KR20150124500A - Production Method of Granular Calcium-Sulfur Fertilizer Having Enhanced Decay Rate and the Granular Calcium-Sulfur Fertilizer Produced This Method - Google Patents

Abstract

The present invention relates to a method for producing a granular calcium sulfur fertilizer having an improved decay rate by using dihydrate gypsum, and the granular calcium sulfur fertilizer produced thereby. More specifically, the present invention relates to: a method for producing a granular calcium sulfur fertilizer having an improved decay rate by using dihydrate gypsum, wherein, as a byproduct generated during a phosphorous (P) producing step, wet sludge selected from the group consisting of phosphoric acid byproduct gypsum (CaSO_4·2H_2O), desulfurization gypsum, waste gypsum, and other side dihydrate gypsum is used alone, or a strong alkali material is added in powdered and dried dihydrate gypsum, and the pH is adjusted to 6 or more and 12 or less, so a fertilizer having an improved decay rate is produced; the granular calcium sulfur fertilizer produced thereby; and a mixed fertilizer (BB fertilizer) using the granular calcium sulfur fertilizer as a filler. In a step of producing hemihydrate gypsum by drying phosphoric acid byproduct gypsum, which is dihydrate gypsum, the same is rapidly hardened with water (H_2O) at room temperature and becomes difficult to be dissolved in water, so the same is dried at a temperature below 100°C. Accordingly, strength expression is weak, a product contains moisture, and a large quantity of fine powder is generated to be a problem of being lumped with powder when the fertilizer is sprayed, so users avoid to use the fertilizer. According to the present invention, the problem has been resolved.

Description

[0001] The present invention relates to a method for producing granular calcium sulfur fertilizer having improved disintegration using the granular calcium fertilizer, a method for producing granular calcium sulfur fertilizer using the granular calcium fertilizer, a method for producing granular calcium sulfur fertilizer using the granular calcium fertilizer,

The present invention relates to a method for producing a granular calcium sulfur fertilizer having improved disintegration degree by using an industrial by-product, and a granular calcium sulfur fertilizer produced by the method. More particularly, the present invention relates to a method for producing granular calcium sulfur fertilizer with improved disintegration using industrial by-products such as Lysosugo, phosphate gypsum, desulfurization gypsum, and Busan liquorice, and a granular calcium calcium fertilizer produced by the method.

In general, gypsum (CaSO ₄ · 2H ₂ O) is deposited naturally in sedimentary form, but mostly occurs as a byproduct when producing phosphate fertilizers. Gypsum as a byproduct of fertilizer production is strongly acidic at pH 2-3 by adding sulfuric acid in fertilizer manufacturing process. The process of gypsum formation is as follows.

Phosphate → crushing → sulfuric acid, water → reaction → filtration tank (separation of H ₃ PO ₄ , used as fertilizer raw material) → gypsum stock

_{CaF (PO 4) 3 + 5H} 2 SO 4 + 2H 2 O → HF + 5CaSO 4 2H ₂ O and

In this process, about 5 tons of gypsum is produced in the process of producing 1 ton of phosphorous fertilizer. At present, 2.3 million tons of gypsum is produced in the fertilizer manufacturing process, and it is used as building materials such as gypsum board and cement raw materials, and the remaining amount is about 20 million tons.

The desulfurization gypsum generated by CaO and liquid slag is also used as a raw material for gypsum board or cement plant.

In addition, a considerable amount of plaster is discarded, and a large amount of plaster that is discarded after half-hydration is used as a semi-gypsum is a by-product of the process as a by-product.

The composition of the gypsum is CaSO ₄ · 2H ₂ O, which is mainly composed of lime and sulfate. Although gypsum is used for the purpose of supplying lime or sulfur to general agricultural land, if gypsum is used in general farmland, lowering soil pH is a problem. Therefore, the feasibility study as a soil remediation agent was carried out by mixing the high pH fly ash and the gypsum, and related patents were disclosed.

In addition, when gypsum is used in a special soil with a high pH such as newly reclaimed soil, the Ca component accelerates the permeation rate by grafting the soil, and Na ⁺ and Mg ^{2 +} , which are problematic in the reclaimed soil soils, It can be expected to rapidly decontaminate by substituting with Ca ^{2 +} , and the effect is recognized through stabilization of clay and balanced supply of base by lowering high pH.

In order to recycle gypsum that is left neglected or buried and to use gypsum properly, Busan Gypsum Fertilizer was established in the fertilizer process standard by the Rural Development Administration Notice No. 2003-13 on August 5, 2003 to manufacture and supply gypsum fertilizer .

As such, Busan gypsum fertilizer, which is currently on the market, has a high moisture content and is powdered. Even if it is granular, it is inadequate in strength, and it is true that a lot of dust is lost due to the generation of a large amount of dust.

Sulfur is not only a constituent of three amino acids, cystine, cysteine and methionine in plant growth, but it is also essential for the root formation of two crops. In crops such as garlic and onion, It has been reported that the lack of these components inhibits plant growth and greatly affects the yield and quality of crops.

Despite the positive effect of using sulfur as described above, the sulfur has toxicity, and because of the fear of secondary contamination due to toxicity, it is not possible to spray a sufficient amount into the crops, so that the effect by sulfur is still insignificant. However, since the efficacy of the sulfur is maintained while the toxicity of the sulfur is removed, the sufficient amount necessary for the growth of the crop can be used, and there is an advantage that the effect of the sulfur can be seen. Research is actively underway.

However, production of fertilizer using refined sulfur is not available for farmers because of high cost and high cost of labor due to toxicity removal and hot reaction.

Chemical composition of phosphate gypsum ingredient content (%) Remarks CaSO ₄ .2H ₂ O 93 or more Drying criterion

Origin: Namhae Chemical East Hanchon SiO ₂ 2.3-4.5 Al ₂ O ₃ 0.7-1.6 Fe ₂ O ₃ 0.07-1.6 CaO 28-30 SO3 43-44 pH 2.5-5.5

Chemical composition of flue gas desulfurization gypsum SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO K ₂ O Na ₂ O MnO TiO ₂ P ₂ O ₅ Igloss SO ₃ NG 0.13 0.26 0.10 40.82 0.11 0.06 0.07 0.003 0.018 0.008 1.25 58.30 FGDA 0.15 0.53 0.24 40.12 0.60 0.11 0.06 0.01 0.025 0.008 0.53 57.20

Phosphate gypsum is produced as a by-product in the process of producing phosphate fertilizer by reacting phosphoric acid (Ca ₃ (PO ₄ ) ₂ ) with sulfuric acid as a raw material. Although these gypsum plaster is partly recycled for the production of cement raw materials and gypsum, its recycling rate is extremely limited, and thus it is left in spite of increasing environmental pollution.

 To remedy this problem, there have been some attempts to utilize Pusan Phosphate Gypsum as a soil amendment agent or calcareous fertilizer although it is limited.

Korean Patent Publication No. 10-099307 discloses a direct fertilization fertilizer composition comprising a soil fertilizer containing a mixture of a phosphate gypsum and an alkaline soil soil improving agent and a mixture of a cover fertilizer coated with a polymer resin and a cover fertilizer coated with a urea resin And a manufacturing method thereof. However, there is no accurate indication of specific removal methods, pH, disintegration, drying temperature,

 Korean Patent Laid-Open Publication No. 1999-0046573 discloses a gypsum obtained by mixing gypsum produced in the manufacture of compound fertilizer and coal fly ash generated from coal used as a fuel for a thermal power plant, and a mixed soil improving agent using coal fly ash and a method for producing the same. However, it has been pointed out that the pH is strongly acidic and its use range is restricted to some reclamation areas, fields, orchards, etc., and the product form is also divided, resulting in low preference of farmers.

Korean Patent Laid-Open Publication No. 2006-0027110 also discloses a process for producing a lime-based fertilizer by adding a binder selected from calcium oxide (CaO), calcium carbonate, zeolite, or a mixture thereof to wastewater sludge obtained in a phosphate gypsum waste sludge and phosphate gypsum refining process And a method of producing the lime-based fertilizer for improving the soil have been disclosed. However, the range of applicable crops and the effect on actual crop growth have not been tested, and the supply thereof has been limited. In addition, there is no exact specification of drying method, drying temperature, product moisture, strength, and degree of collapse in the manufacturing method.

Korean Patent Laid-Open No. 2008-0018548 has patented a method for producing a soil improvement agent having a pH of 6 or less with a patent for the production of a phosphate gypsum soil improving agent using Mg-geolite, a roadmate, or a pearlite as a main raw material of phosphate gypsum. Although the product itself is acidic, there is no specific collapse, and it is easily collapsed in water, but there is no mention of specific collapse.

Therefore, the conventional fertilizer manufacturing method using the existing algae gypsum is limited to the production method of the soil modifying agent, the coating fertilizer and the coating fertilizer using the by-product phosphorus gypsum, and the degradation caused by the high- The problem of badness is not mentioned and no solution has been presented. When granular fertilizer is applied to soil, if the fertilizer component can not be absorbed into the soil and remains in the soil, it is considered to have lost its function as fertilizer.

On the other hand, the application of proper phosphate gypsum is promoted by 1) facilitating the aggregation of soil by promoting aggregation between soil particles by calcium dissolved in phosphate gypsum, 2) calcium component is dissolved in soil water due to high solubility of phosphate gypsum, Improving the environment to be suitable for growing crops; 3) improving the soil of the reclaimed soil by removing the sodium ion from the calcium ion supplied under the phosphate gypsum fertilization to the underground; and 4) the high solubility of the calcium phosphate and gypsum Fertilizer supply effect can be expected, and it is known that there is a useful effect.

Accordingly, the present inventors have made efforts to develop a granular calcium sulfur fertilizer using calcium and sulfur components of gypsum, and have found that the granular calcium sulfur fertilizer was prepared by using Lee Suk Seok, and the disintegration degree of the fertilizer was remarkably improved, .

An object of the present invention is to provide a method for producing a cemented carbide (CaSO ₄ .1H ₂ O) by mixing a _semi- gypsum (CaSO ₄ .1H ₂ O) with a dry heat source ₂ O) so that the molded product is not dissolved in water (H ₂ O), that is, it is not collapsed.

More specifically, as an object of the present invention yisuseok finishing deceased phosphate, desulfurization, approximately half of gypsum development process 200 ℃ number of crystals of high yisuseok start dehydration at 100 ℃ from occurring while drying the pyeseokgo, water at room temperature (H ₂ O ) And rapid curing, the product is dried at a temperature of 100 ° C or lower during the drying operation due to the phenomenon that the product is not released into water. Therefore, the product exhibits insufficient strength and contains moisture and generates a large amount of fine powder. And a granular calcium sulfur fertilizer produced by the method. The present invention also provides a method for producing granular calcium sulfur fertilizer which solves the problem of avoiding use due to high temperature and high temperature (lump) at room temperature.

In order to achieve the above object, the present invention provides a method for producing a conventional granular calcium sulfur fertilizer, which comprises, as a byproduct generated in the manufacturing process of phosphorus (P), phosphorus acid gypsum (CaSO ₄ .2H ₂ O), desulfurization gypsum, Wherein the pH is adjusted to 6 or more and 12 or less by adding a wet alkali sludge selected from the group consisting of byproducts or by-products selected from the group consisting of by- .

The present invention also provides a granular calcium sulfur fertilizer produced by the above method.

Further, the present invention provides a mixed fertilizer (BB fertilizer) characterized by using the granular calcium sulfur fertilizer as a filler.

Hereinafter, the present invention will be described in detail.

When dried at about 100 캜 during the molding of plaster of gypsum and drying, there is a problem that a large amount of dust is generated due to insufficient strength, moisture content, and insufficient strength. However, it is good in the degree of disintegration and has a property of being dissolved well in water. (H ₂ O, solved)

On the other hand, when it is dried at about 100 캜 at the time of molding and drying, strength is good, water content is less than 1%, and minute generation is less. However, there is a disadvantage in that the degree of collapse is poor. (About 43% decomposition)

Accordingly, the present invention relates to a method for producing a steel sheet, comprising the steps of mixing gypsum phosphate (CaSO ₄ .2H ₂ O) with a _semi- dry gypsum (CaSO ₄ 1 / 2H ₂ O) to prevent the molded product from being unwound (i.e., not collapsed) in water (H ₂ O).

As mentioned above, due to the drying process of the fertilizer, it is not dissolved in water due to the transition of the alumite to the half-gypsum due to the drying process, the fertilizer component is not absorbed into the soil and remains as fertilizer However, the present invention uses a strong alkali material to coat the pores caused by the evaporation of crystalline water of aqua gypsum so as to stop the gypsum gypsum formation, and when the water is immersed in water, the "collapse degree" 98% or more at the time of immersion) "and a granular calcium sulfur fertilizer produced by the above method.

The present invention relates to a method for producing a conventional granular calcium sulfur fertilizer, which comprises the steps of: (a) selecting a phosphorus-containing gypsum (CaSO ₄ .2H ₂ O), a desulfurizing gypsum, a scum and other by- Wherein the pH is adjusted to 6 or more and 12 or less by adding a strong alkaline substance to the wet sludge alone or to the powder-dried alumite high so that a fertilizer having improved degree of collapse is produced.

In the process for producing the granular calcium sulfur fertilizer of the present invention, it is preferable that the granular calcium sulfur fertilizer is composed of raw material mixing-mixing-molding-drying-cooling-packing step and the strong alkaline material is Ca CaO, Ca OH) ₂ , CaCO ₃ ), slag powder, NaOH, sodium silicate, cement series (OPC, crude steel, slag / cement), fly ash and charcoal fine powder.

Further, in the method for producing granular calcium sulfur fertilizer according to the present invention, it is preferable to use 0.2 to 20 parts by weight of the strong alkaline substance with respect to 100 parts by weight of the alumina solids, More preferably 10-20% by weight based on 100 parts by weight of wet sludge, 0.5-5 parts by weight of pH 12, and 0.2-1.0 parts by weight of pH 13.

In the method for producing granular calcium sulfur fertilizer according to the present invention, the powder drying is selected from the group consisting of light oil, bark oil, refined oil and LNG as a heat source, It is preferable that the dry heat source is converted into an aquatic high-gypsum plaster.

In the method for producing granular calcium sulfur fertilizer according to the present invention, the granular calcium sulfur fertilizer or the mixed fertilizer (Bulk fertilizer / BB fertilizer) is used as a basic base or the BB fertilizer in which other fertilizer is partially mixed, It is preferable to mix the entire sulfur fertilizer.

The present invention relates to the production of fertilizer using phosphoric acid gypsum, which is pH acid (2-4), which occurs during the production of phosphorus (P) using phosphorus (Ca ₃ (PO ₄ ) ₃ ) or flue gas desulfurization Gypsum, and waste stones.

The present invention also provides a granular calcium sulfur fertilizer produced by the above method.

In the granular calcium sulfur fertilizer of the present invention, it is preferable that the fertilizer contains 23% by weight of calcium and 13% by weight of sulfur and is capable of adjusting the pH to 6 or more and 12 or less. The fertilizer preferably has a moisture content of 1% The generation rate is less than 10%, and the decay rate (%) after 24 hours from immersion in water (H ₂ O) is preferably 98% or more.

Further, in the granular calcium sulfur fertilizer of the present invention, it is preferable that the fertilizer additionally contains at least one selected from the group consisting of silicate, nitrogen, phosphoric acid, potassium and trace elements based on the sulfur fertilizer.

Further, the present invention provides a mixed fertilizer (BB fertilizer) characterized by using the granular calcium sulfur fertilizer as a filler.

As a raw material of the present invention, it is a by-product of phosphorus acid gypsum (CaSO ₄ .2H ₂ O), desulfurized gypsum, scum and other byproducts which are produced during the phosphorus (P) production process. Desulfurization gypsum, , And other by-products as gypsum. It can be used after wet sludge alone or after powder drying. It is possible to use 0.2 to 20 parts by weight of a strong alkaline substance based on 100 parts by weight of the sludge. It is preferable that the pH range is limited to 6 or more and 12 or less when using a single fertilizer or a mixed fertilizer. When the pH is less than 6, the degree of decay is about 45% and the degree of decay is insufficient. When the pH is 12 or higher, there is a possibility of gas generation due to the molded liquid binder.

The strong alkaline materials include Ca-based (CaO, Ca (OH) ₂ , CaCO ₃ ), slag powder, NaOH, sodium silicate, cement series (OPC, crude steel, slag / cement), fly ash, It can be used singly or in combination. It can be used when there is no problem of a heavy metal of pH 10 or more, but it is possible to use a strong alkali substance in a general manner depending on the use of the fertilizer. For example, when using as a filler for compound fertilizer, pH range should be produced at 5-7, so strong alkaline substance should be used selectively. PH range should be adjusted to 6-7 when used for reclaimed land or field crops. The pH range can be selected to be about 8-10.

The mixing ratio of the strong alkaline substance may be 10-20 parts by weight based on 100 parts by weight of the wet sludge when the alkaline pH is about 11 and 0.5-5 parts by weight or less of the pH of the strong alkaline substance, If the pH of the solution is about 13, 0.2-1.0 parts by weight can be added. With the exception of special cases, it is often desirable to have fertilizer in the neutral zone, so proper measures of the input rate of the strong alkali are needed.

The degree of decay shall be applied to all fertilizers. The degree of decay (%) shall be 98% or more after 24 hours from immersing the dried and cooled product in water (H ₂ O). This is in accordance with the legal regulations of silicate fertilizer (Ministry of Agriculture, Forestry and Fisheries), and if it is not enough, return it and dispose of it.

The method for producing the granular fertilizer of the present invention is based on a common and common method. Specifically, it follows a general method of raw material mixing-mixing-molding-drying-cooling-packaging. In addition, all fertilizers should have a moisture content of 1% or less at the time of shipment, a product with a certain strength or more, a yield of 10% or less, and a product with a degree of collapse of 98% or more as ordinary granular fertilizer.

The calcium sulfur fertilizer produced by the present invention is a granular fertilizer containing calcium (23%) and sulfur (13%) and capable of pH control, basically maintaining the pH range at neutral (6-7) Or more of the calcium and magnesium fertilizer.

The drying method proposed by the present invention uses a kiln dryer used in a general fertilizer maker. As a heat source, a general heat source such as light oil, bark oil, refined oil and LNG is used as a heat source such as burner flame or indirect heat, The present invention provides a granular calcium sulfur fertilizer which improves the degree of disintegration by preventing the collapse and failure caused by the semi-hydration process caused by the transition to high-cost semi-gypsum.

The present invention relates to a method for producing a fertilizer using phosphorus-containing gypsum, comprising the steps of applying a strong alkaline substance to a pH region So that the granular pore is closed, and granular calcium sulfur fertilizer having a degree of collapse of 98% or more is produced even after the shaping work and the drying work. In order to overcome the problem that the dissolution of the fertilizer component is not performed when the disintegration of the fertilizer of the present invention is poor, the fertilizer itself does not play a role. As an invention, after the drying process (over 150 ° C) To provide granular calcium sulfur fertilizer with good collapse degree.

(BB fertilizer) using the calcium sulfur fertilizer as a filler which overcomes the problem of the collapse and badness generated by the semi-hydration process when producing the granular calcium sulfur fertilizer produced by the present invention produced by the present invention.

The present invention constituted as described above is yisuseok as deceased phosphate in half gypsum development process that occurs while drying the Busan gypsum can determine a high yisuseok finishing degree to start 200 ℃ dehydrated at 100 ℃, water at room temperature (H ₂ O) and Due to the phenomenon of rapid curing and not being released into water, drying at a temperature of 100 ° C or less during the drying operation results in insufficient strength development. As the product contains moisture and generates a large amount of fine powder, And solved the problem of avoiding the use due to the phenomenon (agglomeration). In addition, the function of calcium as a fertilizer component and the function of sulfur fertilizer are combined with the soil to promote the coloring of soil and rice field / field crops, and to improve soil properties of reclaimed soil. It is possible to improve the basic degree of collapse leading to appropriate elution and to have the beneficial effect that the effect of calcium and sulfur fertilizer supply can be expected.

1 is a flow chart of the granular calcium sulfur fertilizer production process of the present invention
2 is a graph showing the change in hot gypsum of CaSO ₄
3 is a graph showing changes in physical properties of the high-hemi-gypsum-anhydrous gypsum in hot weather,
FIG. 4 is a photograph showing the curing ability of the gypsum powder according to the drying temperature,
FIG. 5 is a photograph showing the degree of collapse after the binder was added to the gypsum phosphate according to the drying temperature,
FIG. 6 is a photograph showing the degree of collapse when pH of the phosphate gypsum dried at 150 ° C. is adjusted to pH 5.64 by administration of weak alkali,
7 is a photograph showing the degree of collapse when adjusted to pH 6.18 by administration of strong alkali to gypsum phosphate dried at 150 ° C.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art may understand the present invention without departing from the scope and spirit of the present invention. It is not.

<Example 1> pH change due to administration of alkaline substance to wet sludge

Strong alkaline substances were added to the wet sludge to change the pH, and the binder was added to the mixture for molding, and the disintegration and strength were measured. Specifically, the pH change of the wet sludge was measured by administering various kinds of alkaline substances as shown in Tables 3 to 5 below.

The strong alkaline materials include Ca-based (CaO, Ca (OH) ₂ , CaCO ₃ ), slag powder, NaOH, sodium silicate, cement series (OPC, crude steel, slag / cement), fly ash, It can be used singly or in combination.

First, as shown in Table 3 below, the alkaline substance was administered to the wet sludge, and the pH was adjusted by mixing with a shaker.

Raw material condition Initial pH After 30 minutes pH  Remarks Wet sludge + alkaline (100/5) 4.87 5.83 Alkaline pH / 11.76
Wet sludge pH / 4.12 Wet sludge + alkaline agent (100/10) 5.18 6.11 Moisture sludge + alkali (100/15) 6.17 6.36 Wet sludge + alkaline agent (100/20) 6.41 6.84

Further, as shown in Table 4 below, a strong alkaline substance was administered to the wet sludge, and pH was controlled by mixing with a shaker.

Raw material condition  Initial pH After 30 minutes and after pH Remarks Wet sludge + hard alkaline (100/1) 8.45 9.24 Alkaline pH / 13.12
Wet sludge pH / 3.86
Wet sludge + strong alkali (100/2) 12.60 12.81 Wet sludge + strong alkali (100/3) 12.76 12.96

In addition, as shown in Table 5 below, another strong alkaline substance was added to the wet sludge, and the pH was adjusted by mixing with a shaker.

Raw material condition Initial pH After 30 minutes and after pH Remarks Wet sludge + hard alkaline (100/1) 8.45 9.45 Alkaline pH / 12.77
Wet sludge pH / 3.86
Wet sludge + strong alkali (100/3) 12.60 10.03 Wet sludge + strong alkaline (100/5) 12.76 10.38

&Lt; Example 2 > Measurement of curability and collapse degree of phosphorus gypsum plaster

The pH range was adjusted on the basis of the results of the above silylation 1, and the degree of disintegration and strength was measured through a binder injection molding operation. Also, we tried to find a way to prevent the transition of the gypsum ash after drying by setting the temperature above 150 ℃.

The curability of the phosphorus acid gypsum was measured under the conditions shown in Table 6 below. (Figure 4)

Working condition Drying time (HDR)  Remarks 1HDR 2HDR 3HDR Dry at 150 ℃ Hardening Hardening Hardening H ₂ O 30% input Not loosened Not loosened Not loosened 100 ℃ drying Lee Kyung Hwa Lee Kyung Hwa Lee Kyung Hwa Deposition: 24HDR Loosening Loosening Loosening

As can be seen from the above results, the phosphate gypsum dried at 150 ° C immediately cured the reaction with water, but the sample dried at 100 ° C is not cured. In conclusion, it was confirmed that the phosphate gypsum was transferred to high-gypsum → semi-gypsum at 150 ℃.

In addition, binder was added by using the phosphorus acid gypsum dried at 100 DEG C and 150 DEG C under the conditions shown in Table 7 below, and the degree of collapse after the pellet operation was measured. (Fig. 5)

Raw material condition B I N D E R H ₂ O Molasses CM 150 ℃
Dry sample 100 ℃ 150 ℃ 100 ℃ 150 ℃ 100 ℃ 150 ℃ Non Non Non Non Non Non 100 ℃
Dry sample 199 ℃ 150 ℃ 100 ℃ 150 ℃ 100 ℃ 150 ℃ collapse collapse collapse collapse collapse collapse

As a result, it was determined that the phosphate gypsum dried at 150 ° C had a poor degree of decay regardless of the binder.

In addition, the collapse and strength of the gypsum plaster of Phosphorus were measured under the conditions shown in Table 8 below. (Figs. 6 and 7)

Raw material condition after drying
pH Torch heating for 10 minutes Dry (150 ° C) * 2HDR Remarks  burglar Collapse Moisture content burglar Collapse  Moisture content Wet plaster + alkali (100/10) 6.11 1.82 collapse 2.35 1.88 collapse 0.23 bookbinder
CMS
burglar
Kg / P Wet plaster + alkali (100/15) 6.39 2.99 collapse 3.01 11.87 collapse 1.02 Wet plaster + alkali (100/20) 6.40 2.66 collapse 2.23 10.15 collapse 0.56 Wet plaster alone 3.8 1.2 NON 2.79 1.75 NON 1.03

The above results show that although the wet strength alone is poor, the degree of disintegration is poor (not solved). However, all of the samples with pH adjusted pH of the wetting gypsum showed good decay. Specifically, the samples were dried at 150 ° C for 2 hours, and although the strength was good, the samples loaded with the alkali pH adjusting agent showed good decay.

In addition, the degree of collapse after the addition of the strong alkaline agent to the gypsum gypsum was measured under the conditions shown in Table 9 below.

Raw material condition after drying
pH Collapse burglar Moisture content (%) Remarks Wet sludge + strong alkaline (100/1) 8.55 Rapid collapse 10.34 0.76 150 ° C * 2Hr after molding
dry
Strong alkaline pH / 13 Wet sludge + strong alkali (100/2) 10.22 Rapid collapse 11.76 0.98

It was shown that the degree of collapse of molded products was very good when 1% and 2% of strong alkaline substances were added and the whole pH range was transferred to alkaline zones. However, since 1% and 2% input is a little problem in field operation, accurate weighing device and weighing method are needed.

In addition, the degree of collapse and related data are summarized in the case of granular fertilizer granulation using the phosphate gypsum under the conditions shown in Table 10 below. (Dried at 150 &lt; 0 &gt; C for 2 hours)

Raw material condition Binder
input(%) PH after drying  Collapse rate (%) Dry moisture burglar
(Kg / P) Remarks Wet sludge alone 10.1 4.86 NON Less than 1% 3.42 bookbinder
Using CMS
Strong alkaline 1 pH
11.21
Strong alkaline 2 pH
13.2
Wet sludge pH
3.62 Wet sludge + strong alkaline 1
(100/10) 10.5% 6.09 98% or more " 6.4 Wet sludge + strong alkaline 1
(100/15) 10.4% 6.21 98% or more " 10.52 Wet sludge + strong alkaline 1
(100/20) 10.1% 6.27 98% or more " 13.07 Wet sludge + strong alkaline 2
(100/1) 9.34% 7.76 98% or more " 9.85 Wet sludge + strong alkaline 2
(100/2) 9.72% 9.91 98% or more " 10.21 (Wet 80 + dry gypsum 20)
River Alkali 1 15 15.3% 6.00 98% or more " 6.25

When the above data are summarized, there is no difference in the degree of collapse according to the strength or the kind of the binder, but the difference in the rate of decay according to the pH range of the raw material is shown, and the higher the pH, the faster the decay rate is. Therefore, we have secured a method to connect the fertilizer characteristics of calcium and sulfur to the crops by controlling the pH of the raw materials during fertilizer granulation using Phosphate gypsum gypsum.

The semi-hydration process of half-hydration, which is a problem that the fertilizer component is not absorbed into the soil due to the unfiltered water due to the transition to the gypsum, The use of a strong alkaline material to coat the pores caused by the evaporation of crystal water in the pore water and stop the half gypsum formation. When the water is immersed in the water, the "degree of decay (more than 98% A method for producing calcium sulfur fertilizer, and a method for producing the granular calcium sulfur fertilizer manufactured thereby.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, This is possible.

Claims (12)

In a typical method for producing a granular calcium sulfur fertilizer,
As a by-product generated in phosphorus (P) production, a wet sludge alone or a powder-dried alumite selected from the group consisting of phosphorus acid gypsum (CaSO ₄ .2H ₂ O), desulfurization gypsum, And adjusting the pH to 6 or more and 12 or less to produce a fertilizer having improved degree of collapse.
The method of claim 1, wherein the granular calcium sulfur fertilizer is produced by mixing, mixing, molding, drying, cooling, and packing the granular calcium sulfur fertilizer.
The method of claim 1, wherein the strong alkaline material is selected from the group consisting of Ca based CaO, Ca (OH) ₂ , CaCO ₃ , slag powder, NaOH, sodium silicate, cement based (OPC, crude steel, slag / cement) Fly ash, and charcoal branching fine powder. The method of producing granular calcium sulfur fertilizer according to claim 1,
The method of claim 1, wherein the strong alkaline material is used in an amount of 0.2 to 20 parts by weight based on 100 parts by weight of the alumina.
The method according to claim 3 or 4, wherein, when the alkaline pH is 11, the mixing ratio of the strong alkaline substance is 10-20% based on 100 parts by weight of the wet sludge, 0.5-5 parts by weight when the pH is 12, 1.0 part by weight based on the total weight of the granular calcium sulfate fertilizer.
The method of claim 1, wherein the powder drying is a heat source selected from the group consisting of light oil, bark oil, refined oil, and LNG, and is dried and heat-treated at a temperature of 100 ° C or higher, &Lt; / RTI &gt; wherein the transition is carried out in the presence of a catalyst.
[2] The method according to claim 1, wherein the granular calcium sulfur fertilizer is mixed with BB fertilizer having the granular calcium sulfur fertilizer or mixed fertilizer (Bulk fertilizer / BB fertilizer) By weight of calcium sulfate.
A granular calcium sulfur fertilizer produced by the method of any one of claims 1 to 12.
The granular calcium sulfur fertilizer according to claim 8, wherein the fertilizer contains 23% by weight of calcium and 13% by weight of sulfur and is capable of adjusting the pH to 6 or more and 12 or less.
9. The method according to claim 8, wherein the fertilizer has a water content of 1% or less, an amount of water generated is less than 10%, and a disintegration rate (%) after 24 hours from immersion in water (H ₂ O) Sulfur fertilizer.
The granular calcium sulfur fertilizer according to claim 8, wherein the fertilizer further comprises at least one selected from the group consisting of silicic acid, nitrogen, phosphoric acid, potassium and trace elements based on the sulfur fertilizer.
A mixed fertilizer (BB fertilizer) characterized by using the granular calcium sulfur fertilizer of claim 8 as a filler.

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