KR20080010916A - Calcareous silicate fertilizer and manufacturing method thereof - Google Patents

Abstract

A preparation method of a calcareous silicate fertilizer containing pyroligneous liquor is provided to make best use of effective elements and high water absorption properties of the pyroligneous liquor. A preparation method of a calcareous silicate fertilizer includes the steps of: baking waste shells or egg shells at 1000-1200deg.C and pulverizing the waste shells or the egg shells; mixing 100wt% of the baked waste shell powder or egg shell powder with 80-120wt% of 60-80deg.C water to cause hydration; baking biotite at 900-950deg.C and pulverizing the biotite; and adding 100wt% of a mixture, which is composed of 60-70wt% of the waste shells or egg shells and 40-30wt% of the biotite powder, into 20-35wt% of water containing 4-8% concentration pyroligneous liquor.

Description

Calcium silicate fertilizer containing wood vinegar and its manufacturing method

The present invention relates to a siliceous calcium fertilizer containing wood vinegar and a method for producing the same, and more particularly, by mixing wood vinegar with a shell or egg shell powder and a germanium-containing silicate (biotite) powder and pelletizing it The present invention relates to a siliceous lime fertilizer containing wood vinegar which can produce a functional agricultural product containing each active ingredient efficiently and at the same time, which can increase the income of farmers, and a manufacturing method thereof.

Wood vinegar is a dark brown liquid produced during the capture, cooling, and condensation of smoke from carbonizing oak. Its main components are organic acids such as acetic acid, and minerals such as Ca, Mg, K, Na and 200 kinds of organic compounds. It is composed of new materials that can be used in various fields such as agriculture, livestock, food, and medicine.

Such wood vinegar contains various active ingredients and has excellent permeability and absorption to plants, so it has the advantage of improving the absorption of fertilizer components necessary for plant growth or reducing pests, but it is not easy to handle and use when spread in liquid state. There was no discomfort.

Silicate is a kind of mica whose main component is SiO _{2. It} is a mineral that contains a large amount of minerals. It has various effects such as improving rooting ability of plant roots, increasing resistance to diseases, and improving soil environment by releasing large amounts of anions. In addition, the silicate (biotite) contains a variety of components that can be used as a direct fertilizer, such as SiO ₂ · Fe ₂ O ₃ · CaO · MgO · K ₂ O · Na ₂ O in addition to germanium, among which germanium supply of oxygen in the cell, the blood purification, which is effective in vivo heavy metal emissions, inhibition of tumor development and metastasis, aging retardation, immune system enhancement, natural healing enhancement, such as, SiO ₂ is excessively absorbed nitrogen is weak crop disease resistance By suppressing the absorption of nitrogen to increase the physiological resistance to germs, MgO plays a leading role in the formation of photosynthesis and chlorophyll is characterized by excellent effects in improving the color and sugar content of plants. In particular, the Ge component contained in the silicate is absorbed and accumulated in the plant, so that the organic germanium is made, thereby enabling the production of functional agricultural products. However, when it is just used in the soil, crops have a disadvantage in that the efficiency of directly absorbing and using it is inconvenient when it is used as a powder.

On the other hand, shells and egg shells, such as shells and oyster shells, contain a large amount of CaO, which is excellent in preventing the fall and decay by maintaining the rooting environment of plants and maintaining strong bonds between plant cells. It can be used as a soil improver that can neutralize the soil. However, when the waste shell or egg shell powder is used simply, the absorption and utilization efficiency of the crop is low, and there is a problem in that the user avoids the use due to the inconvenience of using the powder.

The present invention has been made to solve the above problems, wood vinegar solution and waste shell or egg shell powder, silicate fertilizer containing wood vinegar solution, which takes full advantage of the various active ingredients contained in the silicate to solve the inconvenience of use, and It aims at providing the manufacturing method.

It is another object of the present invention to provide a siliceous calcined fertilizer containing wood vinegar and a method for producing the same, which can induce mechanized farming and increase farm income by producing functional agricultural products.

The above object of the present invention is to provide a silicate fertilizer fertilizer containing wood vinegar, and a method for producing the wood vinegar dilution of the shell or egg shell powder and germanium-containing silicate powder and pelletized (granulated) To achieve the above, the siliceous lime fertilizer containing the wood vinegar not only efficiently contains various active ingredients, but also has a high absorption rate and is easy to use, which can greatly contribute to increasing the income of the farm.

The present invention comprises wood vinegar solution made of pellets by mixing 100 parts by weight of the mixture consisting of 60 to 70 parts by weight of waste shell or egg shell powder and 40 to 30 parts by weight of silicate powder and 20 to 35 parts by weight of water containing 4 to 8% of wood vinegar solution. One is about silicate calcareous fertilizer.

In the present invention, the waste shell or egg shell powder and the silicate powder are mixed at a ratio of 60 to 70 parts by weight and 40 to 30 parts by weight, respectively, and when this ratio is out of the range of the component in the fertilizer process standard, it can be used as wollastonite or calcium fertilizer. Difficult to use

In addition, in the present invention, it is preferable to make a pellet by mixing 20 to 35 parts by weight of wood vinegar-containing water at a concentration of 4 to 8% with respect to 100 parts by weight of the mixture of waste shell or egg shell powder and silicate powder. Using water containing 4 ~ 8% concentration is the best way to economically use expensive wood vinegar, and considering the rate of extruding material from the pellet mill and the abrasion of the machine, the water content is mixed at the above ratio. Adjusting (preferably 20-25%) can produce pellets of good quality.

In the present invention, the particle size of the closed shell or egg shell powder is preferably 0.5 to 2㎛, and the particle size of the silicate powder is preferably 0.5 to 2㎛, within which the particles are evenly mixed and the pellet production rate is Faster.

Since the step of making the pellet by mixing the mixture and wood vinegar is not significantly affected by the temperature it can be obtained pellets of excellent quality even in the temperature range from room temperature to 80 ℃.

The silicic acid calcium fertilizer containing the wood vinegar of the present invention is preferably a pellet having a water content of 15% or less from the viewpoint of ease of storage and use of the fertilizer.

The silicic acid lime fertilizer containing the wood vinegar of the present invention as described above, the step of pulverizing the waste shell or egg shell at 1,000 ~ 1,200 ℃; Mixing the calcined waste shell or egg shell powder with 100 parts by weight and 80 to 120 parts by weight of water at 60 to 80 ° C. to cause a hydration reaction; Calcining the silicate (biotite) by firing at 900 to 950 ° C; 60 to 70 parts by weight of the waste shell or eggshell powder and 40 to 30 parts by weight of the silicate powder, and 100 to parts by weight and 4 to 8% by weight of 20 to 35 parts by weight of wood-containing water composition comprising the step of making a pellet It is manufactured by the method.

In the present invention, the waste shell or egg shell powder is calcined at 1,000 to 1,200 ℃ and cooled to room temperature and then subjected to a hydration reaction with water of 60 to 80 ℃, the silicate (biotite) powder is 900 to 950 ℃ Use calcined ones.

Shells, egg shells, and silicates have a large increase in water-soluble components that can be directly absorbed and used in animals and plants when firing at the firing temperature as described above.

In the case of shells or egg shells, firing at a temperature higher than 1,200 ° C. does not cause any increase in water-soluble components, which is uneconomical. On the other hand, when the silicate is calcined at a temperature higher than 950 ℃ is a problem that the germanium component is volatilized and lost, and the firing effect does not appear at a temperature lower than 900 ℃.

The calcined waste shell or eggshell powder is hydrated by mixing in a ratio of 60 to 80 ℃ water and 100 parts by weight: 80 to 120 parts by weight. At this time, if the water temperature is lower than 60 ℃ hydration reaction takes more than 1 hour If the temperature of the water is higher than 80 ℃, violent hydration reaction generates scattering dust. When the calcined waste shell or egg shell powder at room temperature and the water of 60-80 ° C. hydration reaction, the temperature rises to 200-300 ° C., and due to this high temperature, the powder is dried to obtain a finer powder than the first. .

In addition, when the calcined waste shell or egg shell powder is not hydrated or hydrated under conditions outside the temperature and mixing ratio, adhesive force does not occur when pellets are manufactured, so that pellets are not easily formed and are easily broken into powder.

Therefore, in order to make pellets of good quality without the addition of organic matter, it is essential to hydrate the calcined waste shell or egg shell powder, which facilitates the manufacture of pellets by improving the viscosity during pellet production.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.

Example 1

1. The collected shells were washed, calcined at 1,200 ° C., cooled to room temperature, and then ground to particles having a size of 1 μm.

2. 20 kg of crushed clams and 20 kg of water at 80 ° C. were mixed, and the hydration reaction started about 1 minute later.

Due to the hydration reaction, the temperature was raised to 295 ° C., thereby drying to obtain a powder having a finer particle size of 0.9 μm than the first.

3. The silicate containing germanium was calcined at 900 ° C., cooled to room temperature, and then ground into particles having a size of 1 μm.

4. The calcined and hydrated clam powder and the calcined silicate powder were blended in a ratio of 70:30 parts by weight.

5. 100 parts by weight of the mixture and 25 parts by weight of water containing 5% wood vinegar were sprayed and mixed in a granulator at room temperature.

6. The blended mixture is molded into pellets 6 ~ 7mm, then crumbled to a certain size, and then dumbled and dried to 15% or less of moisture content. ① 1 ~ 2mm, ② 2 ~ 5mm ③ ③ 1mm or less powder size and sorted and packed.

Example 2

1. The collected shells were washed, calcined at 1,000 ° C., cooled to room temperature, and then ground to particles having a size of 0.6 μm.

2. 10 kg of crushed shellfish and 12 kg of water at 60 ° C. were mixed, and the hydration reaction started after about 5 minutes.

The temperature was raised to 210 ° C. due to the hydration reaction, whereby drying gave a finer powder of 0.5 μm size than the first.

3. The silicate containing germanium was calcined at 950 ° C., cooled to room temperature, and then ground into particles having a size of 0.5 μm.

4. The calcined and hydrated clam powder and the calcined silicate powder were blended in a ratio of 60:40 parts by weight.

5. 100 parts by weight of the mixture and 35 parts by weight of water containing 4% wood vinegar were sprayed and mixed in a granulator at room temperature.

6. The blended mixture is molded into pellets 6 ~ 7mm, crumbled to a certain size, and then dumpled and dried to 15% or less of moisture content. ① 1 ~ 2mm, ② 2 ~ 5mm, ③ 1mm It was packaged by sorting and selecting the following powder sizes.

Example 3

1. The collected oyster shells were washed, calcined at 1,100 ° C., cooled to room temperature, and then ground to particles having a size of 0.8 μm.

2. 15 kg of ground oyster shell and 12 kg of water at 70 ° C. were mixed, and the hydration reaction was started after about 3 minutes.

Due to the hydration reaction, the temperature rose to 253 ° C., thereby drying to obtain a powder having a finer particle size of 0.7 μm.

3. The silicate containing germanium was calcined at 930 ° C., cooled to room temperature, and then ground to particles having a size of 0.8 μm.

4. The calcined and hydrated oyster shell powder and the calcined silicate powder were mixed at a ratio of 65:35 parts by weight.

5. 100 parts by weight of the mixture and 20 parts by weight of water containing 7% of wood vinegar were sprayed and mixed in a granulator at room temperature.

6. The blended mixture is molded into pellets 6 ~ 7mm, crumbled to a certain size, and then dumpled and dried to 15% or less of moisture content. ① 1 ~ 2mm, ② 2 ~ 5mm, ③ Packages were sorted and selected with a powder size of 1 mm or less.

Example 4

1. The collected egg shells were washed, calcined at 1000 ° C., cooled to room temperature, and then ground to particles having a size of 2 μm.

2. 15 kg of ground eggshell and 13.5 kg of water at 75 ° C. were mixed, and the hydration reaction was started after about 2 minutes.

Due to the hydration reaction, the temperature rose to 276 ° C., thereby drying to obtain a powder having a finer particle size of 1.9 μm than the first.

3. The silicate containing germanium was calcined at 920 ° C., cooled to room temperature, and then ground to particles having a size of 2 μm.

4. The calcined, hydrated eggshell powder and calcined silicate powder were mixed in a ratio of 70:30 parts by weight.

5. 100 parts by weight of the mixture and 20 parts by weight of water containing 8% wood vinegar solution were sprayed and mixed in a granulator at room temperature.

6. The blended mixture is molded into pellets 6 ~ 7mm, crumbled to a certain size, and then dumpled and dried to 15% or less of moisture content. ① 1 ~ 2mm, ② 2 ~ 5mm, ③ 1mm It was packaged by sorting and selecting the following powder sizes.

The structure before and after firing of CaO contained in the shell used in Example 1 of the present invention is shown in Table 1 below.

shape Before firing (%) After firing (%) Water soluble 0.10 14.3 Availability 42.61 51.99 Quantity 62.76 62.76

As can be seen in Table 1, the shell powder has a calcium soluble form that can be directly absorbed and used in animals and plants after firing is increased about 140 times or more, and the soluble form also increased by 1.2 times.

In addition, the main component changes before and after firing of the silicate used in Example 1 of the present invention are shown in Table 2 below.

 ingredient Ge (ppm) SiO ₂ (%) CaO (%) MgO (%) K ₂ O (%) Fe ₂ O (%) Anion (Ion / cc) Before firing receptivity 0 0.1 0.1 0.1 0.1 0 574 Availability 0 36.1 4.59 9.5 1.3 5.7 After firing receptivity 31 12.2 1.6 3.3 574 Availability 31 44.1 5.6 11.8 1.6 7.0 Whole quantity 33.2 53.1 6.85 14.18 1.88 8.55 574

When the non-calcined silicate powder is simply fertilized in soil, the water-soluble components that can be absorbed and used by plants are less effective, but after firing, the water-soluble components are increased by about 120 to 140 times as shown in Table 2 above. Soluble ingredients are also improved by about 1.2 times, resulting in maximum fertilizer effect even at low fertilization rates.

Table 3 below shows the composition of the mixture of the calcined, hydrated shell and calcined silicate powder in a proportion of 70 parts by weight and 30 parts by weight, respectively.

CaO (%) SiO ₂ (%) MgO (%) K ₂ O (%) Ge (%) Anion (Ion / cc) receptivity 9.2 3.2 0.9 0.1 9.9 172 Quantity 46 15.9 4.3 0.6 10 172

Table 4 below shows the constituents of the mixed powder prepared in Example 3 and the material mixed with the wood vinegar solution.

      Ingredient composition CaO (%) SiO ₂ (%) MgO (%) K ₂ O (%) Ge (ppm) Anion (Ion / cc) Acetic acid and other organic acid bacteria (%) receptivity 9.6 3.4 1.0 0.1 9.9 172 3.0 Quantity 46 15.9 4.3 0.6 10 172 3.0

As can be seen in Tables 3 and 4 above, when the mixed powder and the wood vinegar is reacted, there is almost no change in the constituents of the wood vinegar and the anionic germanium regardless of the reaction before and after the reaction, while the soluble form of the constituents contained in the powder is generally 1-2. The amount of water-soluble components that can be easily absorbed and used by animals and plants is increased by about 4% to about 6%, so that the maximum fertilizer effect can be expressed even with a small amount of fertilization.

In order to find out the effect of using the silicate lime fertilizer of the present invention as described above, I. Application Test Effect on Rice and Ⅱ. Tests on the effect of treatment for functional watermelon production were conducted.

Test Example 1.

To evaluate the application effect of silicate calcite fertilizer on rice, the test was carried out for about 160 days from May 20, 2003 to October 30, 2003.

* Test Place: Dap-Soil, Dongjin-myeon, Buan-gun, Jeollabuk-do

* Test variety: Nampyeong rice

* Test soil: Soil soil

* According to the conditions of Table 5, soil and plant analysis, growth situation, pest occurrence situation of the test cultivated by soil spraying the control cultivated by the farmhouse standard cultivation method and siliceous lime fertilizer containing wood vinegar solution of Example 1 of the present invention , Quantity and quantity components were observed and the results are shown in Tables 6-14.

division Application time Throughput (Based on 10a) Treatment method Remarks Test 2003.5.20 Leeangjeon 150 kg Soil spraying Silicate Calcium Fertilizer Control 2003.5.20 Leeangjeon Farmhouse Standard Cultivation

Characteristics of Silicate Calcium Fertilizer of the Present Invention      Ingredient composition CaO (%) SiO ₂ (%) MgO (%) K ₂ O (%) Ge (ppm) Anion (Ion / cc) Other organic acid bacteria such as acetic acid (%) receptivity 9.6 3.4 1.0 0.1 10 172 3.0 Quantity 46 15.9 4.3 0.6 10 172 3.0

Seedling Overview  Invasion  sowing  Yiang Silicate Calcium Fertilizer Treatment  Light driving  Yianghu  Growing season  Flusher  After harvest 5.7 5.12 5.24 One-time processing - One-time processing One-time processing -

Soil Chemical Properties Before and After Test  division pH (1: 5) EC (ds / m) OM (g / kg) AV / P ₂ O ₅ (mg / kg) EX, cations (cmol ⁺ / kg) AV / SiO ₂ (mg / kg) Ca Mg K Before the test 5.5 0.43 32 66.2 5.4 2.3 0.35 112 After the test Test 5.1 0.60 63 42.9 5.1 1.6 0.37 86 Control 5.2 0.36 38 35.8 4.8 1.7 0.26 72

Inorganic Component Content in Plants (Water Extractors) division T-N (%) P ₂ O ₅ (%) SiO ₂ (%) CaO (%) MgO (%) K ₂ O (%) Test 1.84 0.98 7.7 0.79 0.36 2.47 Control 1.52 0.42 4.8 0.72 0.33 2.39

Growth-Cattle division Extra long (cm) Coniferous tree (1) In building (mg / object) Fidelity (mg / cm) Rooting length (cm) Root Count (individual / object) Rooting (mg / object) Rooting Amount (cm) Rooting rate (%) Test 13.2 3.74 25.9 198.2 8.6 14.7 15.7 117.6 31.2 Control 12.6 3.68 24.6 196.0 8.4 13.3 14.9 115.7 30.9

Growth situation-answer  division June 29 July 28 Extra long (cm) Hard water Leaf color Extra long (cm) Hard water dyeing Test 52.5 29.1 37.4 91.6 22.6 32.2 Control 46.2 24.3 35.5 80.4 20.1 29.8

Growth-Quantity Components division Soy sauce (cm) Center Height (cm) Soy Sauce (cm) Chief (cm) Sorghum (cm) Lip % Of ripening Verse 3 Verse 4 Test 16.3 8.4 49.2 71.9 17.4 18.9 78.9 84.4 Control 18.1 11.2 44.6 71.6 17.2 18.7 78.8 83.2

Growth-Food division protein(%) Amylose (%) ToYo Food Test 5.7 18.6 71.2 Control 5.5 18.4 72.9

Growth-Quantity division (G) Sine Rate (%) Whiteness (%) White rice grade (%) Rice quantity (kg / 10a) Dobok Index (%) Perfection Powdery matter Blight Damage Sami Test 25.2 83.9 89.7 94.9 0.7 3.5 0 0.9 529 (100) 0 Control 24.9 83.8 90.6 93.8 0.8 4.4 0 1.0 514 (97) 23

The results shown in Tables 6 to 14 are briefly summarized as follows.

end. Seedlings were slightly larger in plant height, leaves, rooting, and rooting than control.

I. Growth rate and soy sauce, sorghum, succulents, granules, and ripening ratios were slightly better than those of the control group. .

All. Yield was increased by 3% to 529kg / 10a compared to the control 514kg / 10a, which is a result of stabilizing the crops and increasing the yield of siliceous lime fertilizer.

Test Example 2

In order to investigate the treatment effect of silicate calcite fertilizer for the production of functional watermelon, the following test was performed for about 148 days from April 2, 2004 to August 30, 2004.

* Test location: Gochang-gun watermelon test site in Jeollabuk-do

* Test variety: Large watermelon

* In accordance with the conditions shown in Table 15, the soil and the excess characteristics of the test cultivated by soil spraying the control cultivated by the standard farming method and siliceous lime fertilizer containing wood vinegar of Example 2 of the present invention and observed the results Tables 16-20 are shown below.

division Application time Throughput (10a) Treatment method Remarks Test 2004.3.28 200 kg Soil spraying Silicate Calcium Fertilizer Control Farmhouse Standard Cultivation

Characteristics of Silicate Calcium Fertilizer  pH (1: 5)  OM (%) P ₂ O ₅ (mg / kg) EX.cation (cmol ⁺ / kg) NO ₃ (mg / kg)  Ge (mg / kg) K Ca Mg Total amount Effective 7.6 ND 19.9 0.6 46 4.3 24 10 9.9

Soil characteristics before the test  pH (1: 5)  OM (%) P ₂ O ₅ (mg / kg) EX.cation (cmol ⁺ / kg) NO ₃ (mg / kg) Cl ^- (mg / kg) SO ₄ ^-2 (mg / kg) K Ca Mg 6.7 3.3 9.5 1.95 5.4 3.2 144 63 340

Soil properties after testing  Treatment  pH (1: 5)  OM (%) P ₂ O ₅ (mg / kg) EX.cation (cmol ⁺ / kg) NO ₃ (mg / kg) Cl ^- (mg / kg) SO ₄ ^-2 (mg / kg) Remarks K Ca Mg Control 6.4 3.2 1105 2.30 4.9 3.1 408 112 247 Test Zone 200kg / 10a  6.5  2.8  2004  1.30  24.7  3.6  553  122  226

Ge content in soil and watermelon (mg / kg Treatment soil watermelon Extractable Tatal Control 0.18 24.1 ND Test 0.24 30.6 0.89

※ 0.1N HCl

Watermelon and character Treatment District Overweight (kg) Brix Control 7.3 11.8 Test strip 8.1 12.1

A brief summary of the results shown in Tables 15 to 20 is as follows.

end. Ge at the level of 0.89 mg / kg (FW) was detected in the test zone treated with the silicate calcite fertilizer of the present invention.

I. The weight and sugar content of the test group treated with the silicate lime fertilizer of the present invention was higher than the control.

The silicic acid calcium fertilizer containing wood vinegar of the present invention is excellent in soil improvement effect, and the organic acid group and complex organic compound group contained in the wood vinegar are important coenzyme catalysts for the metabolic system TCA cycle in vivo. Not only does it show an excellent effect on its physiological activity, but it also maintains the rooting environment of soil due to the calcium component contained in the shell shell or eggshell powder, and also maintains the tissues between plant cells to prevent decay or falling fruits. Exert.

In addition, in the siliceous lime fertilizer containing the wood vinegar of the present invention, SiO ₂ component in the silicate powder acts on the growth point of the plant root to silice the plant cells and maintain the plant robustly, and the MgO component forms photosynthesis and chlorophyll. It plays a leading role in improving the color and sugar content of plants, and in particular, it allows the plants to absorb the germanium in silicate directly, thereby accumulating organic germanium useful in the human body in the crops and influencing the health of human beings. It is possible to produce functional agricultural products that can contribute.

In addition, the siliceous lime fertilizer containing the wood vinegar of the present invention is a pelletized (granulated) fertilizer, not a powder, in order to facilitate the convenience of use by the consumer, thereby enabling mechanical application, thereby reducing the labor force of an aging farming village. Not only that, but also the cost of production can be reduced, resulting in a significant income increase.

Claims (3)

Silicic lime containing wood vinegar, made from pellets by mixing 100 parts by weight of a mixture consisting of 60 to 70 parts by weight of waste shell or egg shell powder and 40 to 30 parts by weight of silicate powder and 20 to 35 parts by weight of water containing 4 to 8% of wood vinegar. Fertilizer. The method of claim 1, wherein the waste shell or egg shell powder is calcined at 1,000 to 1,200 ℃ cooled to room temperature and then subjected to a hydration reaction with water of 60 to 80 ℃, the silicate (biotite) powder is 900 to 950 ℃ Silica fertilizer containing wood vinegar, characterized in that calcined with. Firing the waste shells or egg shells at 1,000 to 1,200 ° C. for pulverizing; Mixing the calcined waste shell or egg shell powder with 100 parts by weight and 80 to 120 parts by weight of water at 60 to 80 ° C. to cause a hydration reaction; Calcining the silicate (biotite) by firing at 900 to 950 ° C; 60 to 70 parts by weight of the waste shell or eggshell powder and 40 to 30 parts by weight of the silicate powder, and 100 to parts by weight and 4 to 8% by weight of 20 to 35 parts by weight of wood-containing water composition comprising the step of making a pellet Method for producing siliceous calcareous fertilizer containing wood vinegar.