JP5561326B2 - Cleaning method of incineration ash - Google Patents

Description

  The present invention relates to a method for cleaning incineration ash, and more specifically, an incineration ash capable of efficiently removing chlorine contained in incineration ash and effectively utilizing coarse particles in the incineration ash as a raw material for cement. The present invention relates to a cleaning method.

Conventionally, the reuse of incineration ash, incineration fly ash, and the like generated from incineration facilities such as a garbage incinerator as a raw material for cement has been put into practical use.
The incineration ash and incineration fly ash contain a large amount of chlorine and toxic organic compounds such as chlorinated organic compounds. When these are used as cement raw materials for cement firing equipment, they are usually washed with water and then incinerated ash or incineration fly ash. After removing the chlorine contained in the ash, the chlorine-based organic compound remaining in the slurry is incinerated by directly putting it into a kiln bottom of a cement kiln in a slurry state.

For example, as a cement manufacturing method using main ash discharged from a garbage incinerator or the like and waste containing water-insoluble chlorine compounds such as home appliances and automobile shredding dust as a partial substitute for cement raw materials, After removing iron scraps and foreign substances from waste containing volatile chlorine compounds using a magnetic separator and a sieving device, it is put into a cement kiln, and the kiln exhaust gas containing chlorine vaporized in the cement kiln is sent to the cement kiln using a desalination bypass facility. A method for producing cement using a poorly water-soluble chlorine compound-containing waste that removes the problematic chlorine compound from the cement kiln by bleeding outside and rapidly cooling to a temperature below the melting point of the chlorine compound has been proposed (patent) Reference 1).
In addition, as a method of removing chlorine from the incinerated ash in advance, the incinerated ash slurry has a slurry concentration of less than 20% by mass, wet pulverized using a wet pulverizer such as a tower mill, and then filtered, etc. The incineration ash slurry is solid-liquid separated using a solid-liquid separator, the chlorine compound in the incineration ash slurry is discharged to the outside together with dehydrated water, and the resulting solid matter is used as a cement raw material for wet grinding. A method has been proposed (Patent Document 2).

Japanese Patent Laid-Open No. 11-171605 JP 2006-297316 A

By the way, in the cement manufacturing method using the poorly water-soluble chlorine compound-containing waste of Patent Document 1 described above, when the amount of incinerated ash used is increased, the amount of chlorine that the incinerated ash brings into the cement kiln increases. In order to remove the increased amount of chlorine, the extraction amount of the desalination bypass facility must be increased, and there is a problem that chlorine contained in the incinerated ash cannot be removed efficiently.
Further, when the amount of incinerated ash used is increased, there is a problem that fuel consumption is deteriorated due to heat loss in the cement kiln.
In the wet pulverization method of incineration ash described in Patent Document 2 described above, when a large amount of incineration ash is processed, the entire amount must be separated into solid and liquid using a solid-liquid separation device such as a filter press. There is a problem that the apparatus becomes large and the initial investment for introducing this equipment also becomes large. Moreover, since the coarse-grained part with low chlorine concentration will also be grind | pulverized, there existed a problem that a wet grinding apparatus will become unnecessarily large.

  The present invention has been made to solve the above-described problems, and can remove chlorine contained in incineration ash more efficiently than when removing all incineration ash without distinction. It is an object of the present invention to provide a method for cleaning incineration ash that can effectively use the incineration ash as a raw material for cement.

  As a result of intensive studies to solve the above problems, the present inventors have found that incinerated ash is in a state where coarse particles and fine particles are aggregated, and the cohesive force is easily obtained only by mixing with water. I learned that it was strong enough not to disperse. Then, by subjecting the incinerated ash in such a particle state to a specific process, the aggregated coarse particles and fine particles can be dispersed in water, and the coarse particles and fine particles can be separated. I found out that I can do it. Then, the fine particle-containing slurry is separated from the slurry in which such coarse particles and fine particles are dispersed, and the separated fine particle-containing slurry is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, and carbon dioxide. Or, if two or more types are added to adjust the hydrogen ion index to 3 or more and 10.5 or less, the chlorine contained in the incineration ash is more efficient than removing all the incineration ash without distinction. It was found that the incinerated ash can be effectively used as a cement raw material, and the present invention has been completed.

That is, the incineration ash cleaning method of the present invention is a cleaning method for removing chlorine from incineration ash in which coarse particles and fine particles are aggregated, and removes foreign substances having magnetism that can be removed by magnetic sorting. A slurrying step of grinding the incinerated ash into a slurry by adding water of 1 to 10 times the weight of the incinerated ash to the incinerated ash and stirring and mixing the resulting mixture; Separation using a water sieve to separate a coarse particle-containing slurry whose main component is coarse particle having a particle size of 0.5 mm or more and a fine particle-containing slurry whose main component is fine particle whose particle size is less than 0.5 mm And one or more selected from the group of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid and carbon dioxide are added to the fine particle-containing slurry separated in the separation step and the hydrogen ion index is 3 or more and 10 Adjust to below 5 Step and said separated in the separation step the coarse particle-containing slurry was subjected to solid-liquid separation, obtaining a solid that coarse particles mainly, fine hydrogen ion exponent is adjusted to 3 or more and 10.5 or less the particle-containing slurry to solid-liquid separation, obtaining a solid composed mainly of fine particles, the solids mainly composed of solids and fine particles mainly composed of these coarse particles, a cement burning the cement material And a cement raw material process to be introduced into the facility.

In this incineration ash cleaning method, water of 1 to 10 times the weight of the incineration ash is added to the incineration ash, and the resulting mixture is stirred and mixed, whereby the incineration ash is ground and agglomerated. The coarse particles and fine particles in a state are separated, and a slurry in which these coarse particles and fine particles are dispersed in water is obtained.
This slurry is in a state where coarse particles and fine particles are dispersed in water, but since chlorine contained in incineration ash is contained in a large amount of fine particles, this slurry is made into coarse particles having a particle size of 0.5 mm or more. A coarse particle-containing slurry having a low chlorine concentration by separating the coarse particle-containing slurry containing as a main component and a fine particle-containing slurry mainly containing fine particles having a particle size of less than 0.5 mm using a water sieve And a fine particle-containing slurry having a high chlorine concentration.

  In this incineration ash cleaning method, the incineration ash contained in this mixture is efficiently ground by adjusting the hydrogen ion index of the mixture to 3 or more and 10.5 or less. Separation becomes easier.

In this incineration ash cleaning method, the slurry containing the coarse particles separated in the separation step is subjected to solid-liquid separation, and a solid content mainly composed of coarse particles is obtained, and the hydrogen ion index is 3 or more and 10.5 or less. It was obtained by solid-liquid separation by adding the water obtained in the step of obtaining a solid content mainly composed of fine particles to the incinerated ash by solid-liquid separation of the fine particle-containing slurry adjusted to Water is used effectively and resources are saved.

In this incineration ash cleaning method, solid content mainly composed of coarse particles obtained by the above method and solid content mainly composed of fine particles are mainly composed of particles having a low chlorine concentration.
Therefore, by introducing a solid material mainly composed of particles having a low chlorine concentration into the cement firing facility as a cement raw material, particles having a low chlorine concentration in the incinerated ash are effectively used as the cement raw material.

It is preferable to add 10 parts by weight or less of incinerated fly ash having a higher chlorine concentration than the incinerated ash to 100 parts by weight of the incinerated ash.
In this incineration ash cleaning method, the incineration fly ash is slurried together with the incineration ash by adding the incineration fly ash having a high chlorine concentration to the mixture containing the incineration ash having a low chlorine concentration. Can be divided into a coarse particle-containing slurry having a low concentration and a fine particle-containing slurry having a high chlorine concentration.

According to the incineration ash cleaning method of the present invention, water that is 1 to 10 times the weight of the incineration ash was added to the incineration ash from which foreign substances having magnetism that can be removed by magnetic separation were removed. A slurrying step in which the incinerated ash is ground and made into a slurry by stirring and mixing the mixture, and the slurry is made up of a coarse particle-containing slurry mainly composed of coarse particles having a particle size of 0.5 mm or more and a particle size of 0. A separation step of separating the fine particle-containing slurry mainly containing fine particles of less than 5 mm using a water sieve, and the fine particle-containing slurry separated in the separation step into hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, The process of adjusting the hydrogen ion index to 3 or more and 10.5 or less by adding one or more selected from the group of carbon dioxide and solid-liquid separation of the coarse particle-containing slurry separated in the separation process , and mainly composed of coarse particles Obtaining a solid that, the hydrogen ion exponent is 3 or more and subjected to solid-liquid separation the adjusted fine particle-containing slurry to 10.5 or less, obtaining a solid composed mainly of fine particles, with a Therefore, the slurry mainly composed of incineration ash can be divided into a slurry containing coarse particles with low chlorine concentration and a slurry containing fine particles with high chlorine concentration. Chlorine contained in incineration ash Compared with the case of removing without distinction, it can be removed efficiently.
Moreover, since the solid material mainly composed of these coarse particles and the solid content mainly composed of fine particles are provided as a cement raw material to a cement firing facility, these coarse particles are mainly used. By introducing a solid content mainly composed of a solid content and fine particles into a cement firing facility as a cement material , a solid material having a low chlorine concentration can be effectively used as the cement material.

It is process drawing which shows the cleaning method of the incineration ash of one Embodiment of this invention. It is a figure which shows the difference in the chlorine (Cl) density | concentration by the presence or absence of washing | cleaning of each of a coarse particle and a fine particle.

The form for implementing the cleaning method of the incineration ash of this invention is demonstrated based on drawing.
The present embodiment is specifically described for better understanding of the gist of the invention, and does not limit the invention unless otherwise specified.

An incineration ash cleaning method according to an embodiment of the present invention will be described with reference to FIG.
The incineration ash cleaning method of the present embodiment is a cleaning method for removing chlorine from the incineration ash in which coarse particles and fine particles are aggregated, and the incineration ash from which foreign substances having magnetism that can be removed by magnetic selection are removed. 1 to 10 and less than or equal to 10 times the weight of the incinerated ash, and by stirring and mixing the resulting mixture, the incinerated ash is ground to make a slurry, and the slurry is coarsened. A separation step of separating into a particle-containing slurry and a fine particle-containing slurry.

The incineration ash used here is generated by incineration of general waste or industrial waste, and aggregates of coarse particles and fine particles, for example, on the surface of the coarse particles. It is comprised by the aggregate which the some fine particle adhered.
Here, the coarse particles are particles having a particle size of 0.5 mm or more and 30 mm or less, preferably 0.5 mm or more and 5.0 mm or less, and the fine particles are particles having a particle size of less than 0.5 mm, The particles are preferably 0.2 mm or less.

General waste refers to household general waste such as garbage, non-combustible waste, and bulky waste that is generated in the daily life of general households, and industrial waste that is generated from business activities. This includes so-called municipal waste.
Industrial waste includes burning husk, sludge, waste oil, waste acid, waste alkali, waste plastic, rubber scrap, metal scrap, glass scrap, and the like generated from business activities.

  Depending on the type of municipal waste and industrial waste, the incineration ash usually has a heavy metal such as Cr of about 0.3 to 3% and an inorganic component of silica and the like of about 40 to 60%. In addition, about 0.5 to 20% chlorine (0.5 to 2% for main ash, 10 to 20% for fly ash) is contained, and in some cases, it is harmful to dioxins and their precursor compounds. Substances are also included.

Therefore, when applying the cleaning method of the present embodiment to the incinerated ash, foreign substances having magnetism that can be removed by magnetic separation from the incinerated ash are removed in advance.
The foreign matter having magnetism is a foreign matter containing a magnetic material such as Fe or Ni, and cans, tin pieces, nails, bolts, nuts, washers, paper clips, staples, cutter knife blades, thumbtacks, It is a foreign substance contained in incineration residue when municipal waste including hinges, wires, clasps, fasteners, various bottle lids, springs, etc. is incinerated.
There is no particular limitation on the magnetic separation, but the selection is performed using a drum-type magnetic separation machine using a permanent magnet or an electromagnet, a pulley-type magnetic separation machine, a suspended magnetic separation machine, a counter-polar magnetic separation machine, etc. A method is mentioned.

Next, the incineration ash from which the foreign matter has been removed is mixed with water that is at least 1 and at most 10 times the weight of the incineration ash to form a mixture, and this mixture is stirred and mixed using a stirring mixer. Is ground into a slurry.
Here, the reason for limiting the amount of water added to the incineration ash from which foreign substances have been removed to be not less than 1 and not more than 10 times the weight of the incineration ash is that if the amount of water is outside the above range, the incineration ash is polished. This is because the crushing effect is reduced, and it becomes difficult to separate coarse particles and fine particles that are in an agglomerated state, and a slurry in which these coarse particles and fine particles are dispersed in water cannot be obtained.
As water, in addition to fresh water newly introduced from the outside, circulating water obtained by a separation device described later is used.

To the above mixture, one or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid and carbon dioxide is added, and the pH (hydrogen ion index) of the above mixture is adjusted to 3 or more and 10.5 or less. It is preferable to do.
By adjusting the pH of the mixture to 3 or more and 10.5 or less, the incineration ash contained in the mixture is efficiently ground during the stirring and mixing described later, thereby separating coarse particles and fine particles. As a result, in a shorter time, it can be divided into a coarse-grained portion slurry having a low chlorine concentration and a fine-grained portion slurry having a high chlorine concentration.

Incineration fly ash having a chlorine concentration higher than that of the incinerated ash may be added to the above mixture, preferably 10 parts by weight or less with respect to 100 parts by weight of the incinerated ash.
The target incineration fly ash is generated by incineration of general waste, and aggregates of coarse particles and fine particles, for example, a plurality of fine particles adhere to the surface of the coarse particles. It is comprised by the aggregate.

  Here, the reason why the addition amount of incineration fly ash is preferably 10 parts by weight or less with respect to 100 parts by weight of incineration ash is that when the addition amount exceeds 10 parts by weight, the chlorine concentration in the obtained slurry is This is because the chlorine concentration of the solid matter obtained from the coarse particle slurry and the solid matter obtained from the fine particle slurry becomes high and becomes unsuitable as a cement raw material.

  Examples of the agitating and mixing machine generally include a wet tower mill, a vibration mill, a pan mixer, and a tilting mixer. In these apparatuses, a grinding medium such as a Ryukyu, an iron ball, a resin-coated metal sphere, or the like is used. Is customary. However, in the case of the present invention, it is necessary to disperse and separate the agglomerated coarse particles and fine particles from the incinerated ash from which foreign substances have been removed. Coarse particles having a low chlorine concentration are also crushed and may be mixed with fine particles having a high chlorine concentration.

  In the present invention, although a commonly used stirring mixer such as a wet tower mill, a vibration mill, a pan mixer, and a tilting mixer is used, in order to prevent coarse particles having a low chlorine concentration from being crushed, It is preferable to stir and mix incinerated ash in which fine particles are aggregated without using a grinding medium. In this stirring and mixing process, only the surface of each of the coarse particles and the fine particles is ground by the weak force generated during the stirring and mixing, and there is no possibility that the coarse particles having a low chlorine concentration are crushed.

  The stirring and mixing time should be set as appropriate depending on the type and volume of the stirring mixer to be used. In general, in the case of a batch type, it is about 10 to 120 minutes, preferably about 30 to 60 minutes. In the case of the continuous type, the residence time is appropriately adjusted so as to be about 10 minutes to 120 minutes, preferably about 30 minutes to 60 minutes.

For example, in the case of a wet tower mill, the incineration ash is introduced after removing the grinding medium, and further, water of 1 to 10 times the weight of the incineration ash is introduced, and about 10 to 120 minutes, preferably Stir and mix for about 30-60 minutes.
As a result, the incinerated ash is ground to separate the coarse particles and fine particles that are in an aggregated state, and the coarse particles and fine particles are dispersed in water.

This slurry is in a state where coarse particles and fine particles are dispersed in water, but since chlorine contained in incineration ash is contained in a large amount of fine particles, the slurry is added to a stirrer mixer. Used to separate into a slurry containing coarse particles and a slurry containing fine particles.
Thereby, said slurry is divided into a coarse-grained portion slurry (coarse particle-containing slurry) having a low chlorine concentration and a fine-grained portion slurry (fine particle-containing slurry) having a high chlorine concentration.

Further, by adding one or more selected from the group of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid and carbon dioxide to the slurry, the pH of the slurry may be adjusted to 3 or more and 10.5 or less. Good.
By adjusting the pH of the slurry to 3 or more and 10.5 or less, in this slurry, separation of coarse particles and fine particles becomes easier, and as a result, in a shorter time, the concentration of chlorine is low. It can be divided into a grain part slurry and a fine grain part slurry having a high chlorine concentration.
If the pH of the mixture is adjusted at the previous stage, the pH adjustment at this stage may not be performed.

Of these slurries, the coarse portion slurry having a low chlorine concentration is subjected to solid-liquid separation using a separator such as a filter such as a filter press or a centrifugal separator, and solids containing coarse particles having a low chlorine concentration , Get with water.
This solid-liquid separation can also be performed by, for example, piling up and draining water naturally when the coarse particles are coarse.
The obtained water is used effectively as a mixture of the incinerated ash from which the above foreign substances have been removed as circulating water.
In addition, the cake-like solid containing coarse particles is directly or after removing moisture with a dryer or the like, and then put into a cement raw material mill together with the cement raw material, pulverized and mixed, and then the 800 ° C. of the cement kiln. It is put into the above high temperature part and becomes a cement clinker.

On the other hand, for the fine-grained portion slurry having a high chlorine concentration, one or more selected from the group of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid and carbon dioxide is added, and the pH of the fine-grained portion slurry is 3 or more and It is preferable to adjust to 10.5 or less to further dissolve and remove chlorine. Thereby, the density | concentration of the chlorine in this fine grain part slurry becomes comparable as said coarse grain part slurry, for example.
In the case where the pH of the mixture is adjusted in the previous stage or the pH of the slurry in a state where coarse particles and fine particles are dispersed in water, the pH adjustment in this stage may not be performed.
Next, this fine-grain slurry with reduced chlorine concentration is subjected to solid-liquid separation using a separator such as a filter such as a filter press or a centrifuge, and a cake-like solid containing fine particles with a low chlorine concentration. Get things and water.
The obtained water is used effectively as a mixture of the incinerated ash from which the above foreign substances have been removed as circulating water.

In addition, the cake-like solid containing fine particles with low chlorine concentration is removed with a dryer or the like, and then put into a cement raw material mill together with the cement raw material. Cement clinker is put into the high temperature part above ℃. In the case of a small amount, the cake-like solid containing the fine particles can be directly put into a high temperature part of the cement kiln at 800 ° C. or higher.
Of the water discharged from this separation device, those other than those that are reused as recycled water are subjected to water treatment and discharged into sewers as water having a quality below the discharge standard.

Table 1 shows the classification test results of each of the incineration ash from which the above foreign matter was removed and the mixture containing the incineration ash. In Table 1, “dry sieve” is obtained by classifying the incineration ash by sieving. The “dispersion / water sieve” is a particle size distribution obtained by dispersing incinerated ash in water to obtain a mixture and then classifying with a water sieve. It is a particle size distribution obtained by stirring a mixture in which incinerated ash is dispersed in water for 2 hours and then classifying with a water sieve.
According to Table 1, the incinerated ash is easily separated into coarse particles and fine particles by being dispersed in water, and by further stirring, coarse particles and fine particles are further easily separated. As a result, it can be seen that the percentage of fine particles in the particle size distribution is very high.

Table 2 shows the chlorine (Cl) concentration in the particle size of the incinerated ash from which the above foreign matters have been removed and the above mixture. In Table 2, “dry sieve”, “dispersion / water sieve” and “stirring / water” “Sieving” is the same as in Table 1.
According to Table 2, it can be seen that the incinerated ash from which the foreign matters have been removed is gradually reduced in chlorine concentration by being dispersed in water and further stirred.
Further, it can be seen that the chlorine concentration is low for coarse particles, the concentration increases as the particle size decreases, and the concentration is highest when the particle size is less than 180 μm.

  FIG. 2 is a diagram showing the results of measuring the chlorine (Cl) concentration in the solid matter for each of the coarse particles and fine particles with or without washing with the washing water. In FIG. Coarse particles obtained by liquid separation (without washing with washing water), ■ ■ washed with washing water with coarse particles obtained by solid-liquid separation of the coarse particle slurry (with washing with washing water) ), ◇ indicates the fine particles obtained by solid-liquid separation of the fine particle slurry (without washing with washing water), and ◆ indicates the fine particles obtained by solid-liquid separation of the fine particle slurry. Each of them washed with water (washed with washing water) is shown.

  In addition, the “water added slurry” is the one that was not adjusted for pH when incinerated ash was slurried, and the “pH adjusted slurry” was the one that was adjusted for pH when incinerated ash was slurried. Show. Also, “new water” means that the water used for slurrying is fresh water, and “circulated water” means circulating water that repeatedly uses water obtained after solid-liquid separation. Each shows that. In addition, the frequency | count of "circulation water" is the frequency | count which was repeatedly used as circulation utilization water.

  According to FIG. 2, it can be seen that the coarse particles have a low chlorine concentration and a low chlorine content even when circulating water is used. Further, it can be seen that the fine particle fraction has a high chlorine concentration just by mixing with water, and it is possible to reduce the chlorine to a level usable as a cement raw material by adjusting the pH.

As described above, according to the cleaning method for incineration ash of the present embodiment, the incineration ash from which magnetic foreign matter is removed by magnetic separation is added to water that is 1 to 10 times its weight. The incinerated ash is ground and mixed into a slurry by stirring and mixing the resulting mixture, and then the slurry is separated into a coarse particle-containing slurry and a fine particle-containing slurry, so that the slurry containing the incinerated ash has a low chlorine concentration. The slurry can be divided into a coarse particle-containing slurry and a fine particle-containing slurry having a high chlorine concentration, and chlorine contained in the incinerated ash can be efficiently removed.
Therefore, the solid particles obtained by solid-liquid separation of the coarse particle-containing slurry having a low chlorine concentration are introduced as cement raw materials into a cement firing facility, thereby effectively using the coarse particles having a low chlorine concentration directly as cement raw materials. can do.
Even fine particles with a high concentration of chlorine can be effectively used as a cement raw material by adjusting the pH after slurrying the fine particles and further dissolving and removing chlorine.

Claims (2)

A cleaning method for removing chlorine from incinerated ash in which coarse particles and fine particles are aggregated,
The incineration ash from which magnetic foreign substances that can be removed by magnetic separation have been removed is added with water at least 1 to 10 times the weight of the incineration ash, and the resulting mixture is stirred and mixed to polish the incineration ash. A slurrying step for crushing slurry;
A water sieve is used for the slurry containing a coarse particle-containing slurry mainly composed of coarse particles having a particle diameter of 0.5 mm or more and a fine particle-containing slurry mainly comprising fine particles having a particle diameter of less than 0.5 mm. A separation step of separating;
One or more selected from the group of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid and carbon dioxide is added to the fine particle-containing slurry separated in the separation step, so that the hydrogen ion index is 3 or more and 10.5 or less. Adjusting the process to
A step of solid-liquid separation of the coarse particle-containing slurry separated in the separation step to obtain a solid content mainly composed of coarse particles;
A step of solid-liquid separation of a fine particle-containing slurry having a hydrogen ion index adjusted to 3 or more and 10.5 or less to obtain a solid content mainly composed of fine particles;
A method for cleaning incinerated ash, comprising: a solid material mainly composed of coarse particles and a solid material mainly composed of fine particles as a cement raw material, which is introduced into a cement firing facility. .   The incineration ash cleaning method according to claim 1, wherein incineration fly ash having a chlorine concentration higher than that of the incineration ash is added to the mixture by 10 parts by weight or less with respect to 100 parts by weight of the incineration ash.

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