JP5598745B2 - Purified chicken manure combustion ash and method for producing the same - Google Patents

Description

  The present invention relates to a purified chicken manure ash, a method for producing the same, and a phosphorus fertilizer comprising the purified chicken manure ash. More specifically, it is a chicken dung combustion ash purified product obtained by washing and dehydrating chicken dung burning ash, and the ratio (by weight) of sulfate radicals and hydrochloric acid radicals contained in the chicken dung combustion ash purified product is as follows: It is less than the ratio (weight conversion) of each of the sulfate radical and hydrochloric acid root contained in the said chicken manure combustion ash, It is related with the phosphorus fertilizer which comprises the chicken manure combustion ash refined product, its manufacturing method, and a chicken manure combustion ash refined product .

  Conventionally, chicken manure has been used as an organic fertilizer as a dried chicken manure fertilizer or a fermented chicken manure compost that has been fermented. On the other hand, chicken manure has problems such as a bad odor and a source of sanitary pests, and appropriate treatment is required from an environmental point of view.

  In recent years, as a method for treating chicken manure, it has been burned with a dedicated chicken manure boiler and used for heat recovery or power generation, etc. That is, the method of using chicken manure burning ash is applied.

  Chicken manure combustion ash can be used directly as a fertilizer, but it is highly alkaline, and most of the phosphorus component of the combustion ash is insoluble in water, and part of it is a compound with low fertilizer value. The application range of was narrow. Therefore, fertilizers have been proposed in which mineral acids such as sulfuric acid or phosphoric acid are added to chicken manure combustion ash, and a part of the phosphorus component in the combustion ash is changed to water-soluble (for example, see Patent Documents 1 to 3) . However, these proposals are used by adding mineral acids without refining chicken manure burning ash, and there is no description about the reduction of sulfate radicals and hydrochloric acid roots in chicken manure burning ash.

  On the other hand, phosphate ore has been conventionally used as a raw material for the production of phosphorus fertilizers, but since no industrially usable products are produced in Japan, the total amount depends on imports from overseas. However, in recent years, worldwide exhaustion of phosphate ore resources has become a problem, and it is desirable to manufacture phosphate fertilizers by substituting or reducing the use of phosphate ore by using phosphorus raw materials instead of phosphate ore. ing.

  As phosphorus raw materials for phosphorus fertilizer that replaces phosphorus ore, the use of incinerated ash such as sludge, municipal waste or industrial waste has been proposed (see, for example, Patent Documents 4 to 5). However, these proposals use incineration ash such as sludge, municipal waste, or industrial waste without purification, and there is no description regarding reduction of sulfate radicals and hydrochloric acid radicals in chicken manure combustion ash.

  Regarding the use of incineration ash such as waste, a method has been proposed in which incineration ash is subjected to processing such as removal of metal fragments and processing such as washing with water, and used as ferrous scrap, non-ferrous metal scrap, concrete aggregate or cement raw material. (For example, refer to Patent Documents 6 and 7). However, these proposals do not describe the production of phosphorus fertilizer using incinerated ash as a raw material.

  In addition, there has been proposed a method in which sludge incinerated ash is mixed with a reaction liquid containing an alkali metal or alkaline earth metal hydroxide or an alkaline reaction liquid, and a phosphorus component is extracted and separated in the liquid (for example, Patent Document 8). And 9). These proposals are methods for extracting phosphorus components from sludge incineration ash, and sludge incineration ash itself is not used for the production of phosphorus fertilizer.

Japanese Patent Laid-Open No. 57-140387 JP 2005-126252 A JP 2005-145785 A JP 2001-80979 A Japanese Patent Laid-Open No. 2003-112988 JP 7-155737 A Japanese Patent Laid-Open No. 11-319769 JP 2007-261878 A JP 2008-229576 A

  Chicken manure burning ash contains phosphorus and is promising as a phosphorus raw material for phosphorus fertilizer. However, phosphate ore generally contains only a small amount of sulfate and hydrochloric acid radicals, whereas chicken manure combustion ash contains a large amount of these, and is heated in an electric furnace or flat furnace during the production of phosphorus fertilizer. If processing such as melting is performed, problems such as corrosion of the manufacturing apparatus due to the generated gas occur. For this reason, it has been desired to reduce the content of sulfate radicals and hydrochloric acid radicals in chicken manure combustion ash.

  Accordingly, an object of the present invention is to provide a purified product of chicken dung burned ash having a reduced ratio of sulfate radicals and hydrochloric acid roots contained in the chicken dung burned ash, a method for producing the same, and a phosphorus fertilizer comprising the purified chicken dung burned ash. .

  As a result of intensive studies to solve the above problems, the inventors of the present invention are purified chicken ash combustion ash obtained by washing and dehydrating chicken stool combustion ash, which is included in the purified chicken stool combustion ash The ratio of sulfate radicals and hydrochloric acid roots (in terms of weight) to be produced is less than the ratio of each of sulfate radicals and hydrochloric acid radicals (in terms of weight) contained in the chicken feces combustion ash, and its production It has been found that the above problems can be solved by using the method, and the present invention has been completed.

  There is no particular limitation on the chicken manure burning ash used in the present invention, and it is an ash obtained by burning chicken manure discharged from the poultry industry etc., and the type is from any of laying hens, breeding chickens, broilers, etc. It can be used even if it exists.

  The method for producing a purified product of chicken dung combustion ash according to the present invention is characterized by adding water to chicken dung combustion ash, washing with water, and dehydrating.

  In the present invention, the water used to wash the chicken ash combustion ash with water can be water having a pH of about 4.5 to pH 12, preferably water having a pH of about 5 to 11. By washing the chicken dung burning ash with this range of water, the ratio of sulfate radicals and hydrochloric acid radicals (weight conversion) can be reduced, and there is little loss of phosphorus in the chicken dung burning ash, and the chicken dung burning The phosphorus content in the ash refined product can be made higher than that of the original chicken manure combustion ash, and the fluctuation of the phosphorus component can be reduced.

  There is no restriction | limiting in particular in the adjustment method of pH, A various method can be used. The water to be washed is preferably selected from industrially available water, tap water, well water, river water and the like that are generally available. It is also possible to use treated water repeatedly. In this case, although the pH of water rises, it can be used repeatedly up to about pH 12, and is preferably used repeatedly up to about pH 11.

  In the present invention, the amount of water added to wash the chicken dung burning ash with water can be selected as appropriate, but it can be preferably selected from the range of about 1 liter to 500 liters per 1 kg of chicken dung burning ash.

  In the present invention, the temperature of water when washing the chicken dung combustion ash with water can be selected as appropriate, but it can be selected from a water temperature of preferably 80 ° C. or lower, more preferably 70 ° C. or lower.

  In the present invention, the washing treatment operation is not particularly limited, and various treatment operations can be used according to the purpose. For example, either a batch type or a continuous type can be used. There is no restriction | limiting in the mixing method of chicken manure combustion ash, and also processing time, It can select suitably.

  There is no restriction | limiting in particular in the frequency of the water washing process of the chicken manure combustion ash in this invention, Although it can select suitably, Preferably it can select from the range of 1 to 5 times.

  There is no restriction | limiting in particular about the method of dehydration in the manufacturing method of the poultry manure ash refined material of this invention, Various methods can be used, for example, methods, such as filtration, a decantation, centrifugation, a filter press, can be mentioned. Further, these can be combined for dehydration. The water content of the dehydrated chicken manure combustion ash can be appropriately selected.

  After dehydration, a drying operation can be performed as necessary. There are no particular restrictions on the drying operation, and various methods can be used. For example, natural drying such as air drying and sun drying, heating drying, hot air drying, vacuum drying, fluidized drying, and drying by various devices such as a rotary kiln are used. Can do. The moisture content after drying can also be selected as appropriate.

  The refined chicken manure ash obtained in the present invention can be used as a phosphorus raw material for phosphorus fertilizer. Further, it can be used directly or mixed with other fertilizers as a phosphorus fertilizer having few sulfate radicals and hydrochloric acid radicals.

  There is no restriction | limiting in particular as a phosphorus fertilizer which can use the chicken dung combustion ash refinement | purification material obtained by this invention as a phosphorus raw material, For example, a molten manure, a molten phosphorous silicate fertilizer, a compound fertilizer etc. can be mentioned.

When producing the phosphorus fertilizer, the purified product of chicken manure combustion ash according to the present invention can be used as it is in powder form, or can be granulated and formed by various granulation methods. There is no restriction | limiting in the granulation method, For example, a rolling granulation method, an extrusion granulation method, a compression granulation method, a stirring granulation method etc. can be mentioned. Although the particle diameter and length at the time of granulation can also be selected suitably, Preferably a particle diameter and length can each be selected from the range of about 1 mm to 20 mm.

The present invention has the following effects.
1) Purified chicken manure combustion ash of the present invention is a purified chicken manure ash obtained by washing and dehydrating chicken manure ash, and sulfate and hydrochloric acid radicals contained in the purified chicken manure ash Is a purified chicken dung burning ash characterized in that the ratio (weight conversion) of the sulfate dung and hydrochloric acid radicals contained in the chicken dung burning ash is less than the respective ratio (weight conversion), more preferably sulfate radicals and Each of the hydrochloric acid roots is a purified chicken dung ash product in which the ratio (weight conversion) contained in the purified chicken dung ash product is 2% by weight or less, and can be suitably used as a phosphorus raw material for phosphorus fertilizer. In addition, it is possible to replace phosphate ore, or to reduce the amount of phosphate ore used.
2) The method for producing a purified chicken manure ash product of the present invention can easily produce a purified chicken manure ash product useful as a phosphorus raw material for phosphorus fertilizer.
3) The phosphorus fertilizer comprising the purified product of chicken manure combustion ash of the present invention is a conventional fertilizer produced from phosphate rocks in the growth of various grains such as paddy rice, vegetables, feed crops and fruit trees. It can be used in the same way as phosphorus fertilizer and is industrially useful.

It is a flowchart which shows the manufacturing process of the chicken dung combustion ash refined material of this invention.

  Embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 is a diagram for explaining the process outline of the method for producing a purified product of chicken manure combustion ash according to the present invention. The purified chicken manure combustion ash product of the present invention can be used after drying as necessary, as described above.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited only to these Examples.
(Examples 1 to 11)

An analysis example of the components of chicken manure combustion ash and phosphate rock is shown in Table 1 below. In Table 1, other than hydrochloric acid radicals are shown as oxide weights. Here, SO ₃ was a sulfate radical and Cl was a hydrochloric acid radical. P ₂ O ₅ was analyzed by fertilizer analysis, and SO ₃ and Cl were analyzed by fluorescent X-ray analysis. As is clear from Table 1, the phosphate rock contains only a small amount of sulfate and hydrochloric acid radicals, but chicken dung burning ash contains a large amount of both sulfate and hydrochloric acid radicals. In addition, chicken ash-burning ash has a large variation in the components, and in the example of Table 1, the maximum phosphorus content was 1.7 times.

  Table 2 shows the washing treatment conditions and dehydration method of the chicken manure combustion ash. After washing with water and dehydration, a purified product of chicken ash combustion ash of the present invention was obtained as a residue.

Table 3 shows an analysis example of the components of the purified chicken manure ash. As in Table 1, P ₂ O ₅ was analyzed by fertilizer analysis, and SO ₃ and Cl were analyzed by fluorescent X-ray analysis. As is clear from the comparison between Table 1 and Table 3, the sulfate radical and the hydrochloric acid radical are greatly reduced by washing the chicken dung burning ash with water. Since the sulfate radicals and hydrochloric acid radicals are reduced, problems such as corrosion of the apparatus due to the generated gas when the phosphorus fertilizer raw material is heated and melted in an electric furnace or a flat furnace, for example, are eliminated or reduced. Furthermore, the phosphorus content in the purified chicken manure ash product is clearly increased, and when the fertilizer is produced using the purified chicken manure ash product of the present invention as a phosphorus raw material, the efficiency of fertilizer production can be improved. In addition, the phosphorus content was 1.3 times as much as the maximum, and the variation was reduced compared to the raw material chicken ash combustion ash, making it easier to use as a raw material.

The ratio of the phosphorus eluted in the filtrate when the purified chicken dung burning ash was obtained to the amount of phosphorus contained in the used chicken dung burning ash was almost 0 in any of Examples 1 to 11. Less than 2% by weight, the amount of phosphorus that was washed away with water was negligible.
(Reference Examples 1 to 3 and Examples 12 to 16)

Using the dried chicken manure burned ash product of the present invention obtained in Examples 3, 10 and 11 above, phosphorus ore and other auxiliary materials, mixing in accordance with the formulation shown in Table 4 and heating to 1500 ° C. in an electric furnace The molten material was poured into water to prepare a phosphorus fertilizer. In Reference Example 2 and Reference Example 3, in place of the chicken dung burning ash refined product of the present invention, the chicken manure burning ash 1 (unpurified product) shown in Table 1 was used, and a phosphorus fertilizer was produced in the same manner. In Table 4, the phosphate ore used was the phosphate ore 1 shown in Table 1 (composition of main components: P ₂ O ₅ 35.2%, SiO ₂ 8.3%, CaO 43.9%). For a secondary raw material, calcium carbonate is CaO 57.9%, a thing of 0.6% MgO, _slag SiO 2 51.5%, CaO 1.0% , things of 34.3% MgO, heavy grilled Magne The site used was 89.1% MgO. The main components other than the above of the refined chicken ash combustion ash product of the present invention were 9.0% SiO ₂ , 31.6% CaO, 8.0% MgO, and 8.8% SiO _{2 in} Example 10. , CaO 30.9%, MgO 7.8% , example 11 _{SiO 2 9.1%, CaO 31.3%} , was 8.2% MgO. These analytical values are based on the fertilizer analysis method.

  In Reference Example 1, phosphorus fertilizer was produced using only phosphorus ore as a phosphorus raw material. In Reference Example 2, chicken dung burning ash 1 (unpurified product) and phosphorus ore were mixed and used as the phosphorus raw material. In Reference Example 3, only chicken dung burning ash 1 (unpurified product) was used as the phosphorus raw material. In Example 12, Example 13, Example 15 and Example 16, the chicken dung combustion ash refined product of the present invention and phosphorus ore were mixed and used as the phosphorus raw material. In Example 14, the chicken dung burning ash purification of the present invention was used as the phosphorus raw material. Only thing was used.

Table 5 shows the results of analyzing the produced phosphorus fertilizer according to the fertilizer analysis method. In Table 5, TP ₂ O ₅ represents the total phosphorus amount, and C—P ₂ O ₅ represents the soluble (citrate soluble) phosphorus amount. Table 5 shows the situation of chlorine ions and sulfate ions in the waste water from the electric furnace exhaust gas cleaning equipment. Chlorine ions were confirmed by dropping an 8% aqueous silver nitrate solution into the cleaning solution, and sulfate ions were confirmed by dropping 5% aqueous barium chloride solution into the cleaning solution. The state of occurrence of precipitation was observed, and was evaluated in five stages from many to medium to few to slightly to nothing. In Reference Example 2 and Reference Example 3, more chlorine ions and sulfate ions were detected than in Reference Example 1 and Examples 12 to 16.

As is apparent from Table 5, the phosphorus fertilizers produced in Examples 12 to 16 were compared to the phosphorous fertilizer produced in Reference Example 1, including TP ₂ O ₅ and C—P ₂ O _5. This shows that the purified chicken dung combustion ash product of the present invention can be used as a phosphorus raw material for phosphorus fertilizer without any inferior components. It can be said that it is possible to substitute for phosphate ore or reduce the amount of phosphate ore by using the purified product of chicken manure combustion ash of the present invention.

(Reference Example 4 and Examples 17 to 21)
A 1 / 4000a Wagner pot was filled with paddy field soil, water was added and mixed to make a scraped state, and left in a greenhouse. The phosphorus fertilizer obtained in Reference Example 1 and Examples 12 to 16 was sprayed with 3.3 g per pot, ammonium sulfate 4.8 g, and potassium chloride 1.7 g. did. Three days later, three-leaf rice seedlings (Koshihikari) were transplanted by planting two three plants per pot, and then maintained in a submerged condition in a greenhouse. The test was performed in duplicate. The plant height of the above-ground part was measured 40 days after transplantation. The results are shown in Table 6. As is apparent from the results, Examples 17 to 21 fertilized with the fertilizer using the purified chicken manure combustion ash of the present invention grew compared with Reference Example 4 using the phosphorous fertilizer manufactured only with phosphate rock. It was confirmed that there was no difference.

  Purified chicken manure combustion ash obtained in the present invention can be used as a phosphorus raw material for fertilizers such as molten fertilizer, molten phosphorous silicate fertilizer, compound fertilizer, etc. Reduction of usage can be achieved. It can also be used directly as a fertilizer with few sulfate radicals and hydrochloric acid radicals.

Claims (4)

Purified chicken dung burned ash obtained by washing and dehydrating chicken dung burned ash, and the ratio (in weight conversion) of sulfate radicals and hydrochloric acid radicals contained in the purified chicken dung burned ash is 2% by weight or less poultry ash purified product, characterized in that. The method for producing a purified product of chicken dung burning ash according to claim 1 , wherein water is added to the chicken dung burning ash, followed by washing with water and dehydration. The pH of the water to add is 5-11, The manufacturing method of the chicken dung combustion ash refined material of Claim 2 characterized by the above-mentioned.   A phosphorus fertilizer comprising the refined chicken ash combustion ash according to claim 1.

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