step (f) for oxidizing the biomass ash during or after the execution of the step (d). It has a step (e) of pulverizing at least a part of the crude powder obtained in the said step (a), and has.
The step (b) is a step of putting the coarse powder after being crushed by the step (e) into a cement clinker obtained from the cement kiln or a cement after crushing the cement clinker. The cement manufacturing method according to any one of claims 1 to 6, wherein the cement manufacturing method is characterized. The cement manufacturing method according to any one of claims 1 to 7, wherein the step (a) is a step of classifying with 20 μm or more and 100 μm or less as a classification point. The cement manufacturing method according to any one of claims 1 to 8, wherein the biomass ash is fly ash generated from a fluidized bed type combustion furnace and is dry ash. A classification facility that classifies biomass ash into coarse powder and fine powder,
Cement clinker A cement kiln that fires raw materials to produce cement clinker,
It is equipped with a first crushing facility that crushes the cement clinker obtained from the cement kiln to produce cement.
The coarse powder obtained by the classification device is charged into at least one of the cement clinker raw material, the cement clinker obtained from the cement kiln, or the cement obtained from the first crushing facility. A cement manufacturing system characterized by that. The cement manufacturing system according to claim 10, wherein the coarse powder obtained by the classification device is charged into the first crushing facility. A second crushing facility for crushing the coarse powder classified by the classification facility is provided.
The coarse powder after being crushed by the second crushing facility is charged into at least one of the cement clinker obtained from the cement kiln or the cement obtained from the first crushing facility. 10. The cement manufacturing system according to claim 10. Step (a) of classifying biomass ash into coarse powder and fine powder,
In the step (e) of crushing the coarse powder obtained in the step (a),
A method for producing a hardened cement product, which comprises a step (b) of adding the coarse powder after pulverization obtained in the step (e), the cement after the pulverization treatment, and water.

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