JP2006240976A - Method for manufacturing phosphorus-calcium composite material, and phosphorus-calcium composite material as well as heavy metal scavenger using phosphorus-calcium composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily manufacturing a phosphorus-calcium composite material from living organism-derived ingredients such as an animal husbandry waste or a fishery waste or the like composed primarily of phosphorus and calcium, and the phosphorus-calcium composite material manufactured by the manufacturing method. <P>SOLUTION: The method for manufacturing the phosphorus-calcium composite material comprises the acid treatment of the living organism-derived ingredients composed primarily of phosphorus and calcium using a mineral acid. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a phosphorus-calcium complex, a phosphorus-calcium complex, and a heavy metal scavenger using the phosphorus-calcium complex.

  In recent years, environmental issues have been highlighted, and it has become an important issue to treat livestock waste such as chicken manure and bone meal and fishery waste such as fish bones, scales and shells in consideration of the environment. . Conventionally, it has been attempted to incinerate these wastes and use them as fertilizers.

Moreover, since these wastes contain abundant calcium and phosphorus, it has been attempted to produce hydroxyapatite from wastes (see, for example, Patent Document 1).
JP-A-8-48589

  However, in order to produce homogeneous hydroxyapatite from waste, strict raw material management and reaction control are required. For this reason, producing high-quality hydroxyapatite as a recycled product is problematic in terms of cost.

  On the other hand, conventionally, organic chelating agents such as ethylenediaminetetraacetic acid (EDTA) and piperazine dithiocarbamic acid have been used as heavy metal scavengers. In particular, it is necessary to collect harmful metals contained in fly ash in an incinerator. However, the organic part constituting the chelate compound may be decomposed by microorganisms or the like for a long time, and the heavy metal part may be liberated. In addition, since piperazine dithiocarbamic acid contains a sulfur atom in the molecule, there is also a problem that an organic part is decomposed and a harmful gas such as carbon disulfide and hydrogen sulfide is generated depending on the condition where the chelate compound is placed. .

  That is, the present invention has been made in view of the above problems, and its purpose is to easily prepare a phosphorus-calcium complex from biologically derived components mainly composed of phosphorus and calcium such as livestock waste and aquatic waste. It is in providing the manufacturing method and the phosphorus-calcium complex manufactured using this manufacturing method.

  Another object of the present invention is to provide a heavy metal scavenger using a phosphorus-calcium complex produced by using the production method.

  The present inventor has found that a phosphorus-calcium complex can be produced by subjecting a biologically derived component mainly composed of phosphorus and calcium to an acid treatment using a mineral acid or an organic acid.

Further, after the treatment, there may be a step of evaporating and drying the treated product obtained in the step.
It is also effective to recover excess acid from the viewpoint of resource reuse.
The mineral acid or organic acid preferably has a pKa value smaller than that of phosphoric acid.
Furthermore, you may perform the process of neutralizing the processed material after the evaporation to dryness obtained at the said process. And the process obtained by evaporating and drying the processed material obtained by the said neutralization process and the process of baking the processed material obtained by this evaporative drying process at 500 to 1000 degreeC may be included.

The phosphorus-calcium complex of the present invention includes hydroxyapatite (Ca ₅ (PO ₄ ) ₃ (OH)), a reaction intermediate thereof, a mixture thereof, and the like. The phosphorus-calcium complex includes both crystalline and non-crystalline solids, and in the case of crystallinity, the same substance and different crystallinity may be included. The phosphorus-calcium complex of the present invention may contain vitrokite. Furthermore, in the phosphorus-calcium complex, a mixture having different Ca / P composition ratios may be used.

  Such a phosphorus-calcium complex can be used as a heavy metal scavenger. As in the case of using the organic chelating agent, the chelate between the organic chelating agent and the metal is not cleaved by the microorganism, so that heavy metals can be collected over a long period of time. Also, no harmful gas such as carbon disulfide is generated.

  According to the method for producing a phosphorus-calcium complex of the present invention, a phosphorus-calcium complex can be easily produced from a biologically derived component mainly composed of phosphorus and calcium. In particular, waste such as livestock waste and fishery waste can be effectively reused.

  The phosphorus-calcium complex obtained by the production method of the present invention can be used, for example, as a heavy metal scavenger.

[Biological components mainly composed of phosphorus and calcium]
Examples of biologically derived components mainly composed of phosphorus and calcium used in the production of the phosphorus-calcium complex of the present invention include animal excrement such as chicken droppings, pig droppings and cow droppings, chickens, pigs, cows and the like. Examples include animal bones, fish bones, scales, and shells. Preferred is excrement of animal birds such as chicken dung, pig dung and cow dung. Of these living body-derived components, for example, chicken manure has phosphorus and calcium as main components. The biological component that can be used in the present invention is not limited to a biological component mainly composed of phosphorus and calcium, and may be a biological component mainly composed of either phosphorus or calcium. In this case, what is necessary is just to mix two or more types of biological components into a biological component containing phosphorus and calcium as main components. These biological components are used after being burned and ashed or pulverized as they are without being ashed.

[Mineral acid]
As the mineral acid that can be used in the production method of the present invention, inorganic acids having a value smaller than the pKa value of phosphoric acid, such as hydrochloric acid, nitric acid, sulfuric acid, and perchloric acid, can be used. Nitric acid is preferred.

[Organic acid]
Examples of organic acids that can be used in the production method of the present invention include organic acids having a value smaller than the pKa value of phosphoric acid, such as monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid.

(First method)
First, an acid treatment is performed on a biological component mainly composed of phosphorus and calcium using a mineral acid or an organic acid.

  The amount of mineral acid or organic acid added to the biologically derived component containing phosphorus and calcium as main components varies depending on the concentration and strength of the mineral acid or organic acid. Usually, the amount of acid added can be estimated from the amount of components such as Ca and P contained in the biological component. For example, when concentrated nitric acid (61 wt%) is used with respect to 10 g of a biologically derived component mainly composed of phosphorus and calcium, the addition amount is 3 to 30 ml, preferably 5 to 20 ml.

  A biologically derived component mainly composed of phosphorus and calcium and a mineral acid or an organic acid are subjected to an acid treatment by mixing them. This acid treatment may be performed at room temperature or a heat treatment. Preferably, heat treatment is performed. The heat treatment is performed at 60 to 100 ° C., preferably 70 to 90 ° C., for 30 minutes to 4 hours, preferably for 1 hour to 3 hours. By performing the acid treatment in this way, phosphorus contained in the biological component is liberated as phosphoric acid. After the acid treatment, the solid matter may be solid-liquid separated by a known solid-liquid separation technique such as filtration or centrifugation, if necessary, and then the liquid may be evaporated to dryness if necessary. Excess mineral acid or organic acid is removed by evaporating to dryness. The solid obtained after evaporation to dryness is the phosphorus-calcium complex in the present invention. It is also an effective method from the viewpoint of effective use of resources to recover and reuse excess acid during the evaporation to dryness process. For example, when evaporating to dryness, the mineral acid or organic acid contained in the vapor may be absorbed and collected in an absorbing solution such as water or an aqueous sodium hydroxide solution.

(Second method)
In the second method, the phosphorus-calcium complex obtained by the first method is further neutralized. Specifically, this is performed as follows.

  The neutralization treatment uses an inorganic base or an organic base (such as an amine). Examples of the inorganic base include ammonium salts such as ammonium hydroxide and alkali metal hydroxide salts such as sodium hydroxide and potassium hydroxide. Examples of the amine include aliphatic amines such as methylamine, ethylamine and butylamine, and aromatic amines such as aniline. Preferred are amines such as ammonium hydroxide and methylamine, which can easily adjust the pH.

  The neutralization treatment is performed by adding water and the neutralization treatment agent to the evaporated dry product obtained by the first method, and adjusting the pH for 30 minutes to 10 hours, preferably 30 minutes. It is performed by boiling for 4 hours, more preferably 1 hour to 3 hours. By adjusting the pH value, the properties of the resulting phosphorus-calcium complex can be changed. When obtaining hydroxyapatite, the pH may be adjusted to 7 to 13, preferably 9 to 11. After the boiling treatment, a solid content is obtained using a known solid-liquid separation method such as filtration or centrifugation. The obtained solid content is dried by heating to obtain the phosphorus-calcium complex of the present invention. Furthermore, you may bake this solid content at 500-1000 degreeC.

  The phosphorus-calcium complex of the present invention is excellent as a heavy metal scavenger. In addition, depending on the raw material used, it can be applied to various fields such as biomaterials, adsorption / separation materials such as proteins, amino acids, and DNA, catalysts, and inorganic ion exchangers.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this Example.

Example 1
Nitric acid (61%) was added to 10 g of chicken manure combustion ash fly ash having the composition shown in Table 1 below, and the mixture was heat-treated at 80 ° C. for 2 hours. Thereafter, the insoluble portion was separated by filtration, and the filtrate was evaporated to dryness to evaporate excess nitric acid and the like. Water and aqueous ammonia (28%) were added to the solid after evaporation to dryness to adjust the pH to 11.5, followed by boiling for 2 hours. After boiling, it was centrifuged and dried at 250 ° C. What was dried at 250 ° C. was qualitatively determined by X-ray diffraction measurement. Moreover, since the peak is ambiguous at 250 ° C., the properties of the sample were confirmed by firing at 1000 ° C. In addition, when evaporating to dryness, it was confirmed that when 84% of the mineral acid or organic acid contained in the vapor was absorbed by water, 84% of excess nitric acid could be recovered. The same applies to the other examples.

The results are shown in Table 2. The X-ray diffraction measurement results are shown in FIGS.

  When dried at 250 ° C., the amount of nitric acid was 10 mL, and 15 mL was only the peak of the phosphorus-calcium complex other than hydroxyapatite. On the other hand, when the amount of nitric acid was 20 mL or more, a peak of calcium sulfate could be confirmed. Further, when the amount of nitric acid is 10 mL, the diffraction peak of the hydroxyapatite precursor is high and sharp, and the background is relatively flat compared to the other, so that the purity is considered high.

In the sample after baking at 1000 ° C., hydroxyapatite (Ca ₅ (PO ₄ ) ₃ (OH)) and lime (CaO) were produced when the amount of nitric acid was 10 mL. Above 15 mL, the peak intensity of vitrokite (Ca ₃ (PO ₄ ) ₂ ) was high, and hydroxyapatite (Ca ₅ (PO ₄ ) ₃ (OH)) was low.

(Example 2)
Nitric acid concentration was 61%, 30% (61% nitric acid 20 mL + water 28.5 mL), 35.6% (61% nitric acid 20 mL + water 19.642 mL = 61%) to 10 g of chicken manure combustion ash fly ash used in Example 1. Using nitric acid changed with nitric acid (10 mL + 30% nitric acid), a chicken manure incinerated ash phosphorus-calcium complex synthesis experiment was conducted.

The results are shown in Table 3. The X-ray diffraction measurement results are shown in FIGS.

  From the above results, there is almost no difference in the weight after firing between the three methods. Therefore, even if low-concentration nitric acid is used, if the absolute amount of nitric acid is the same, the quality of the phospho-calcium complex treated with high-concentration nitric acid It was found that it was possible to synthesize a product that did not change in quantity.

  As is apparent from FIGS. 13 to 15, the crystals contained in the residues after treatment with nitric acid concentrations of 61%, 30%, and 35.6% are calcium sulfate hydrates although there is a difference in crystal structure. It was.

  Further, as is apparent from FIGS. 16 to 18, hydroxyapatite peaks were confirmed in all treatments with nitric acid concentrations of 61%, 30%, and 35.6%.

  As is clear from FIGS. 19 to 21, the 1000 ° C. dried product has a sharper hydroxyapatite peak than the 250 ° C. dried product in all treatments with nitric acid concentrations of 61%, 30%, and 35.6%. Thus, it can be seen that the purity of hydroxyapatite has increased. Moreover, since the background is flat, it turns out that there are few amorphous parts than 250 degreeC drying.

(Example 3)
The chicken manure incineration ash phosphorus-calcium complex synthesis experiment was conducted by changing the acid treatment time to 13 g of chicken manure burning ash fly ash used in Example 1, using nitric acid with a nitric acid concentration (61%).

The results are shown in Table 4. The X-ray diffraction measurement results are shown in FIGS.

  The X-ray diffraction pattern after firing at 1000 ° C. shows that there is almost no difference in the peak intensity of HAp in all samples. In addition, since there is almost no difference between the three methods in terms of the weight after firing, even if the nitric acid treatment time is short, it is possible to synthesize a nitric acid-treated 2-hour HAp that is equivalent in quality and quantity.

  As is apparent from FIGS. 22 to 24, the crystals contained in the residues of nitric acid treatment time 0.5, 1, and 2 hours were calcium sulfate hydrates although there were differences in the crystal structures.

  As is clear from FIGS. 25 to 27, the peak of hydroxyapatite could be confirmed at all nitric acid treatment times of 0.5, 1, and 2 hours.

  As is clear from FIGS. 28 to 30, the 1000 ° C. dried product has a sharp hydroxyapatite peak compared to the 250 ° C. dried product at all nitric acid treatment times of 0.5, 1 and 2 hours. This shows that the purity of hydroxyapatite has increased. Moreover, it can be seen that the 1000 ° C. dried product has less amorphous parts than the 250 ° C. dried product because the background is flat.

Example 4
Nitric acid (61%) was added to 10 g of chicken manure combustion ash fly ash (hereinafter referred to as “FA”) and bottom ash (hereinafter referred to as “BA”) having the composition shown in Table 5 under the conditions shown in Table 6. Heat-treated. Thereafter, the insoluble portion was separated by filtration, and the filtrate was evaporated to dryness to evaporate excess nitric acid and the like. Water and aqueous ammonia (28%) were added to the solid after evaporation to dryness to adjust the pH, followed by boiling treatment. After boiling, it was centrifuged and dried at 250 ° C.

The X-ray diffraction measurement results are shown in FIGS.

  As apparent from FIGS. 31 to 38, at pH 10.3, calcium sulfate was produced from FA and calcium phosphate was produced from BA. This was thought to be because hydroxyapatite (HAp), which requires an OH group, could not be synthesized because the pH was low at 10.3.

Next, the thing of pH11 which was able to synthesize | combine hydroxyapatite was baked for 30 minutes at 1000 degreeC in order to confirm the purity, and the X-ray-diffraction measurement was performed. Moreover, the weight change before and behind baking was also measured. Table 7 shows the change in weight (g) before and after firing.

  From Table 7, it can be seen that there was no significant difference in the weight change (g) before and after firing for both FA and BA.

  As apparent from FIGS. 39 to 42, although a hydroxyapatite peak was also present, most of them changed to calcium phosphate or vitrokite containing metals such as zinc, magnesium and iron. Similarly to the case of pH 10.3, since pH was low at 11, the OH group was insufficient, and it was considered that after calcination at 1000 ° C., it changed to calcium phosphate having no OH group.

(Example 5)
In Example 4, the filtration separation step was omitted, and a chicken manure incinerated ash phosphorus-calcium complex synthesis experiment was performed under the conditions shown in Table 8 below. The omission of the filtration step is aimed at simplifying the production equipment when put into practical use.
Citation of Example 4 here is as conditions other than the following Table 8, the chicken dung combustion ash fly ash to be used is a component of Table 5, the evaporation step, water, adjusting the pH by adding aqueous ammonia, For example, drying at 250 ° C. and 1000 ° C.

X-ray diffraction measurement results are shown in FIGS. A phosphorus-calcium complex was obtained.

As is clear from FIGS. 43 to 46, a hydroxyapatite peak could be confirmed. Next, in order to confirm these purity, as shown in FIGS. 47-50, after baking for 30 minutes at 1000 degreeC, the X-ray-diffraction measurement was performed. Moreover, the weight change before and behind baking was also measured. Table 9 shows the weight change (g) before and after firing.

  From these results, it can be seen that although hydroxyapatite peaks exist, most of them changed to calcium phosphate or vitrokite containing metals such as zinc, magnesium and iron. As in the case of pH 10.3, since pH is low at 11, it is considered that OH groups were insufficient, and after baking at 1000 ° C., calcium phosphate having no OH groups was changed.

(Example 6)
Take 10g of chicken manure burning ash FA in a 300mL Erlenmeyer flask, add concentrated nitric acid, heat treatment at about 60 ° C, filter, evaporate the filtrate, and adjust the pH by adding water and aqueous ammonia. After boiling for 2 hours and drying at 250 ° C., the product was qualitatively analyzed by X-ray diffraction measurement. Samples that were not heated during the nitric acid treatment were also prepared. The synthesis conditions are shown in Table 10.

The X-ray diffraction measurement results are shown in FIGS.

  As is apparent from FIGS. 51 to 54, the peak of hydroxyapatite peak was confirmed, but calcium sulfate was also present. Since nitric acid was not completely volatilized at the time of evaporation to dryness before pH adjustment, it contained more ammonium nitrate than other reaction systems, so it was thought that nitrate might have inhibited the peak synthesis of hydroxyapatite.

(Example 7)
Take 10 g of chicken manure combustion ash FA in a 300 mL Erlenmeyer flask, add concentrated hydrochloric acid, heat treatment at about 80 ° C, filter, evaporate the filtrate to dryness, add water and aqueous ammonia to adjust pH to 11. After boiling for 2 hours and drying at 250 ° C., X-ray diffraction measurement was performed to qualitatively analyze the product.

  The X-ray diffraction measurement results are shown in FIGS.

As apparent from FIGS. 55 to 56, it is considered that chloroapatite in which Cl ⁻ was bonded to the position of the OH group in hydroxyapatite was synthesized due to the presence of a large amount of Cl ⁻ in the reaction system.

(Example 8)
Take 10 g of chicken manure ash FA in a 300 mL Erlenmeyer flask, add 20 mL of concentrated nitric acid, heat treatment at about 80 ° C., filter, evaporate the filtrate to dryness, add water and aqueous ammonia to adjust pH to 11. After adjustment, the mixture was left overnight and dried at 100 ° C., followed by X-ray diffraction measurement to qualitatively analyze the product.

  The X-ray diffraction measurement results are shown in FIG.

  As is clear from FIG. 57, it was found that a boiling step after pH adjustment is necessary for the synthesis of hydroxyapatite.

Example 9
Take 10g of chicken manure combustion ash FA in a 300mL Erlenmeyer flask, add concentrated nitric acid, heat treatment at about 80 ° C, filter, evaporate the filtrate to dryness, and adjust the pH by adding water and aqueous ammonia. The boiling time was changed to 0.5 hour, 1 hour, and 2 hours, and after boiling, the product was qualitatively analyzed by X-ray diffraction measurement after drying at 250 ° C.

  The X-ray diffraction measurement results are shown in FIGS.

  As is apparent from FIGS. 58 to 60, the peak of hydroxyapatite could be confirmed in all samples with the boiling time changed to 0.5, 1 and 2 hours.

In order to confirm these purities, as shown in FIGS. 61 to 63, X-ray diffraction measurement was performed after firing at 1000 ° C. for 30 minutes. Moreover, the weight change before and behind baking was also measured. Table 11 shows the change in weight (g) before and after firing.

  As is clear from FIGS. 61 to 63, the peak of hydroxyapatite became sharper than that of the dried product at 250 ° C. in all cases where the boiling time was changed to 0.5, 1 and 2 hours. It can be seen that the purity has increased. Moreover, since the background is flat, it turns out that there are few amorphous parts than 250 degreeC drying.

  From the above, from the X-ray diffraction diagram, it was possible to synthesize hydroxyapatite equivalent to when the boiling time after pH adjustment was 0.5 hour, 1 hour or 2 hours. From the weight, it can be seen that most of the samples were boiled for 0.5 hours. It was found that even if the boiling time after the pH adjustment was shortened, it was possible to synthesize hydroxyapatite that was equal to or higher than that boiled for 2 hours in both quality and quantity.

(Example 10)
15 mL of nitric acid (61%) was added to 10 g of chicken manure combustion ash fly ash, and the acid treatment time was changed to 30 minutes, 60 minutes, and 120 minutes, and heat treatment was performed at 80 ° C. Thereafter, the insoluble portion was separated by filtration, and the filtrate was evaporated to dryness to evaporate excess nitric acid and the like. Water and aqueous ammonia (28%) were added to the solid after evaporation to dryness to adjust the pH to 11.5 and 12, followed by boiling for 2 hours. After boiling, it was centrifuged and dried at 250 ° C. What was dried at 250 ° C. was qualitatively determined by X-ray diffraction measurement. Moreover, since the peak is ambiguous at 250 ° C., the properties of the product were confirmed by baking at 1000 ° C.

The results are shown in Table 12. The X-ray diffraction measurement results are shown in FIGS.

  From FIGS. 64 to 75, it can be seen that at pH 11.5, vitrokite and hydroxyapatite coexist, and at pH 12, only hydroxyapatite was produced except for 30 minutes of nitric acid treatment.

  The nitric acid treatment time was 60 minutes, and the peak was high and the yield was high regardless of the pH.

(Example 11)
After adding 15 mL of 61% nitric acid to 10 g of chicken manure ash fly ash and heat-treating at 80 ° C. for 60 minutes, the insoluble part was removed by filtration using filter paper, and the filtrate was evaporated to dryness. After evaporation to dryness, water and 28% aqueous ammonia were added to adjust the pH, followed by boiling for 30 minutes. After boiling, the product was centrifuged and the product was dried. Comparison was made by changing the drying temperature to 105 ° C and 250 ° C. They were also fired at 1000 ° C. to qualify the product.

  The X-ray diffraction measurement results are shown in FIGS.

  As is clear from FIGS. 76 to 79, no significant difference was found in the product, either by comparison with the drying treatment alone or by comparison with the one after firing. That is, it was found that the desired product could be obtained sufficiently even after drying at 105 ° C.

(Example 12)
61% nitric acid was added to 13 g of chicken manure combustion ash fly ash and heat-treated, and then the insoluble part was removed by filtration using filter paper, and the filtrate was evaporated to dryness. After evaporation to dryness, water and 28% aqueous ammonia were added to adjust the pH to 12, followed by boiling for 2 hours. After boiling, the product was centrifuged and the product was dried. The drying temperature was 250 ° C. Further, they were baked at 500, 800 and 1000 ° C. with different calcination temperatures, and X-ray diffraction measurement was performed to qualitatively analyze the products. As a comparative example, the reagent hydroxyapatite was used.

The X-ray diffraction measurement results are shown in FIGS. The reaction conditions are shown in Table 13, and the weight loss after firing is shown in Table 14.

  The 250 ° C. dry product was inferior to the hydroxyapatite synthesized with the reagent, but a peak intensity equivalent to that of the reagent hydroxyapatite was obtained at a firing temperature of 1000 ° C.

  Hydroxyapatite synthesized from chicken manure ash is ocher because it contains iron and manganese as shown in the component values of chicken manure ash. Although it is not suitable for the field where white is required for this coloring, the performance is expected to be sufficiently equivalent to that of the reagent hydroxyapatite, as can be seen from the X-ray diffraction measurement results shown in FIGS. .

(Example 13)
A sample obtained by drying and baking chicken dung ash HAp produced at a pH of 11 and 12 at the time of pH adjustment in a process for producing hydroxyapatite (hereinafter abbreviated as chicken dung ash HAp) obtained from chicken dung burned ash at 250 ° C. and 1000 ° C. (Hereinafter, those dried at pH 11, 250 ° C., 11-250, those baked at 1000 ° C., 11-1000, those dried at pH 12, 250 ° C., baked at 12-250, 1000 ° C. 12-1000).

In a 100 mL plastic container, 11-250, 11-1000, 12-250, and 12-1000 are put in 0.05, 0.15, and 0.25 g respectively, and 50 mL each of heavy metal solution (Cd, Pb, Cr) is added. Then, the mixture was shaken overnight and the concentration of heavy metals in the supernatant after centrifugation was measured by atomic absorption spectrophotometry. This adsorption test was performed in duplicate. The types and concentrations of heavy metals used are shown in Table 15, and the filtrate heavy metal concentrations (Pb and Cd concentrations) after overnight shaking are shown in Tables 16 and 17, respectively.

  Considering that the drainage standard for both lead and cadmium is 0.1 ppm, sufficient adsorption capacity was obtained. Since environmental standards are 0.01 ppm for both lead and cadmium, it can be seen that lead has the ability to clear environmental standards at 11-250.

  Moreover, chromium was not adsorbed at all.

(Example 14)
To a molten fly ash having the composition shown in Table 18 below, calcium phosphate and water obtained from a predetermined amount of chicken manure combustion ash were added and kneaded for 10 minutes. In addition, before adding calcium phosphate, the process which added the sulfuric acid and sodium sulfate as an adjuvant was also performed.

(Comparative Example 1)
The same procedure as in Experimental Example 2 was performed except that a chelating agent was used instead of calcium phosphate obtained from chicken manure combustion ash.

Based on Environmental Agency Notification No. 13, the Pb elution test was conducted with the scale reduced by the method described in the same issue. The results are shown in Tables 19 and 20.

(Example 15)
A lead ion adsorption test was performed using the samples shown below. First, a solution of about 200 ppm Pb ²⁺ was prepared using lead nitrate. Next, 0.05 g of each sample of HAp and its precursor was taken in a 100 mL plastic container, and 50 mL of an aqueous lead nitrate solution was added and shaken for 5 hours. Thereafter, the concentration of lead remaining in the supernatant was measured using an atomic absorption photometer. The results are shown in Table 21.
Sample details 01 Raw material fly ash 02 Raw material bottom ash 03 Fly ash 10g Nitric acid 20mL 80 ℃
04 Fly ash 10g Nitric acid 40mL 80 ℃
05 Bottom ash 10g Nitric acid 20mL 80 ℃
06 Bottom ash 10g Nitric acid 40mL 80 ℃
07 Fly ash 10g No filtration after nitric acid treatment 08 Bottom ash 10g No filtration after nitric acid treatment 09 Fly ash 10g Nitric acid 20mL Room temperature 10 Fly ash 10g Hydrochloric acid 20mL
11 Fly ash 10 g Nitric acid 20 mL 60 ° C. 30 min 12 Fly ash 10 g Nitric acid 20 mL 60 ° C. 120 min 13 Fly ash 10 g No pH adjustment and boiling (100 ° C. drying)
14 10g fly ash No pH after pH adjustment (250 ° C drying)

  From this table, it was found that the apatite-treated material adsorbed lead to almost 0 ppm.

(Example 16)
Each 0.05 ml of hydroxyapatite and vitrokite obtained in Example 1 was placed in a 50 mL centrifuge, and 30 mL of a lead nitrate aqueous solution having a lead concentration of 61 ppm was added and dispersed for 1 minute. Then, it centrifuged and collect | recovered supernatant liquids. 30 mL of a lead nitrate aqueous solution with a lead concentration of 61 ppm was added to the residue after the supernatant was collected, and dispersed for 1 minute. Then, it centrifuged and collect | recovered supernatant liquids. This operation was repeated 6 times. The lead concentration of each collected supernatant was measured using an atomic absorption photometer. The results are shown in Table 22.

  From the above, it was found that Vitrokite has higher lead adsorption capacity.

(Example 17)
Concentrated nitric acid was added to the chicken manure combustion ash used in Example 1, and after heat treatment at about 80 ° C., the mixture was evaporated to dryness at 100 ° C., and then heated at 400 ° C. to remove the nitric acid almost completely. An inventive phosphorus-calcium complex was obtained.

  This phosphorus-calcium complex and a chelating agent (manufactured by Tosoh Corporation: trade name TS-275) were used according to the heavy metal elution test method such as incinerated ash according to Notification No. 13 of the Environment Agency. However, the method of the Environment Agency stipulates that the sample is 50 gr and the amount of the solution at the time of shaking is 500 mL or more. Here, the scale is reduced, and the sample is about 10 grams and water is 100 mL.

The following samples were used.
(Sample to be processed)
1) Molten fly ash 2) Mixed incineration ash of medical waste 1/2 + industrial waste 1/2 3) General waste incineration ash 4) General waste incineration ash

Two series of the above fly ash samples 1) to 4) with 10 gr added to 30 to 50% humidified water are prepared, each of which has the same weight of chelating agent (hereinafter referred to as “TS-275”) and the phosphorus-calcium of the present invention. A complex (hereinafter referred to as “P · Ca complex”) was added and sufficiently kneaded, and then a heavy metal elution test was performed. The results are shown in Tables 23 to 26 and FIGS. However, an appropriate amount of sulfuric acid aqueous solution was added to the P · Ca complex series as a pretreatment.

From the above results, the phosphorus-calcium complex of the present invention was able to suppress the elution amount of Pb with a smaller amount than the existing chelating agent.

  Provided is a method for easily producing a phosphorus-calcium complex from a biological component mainly composed of phosphorus and calcium such as livestock waste and aquatic waste, and a phosphorus-calcium complex produced by using this production method can do.

FIG. 1 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 250 ° C. with 10 mL of nitric acid. FIG. 2 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 250 ° C. with 15 mL of nitric acid. FIG. 3 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 250 ° C. with 20 mL of nitric acid. FIG. 4 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 250 ° C. with 25 mL of nitric acid. FIG. 5 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 250 ° C. with 30 mL of nitric acid. FIG. 6 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 250 ° C. with 35 mL of nitric acid. FIG. 7 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 1000 ° C. with 10 mL of nitric acid. FIG. 8 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 1000 ° C. with 15 mL of nitric acid. FIG. 9 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 1000 ° C. with 20 mL of nitric acid. FIG. 10 is a chart showing the result of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 1000 ° C. with 25 mL of nitric acid. FIG. 11 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 1000 ° C. with 30 mL of nitric acid. FIG. 12 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 1000 ° C. with 35 mL of nitric acid. FIG. 13 is a chart showing the results of X-ray diffraction of the residue after acid treatment with a nitric acid concentration of 61%. FIG. 14 is a chart showing the results of X-ray diffraction of the residue after acid treatment with a nitric acid concentration of 30%. FIG. 15 is a chart showing the results of X-ray diffraction of the residue after acid treatment at a nitric acid concentration of 35.6%. FIG. 16 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention, which was acid-treated at a nitric acid concentration of 61% and then dried at 250 ° C. FIG. 17 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention that was acid-treated at a nitric acid concentration of 30% and then dried at 250 ° C. FIG. 18 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention that was acid-treated at a nitric acid concentration of 35.6% and then dried at 250 ° C. FIG. 19 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention that was acid-treated at a nitric acid concentration of 61% and then dried at 1000 ° C. FIG. 20 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention, which was acid-treated at a nitric acid concentration of 30% and then dried at 1000 ° C. FIG. 21 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention that was acid-treated at a nitric acid concentration of 35.6% and then dried at 1000 ° C. FIG. 22 is a chart showing the result of X-ray diffraction of the residue after acid treatment with nitric acid for 0.5 hour. FIG. 23 is a chart showing the result of X-ray diffraction of the residue after acid treatment with nitric acid for 1 hour. FIG. 24 is a chart showing the results of X-ray diffraction of the residue after acid treatment with nitric acid for 2 hours. FIG. 25 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention that was acid-treated with nitric acid for 0.5 hour and then dried at 250 ° C. FIG. 26 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention which was acid-treated with nitric acid for 1 hour and then dried at 250 ° C. FIG. 27 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention which was acid-treated with nitric acid for 2 hours and then dried at 250 ° C. FIG. 28 is a chart showing the result of X-ray diffraction of the phosphorus-calcium complex of the present invention, which was treated with nitric acid for 0.5 hour and then dried at 1000 ° C. FIG. 29 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention, which was acid-treated with nitric acid for 1 hour and then dried at 1000 ° C. FIG. 30 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention that was acid-treated with nitric acid for 2 hours and then dried at 1000 ° C. FIG. 31 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of FA to 20 mL of nitric acid and then neutralizing at pH 11. FIG. 32 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of FA with 40 mL of nitric acid and then neutralizing with pH 11. FIG. 33 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of BA with 20 mL of nitric acid and then neutralizing at pH 11. FIG. 34 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of BA with 40 mL of nitric acid and neutralizing at pH 11. FIG. 35 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of FA with 20 mL of nitric acid and then neutralizing at pH 10.3. FIG. 36 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of FA with 40 mL of nitric acid and then neutralizing at pH 10.3. FIG. 37 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of BA with 20 mL of nitric acid and neutralizing at pH 10.3. FIG. 37 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of BA with 40 mL of nitric acid and neutralizing at pH 10.3. FIG. 39 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of FA to 20 mL of nitric acid, neutralizing at pH 11 and then drying at 1000 ° C. FIG. 40 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of FA to 40 mL of nitric acid, neutralizing at pH 11 and drying at 1000 ° C. FIG. 41 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of BA with 20 mL of nitric acid, neutralizing at pH 11, and drying at 1000 ° C. FIG. 42 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of BA with 40 mL of nitric acid, neutralizing at pH 11 and drying at 1000 ° C. FIG. 43 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of FA with 15 mL of nitric acid and then neutralizing with pH 11. FIG. 44 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating FA10 g with 20 mL of nitric acid and then neutralizing at pH 11. FIG. 45 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of BA with 15 mL of nitric acid and then neutralizing at pH 11. FIG. 46 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of BA with 20 mL of nitric acid and neutralizing at pH 11. FIG. 47 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of FA to 15 mL of nitric acid, neutralizing at pH 11 and then drying at 1000 ° C. FIG. 48 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of FA to 20 mL of nitric acid, neutralizing at pH 11 and then drying at 1000 ° C. FIG. 49 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of BA with 15 mL of nitric acid, neutralizing at pH 11 and drying at 1000 ° C. FIG. 50 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of BA with 20 mL of nitric acid, neutralizing at pH 11 and drying at 1000 ° C. FIG. 51 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of FA with 20 mL of nitric acid at 80 ° C. for 0.5 hour and then neutralizing with pH 11. FIG. 52 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention, which was acid-treated with 20 mL of nitric acid at 20 ° C. for 1 hour at 80 ° C. and then neutralized at pH 11. FIG. 53 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by acid-treating 10 g of FA with 20 mL of nitric acid at 80 ° C. for 2 hours and neutralizing at pH 11. FIG. 54 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention neutralized at pH 11 after acid treatment at room temperature with 20 mL of nitric acid FA. FIG. 55 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention, which was acid-treated with 20 mL of concentrated hydrochloric acid and then dried at 250 ° C. FIG. 56 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention, which was acid-treated with 20 mL of concentrated hydrochloric acid and then dried at 1000 ° C. FIG. 57 shows the X-ray diffraction of the phosphorus-calcium complex of the present invention, which was treated with 10 g of FA in 20 mL of nitric acid at 80 ° C. for 2 hours, neutralized at pH 11 and then left overnight without boiling. It is a chart showing the result of. FIG. 58 shows the result of X-ray diffraction of the phosphorus-calcium complex of the present invention, which was 10 g of FA with 20 mL of nitric acid, acid-treated at 80 ° C. for 2 hours, neutralized at pH 11 and then boiled for 0.5 hours. It is a chart showing. FIG. 59 shows the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of FA to 20 mL of nitric acid at 80 ° C. for 2 hours, neutralizing at pH 11, and boiling for 1 hour. It is a chart. FIG. 60 shows the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting FA 10 g to 20 mL of nitric acid at 80 ° C. for 2 hours, neutralizing at pH 11, and boiling for 2 hours. It is a chart. FIG. 61 shows the phosphorous-calcium composite according to the present invention, in which 10 g of FA was acid-treated with 20 mL of nitric acid at 80 ° C. for 2 hours, neutralized at pH 11 and then boiled for 0.5 hours and then baked at 1000 ° C. It is a chart showing the result of the X-ray diffraction of a body. FIG. 62 shows the phosphorous-calcium complex of the present invention obtained by subjecting 10 g of FA to 20 mL of nitric acid at 80 ° C. for 2 hours, neutralizing at pH 11, boiling for 1 hour, and then firing at 1000 ° C. It is a chart showing the result of X-ray diffraction. FIG. 63 shows the phosphorous-calcium complex of the present invention obtained by subjecting 10 g of FA to 20 mL of nitric acid at 80 ° C. for 2 hours, neutralizing at pH 11 and then boiling for 2 hours and then firing at 1000 ° C. It is a chart showing the result of X-ray diffraction. FIG. 64 shows the phospho-calcium complex of the present invention, which was 10 g of chicken dung ash treated with nitric acid for 30 minutes, neutralized at pH 11.5, boiled for 2 hours, and dried at 250 ° C. It is a chart showing the result of X-ray diffraction. FIG. 65 shows the phosphorus-calcium complex of the present invention obtained by treating 10 g of chicken dung ash with nitric acid for 60 minutes, neutralizing at pH 11.5, boiling for 2 hours, and drying at 250 ° C. It is a chart showing the result of X-ray diffraction. FIG. 66 shows the phospho-calcium complex of the present invention, wherein 10 g of chicken dung ash was acid-treated with nitric acid for 120 minutes, neutralized at pH 11.5, boiled for 2 hours, and dried at 250 ° C. It is a chart showing the result of X-ray diffraction. FIG. 67 shows the X-ray of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of chicken dung ash to acid treatment with nitric acid for 30 minutes, neutralizing at pH 12 and then boiling for 2 hours and drying at 250 ° C. It is a chart showing the result of diffraction. FIG. 68 shows an X-ray of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of chicken dung ash to acid treatment with nitric acid for 60 minutes, neutralizing at pH 12 and then boiling for 2 hours and drying at 250 ° C. It is a chart showing the result of diffraction. FIG. 69 shows X-ray of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of chicken dung ash to acid treatment with nitric acid for 120 minutes, neutralizing at pH 12 and then boiling for 2 hours and drying at 250 ° C. It is a chart showing the result of diffraction. FIG. 70 shows X of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of chicken dung ash to acid treatment with nitric acid for 30 minutes, neutralizing at pH 11.5, boiling for 2 hours, and firing at 1000 ° C. It is a chart showing the result of a line diffraction. FIG. 71 shows X of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of chicken dung ash to acid treatment with nitric acid for 60 minutes, neutralizing at pH 11.5, boiling for 2 hours, and baking at 1000 ° C. It is a chart showing the result of a line diffraction. FIG. 72 shows X of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of chicken dung ash to acid treatment with nitric acid for 120 minutes, neutralizing at pH 11.5, boiling for 2 hours, and firing at 1000 ° C. It is a chart showing the result of a line diffraction. FIG. 73 shows the X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of chicken manure ash to acid treatment with nitric acid for 30 minutes, neutralizing at pH 12 and boiling treatment for 2 hours, followed by baking at 1000 ° C. It is a chart showing the result of. Fig. 74 shows X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of chicken manure ash to acid treatment with nitric acid for 60 minutes, neutralizing at pH 12 and boiling treatment for 2 hours, followed by baking at 1000 ° C. It is a chart showing the result of. FIG. 75 shows X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting 10 g of chicken manure ash to acid treatment with nitric acid for 120 minutes, neutralizing at pH 12 and then boiling for 2 hours and then baking at 1000 ° C. It is a chart showing the result of. FIG. 76 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 105 ° C. after boiling treatment. FIG. 77 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention dried at 250 ° C. after boiling treatment. FIG. 78 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention, which was dried at 105 ° C. and baked at 1000 ° C. after boiling. FIG. 79 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention, which was dried at 250 ° C. after being boiled and then baked at 1000 ° C. FIG. 80 is a chart showing the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting 13 g of FA to 30 mL of nitric acid at room temperature for 2 hours, neutralizing at pH 12, and boiling for 2 hours. It is. FIG. 81 shows the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting 13 g of FA to 30 mL of nitric acid at 80 ° C. for 1 hour, neutralizing at pH 12 and boiling for 2 hours. It is a chart. FIG. 82 shows the results of X-ray diffraction of the phosphorus-calcium complex of the present invention obtained by subjecting 13 g of FA to 40 mL of nitric acid at 80 ° C. for 2 hours, neutralizing at pH 12 and boiling for 2 hours. It is a chart. FIG. 83 is a chart showing the results of X-ray diffraction of the reagent hydroxyapatite. FIG. 84 shows the phosphorous-calcium composite of the present invention obtained by subjecting 13 g of FA to 30 mL of nitric acid at room temperature for 2 hours, neutralizing at pH 12, boiling for 2 hours, and then firing at 500 ° C. for 1 hour. It is a chart showing the result of X-ray diffraction. FIG. 85 shows the phosphorous-calcium composite of the present invention obtained by subjecting 13 g of FA to 30 mL of nitric acid at room temperature for 2 hours, neutralizing at pH 12, followed by boiling for 2 hours and then baking at 800 ° C. for 1 hour. It is a chart showing the result of X-ray diffraction. FIG. 86 shows the phosphorous-calcium composite of the present invention obtained by subjecting 13 g of FA to 30 mL of nitric acid at room temperature for 2 hours, neutralizing at pH 12, followed by boiling for 2 hours and then firing at 1000 ° C. for 30 minutes. It is a chart showing the result of X-ray diffraction. FIG. 87 is a chart showing the result of X-ray diffraction in which the reagent hydroxyapatite was baked at 1000 ° C. for 30 minutes. FIG. 88 is a graph showing the results of a heavy metal elution test such as incinerated ash between the phosphorus-calcium complex of the present invention and an existing chelating agent. FIG. 89 is a graph showing the results of another heavy metal elution test such as incinerated ash between the phosphorus-calcium complex of the present invention and an existing chelating agent. FIG. 90 is a graph showing the results of another heavy metal elution test such as incinerated ash between the phosphorus-calcium complex of the present invention and an existing chelating agent. FIG. 91 is a graph showing the results of another heavy metal elution test such as incinerated ash between the phosphorus-calcium complex of the present invention and an existing chelating agent.

Claims (8)

A biologically derived component mainly composed of phosphorus and calcium,
A method for producing a phosphorus-calcium complex by acid treatment using a mineral acid. A biologically derived component mainly composed of phosphorus and calcium,
A method for producing a phosphorus-calcium complex by acid treatment using an organic acid. The method for producing a phosphorus-calcium complex according to claim 1 or 2, comprising a step of evaporating and drying the obtained processed product. The method for producing a phosphorus-calcium complex according to claim 3, comprising recovering excess acid during the step of evaporating and drying the obtained treated product. The manufacturing method of the phosphorus-calcium complex in any one of Claim 1 thru | or 4 including the process of neutralizing the said processed material obtained. Evaporating and drying the treated product obtained in the neutralization step;
A method for producing a phosphorus-calcium complex according to claim 5, further comprising a step of firing the processed product obtained by the step of evaporating to dryness at 500 ° C to 1000 ° C.   A phosphorus-calcium complex produced by the production method according to any one of claims 1 to 6. A heavy metal scavenger using the phosphorus-calcium complex according to claim 7.

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