KR20030048660A - The Preparation of Calcium Polysulfides - Google Patents
The Preparation of Calcium Polysulfides Download PDFInfo
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- KR20030048660A KR20030048660A KR1020010078632A KR20010078632A KR20030048660A KR 20030048660 A KR20030048660 A KR 20030048660A KR 1020010078632 A KR1020010078632 A KR 1020010078632A KR 20010078632 A KR20010078632 A KR 20010078632A KR 20030048660 A KR20030048660 A KR 20030048660A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/02—Sulfur; Selenium; Tellurium; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
Abstract
Description
본 발명은 석회유황합제의 제조방법에 관한 것이다. 보다 구체적으로는 본 발명은 생석회를 물과 반응시켜 여과하여 제조한 20% 액상수산화칼슘을 액상유황과 반응시켜 슬러지와 폐수가 발생되지 않고 유독가스가 발생되지 않으며 슬러지, 폐수 또는 유독가스를 제거하기 위한 별도의 제거장치를 설치할 필요가 없는 석회유황합제의 제조방법에 관한 것이다.The present invention relates to a method for producing a lime sulfur mixture. More specifically, the present invention reacts 20% liquid calcium hydroxide prepared by reacting quicklime with water and liquid sulfur to react with liquid sulfur so that sludge and wastewater are not generated, no toxic gas is generated, and sludge, wastewater or toxic gas is removed. It relates to a method for producing a lime sulfur mixture that does not need to install a separate removal device.
석회유황합제는 18881년 프랑스에서 포도 병충해 방제용으로 사용된 이후 값이 싸고 각종 과수 병해충 방제용으로 널리 사용되고 있다. 특히 석회유황합제는축엽병, 동고병, 흑성병, 흰가루병, 모니리아, 부란병, 깍지벌레 및 응애의 방제에 널리 사용되고 있다.Lime sulfur compounds have been used for the control of grape pests in France in 18881 and are inexpensive and widely used for controlling various fruit orchard pests. In particular, lime sulfur mixtures are widely used for the control of foliar disease, frostbite disease, blackness disease, powdery mildew, moniria, ovule disease, cockroach and mites.
석회유황합제는 CaS5, CaS2O5및 물로 구성되어 있으며, 석회유황합제의 주성분 다황화칼슘(CaS5)은 불안정한 화학물질로서 공기 중에서 산소 및 이산화탄소와 접촉하면 활성화된 하기 반응식에서와 같이 활성유황이 생성되는데 이 때 생성된 활성유황은 강력한 살균력을 발휘한다.The lime sulfur mixture is composed of CaS 5 , CaS 2 O 5 and water, and the main component of calcium sulfur sulfide (CaS 5 ) is an unstable chemical which is activated when contacted with oxygen and carbon dioxide in air. Sulfur is produced, and active sulfur produced at this time has a strong bactericidal power.
CaS5+ CO2+ H2O →CaCO3+ H2S + 4SCaS 5 + CO 2 + H 2 O → CaCO 3 + H 2 S + 4S
석회유황합제의 살균작용은 본제의 유효성분인 다황화칼슘(CaS5)이 공기 중에서 산소와 접촉하여 산화될 때 생기는 활성유황의 작용에 의해서 살균작용이 일어나는데 활성유황은 병원균의 호흡계에 작용하여 전자전달이 저하되므로 ATP의 생성이 저해될 뿐만 아니라 병원균의 호흡계에서는 ATP의 생성을 위하여 호흡이 촉진되므로 균체의 에너지 소비가 증가되어 결국 병원균은 사멸하게 된다.The bactericidal action of the lime sulfur mixture is caused by the action of active sulfur produced by the oxidation of calcium polysulfide (CaS 5 ), which is an active ingredient of this agent, in contact with oxygen in the air, which acts on the respiratory system of pathogens. As the delivery is reduced, not only the production of ATP is inhibited, but also the respiration of the pathogen promotes respiration for the production of ATP, thereby increasing the energy consumption of the cells and eventually killing the pathogen.
석회유황합제의 살균작용은 본제의 유효성분인 다황화칼슘(CaS5)이 공기 중에서 산소 및 이산화탄소와 접촉할 때 생기는 활성황의 작용에 의해서 살균작용이 일어나는데 이 약제의 강한 알칼리성은 균체나 환부조직을 부식시켜서 균체조직을 기계적으로 파괴시키고 황의 침입을 쉽게 만든다. 이 경우 균체속으로 들어간 황은조직내에서 탈탄소작용을 일으키게 하고 산화물 및 황화수소에 의해서 살균작용을 하게 된다. 석회유황합제에서 발생되는 활성황은 응애류나 까지벌레의 속으로 들어가서 조직내에서 탈탄소작용을 일으키게 하고 산화물 및 황화수소에 의해서 살균작용을 하게 된다.The bactericidal action of the lime sulfur mixture is caused by the action of active sulfur generated when calcium polysulfide (CaS 5 ), an active ingredient of this agent, comes into contact with oxygen and carbon dioxide in the air. Corrosion mechanically destroys cell structure and makes sulfur easier to invade. In this case, sulfur entered into the cells causes decarbonization in the tissues and is sterilized by oxides and hydrogen sulfide. Active sulfur generated from lime sulfur mixture enters the genus of mites and even insects, causing decarbonization in tissues and sterilizing by oxides and hydrogen sulfide.
기존의 석회유황합제는 생석회(CaO)와 유황분말을 1 : 1.5 중량비로 혼합하여 물을 가한 후 원통회전식의 가마솥(약 10m3, 3기압)에서 120 내지 130℃로 약 2시간 이상 동안 가열시켜 고체 유황을 용해시킨 후 30분간 숙성시켜 냉각시키고 불순물을 가압여과기로 여과시켜 제거한 후 제조된 석회유황합제를 포장하여 판매한다.Existing lime sulfur mixture is mixed with quicklime (CaO) and sulfur powder in a weight ratio of 1: 1.5, water is added, and then heated in a rotary cauldron (about 10 m 3 , 3 atm) to 120 to 130 ℃ for about 2 hours or more After dissolving the solid sulfur, it is aged for 30 minutes to cool, the impurities are filtered off with a pressure filter, and then the prepared lime sulfur mixture is packaged and sold.
CaO(고상) + S(고상) + H2O →Ca(OH)2+ S(액상)CaO (solid phase) + S (solid phase) + H 2 O → Ca (OH) 2 + S (liquid phase)
3Ca(OH)2+ 12S →2CaS5+ CaS2O5+ 3H2O3Ca (OH) 2 + 12S → 2CaS 5 + CaS 2 O 5 + 3H 2 O
상기와 같이 제조한 석회유황합제는 적갈색의 투명한 액체로서 pH 12.5 이상의 강한 알칼리성이며, 비중은 1.29(32 내지 33Be)이다. 또한 상기와 같이 제조된 석회유황합제는 공기 중에서 분해되기 쉬우므로 공기를 차단한 상태로 저장하여야 한다.The lime sulfur mixture prepared as described above is a reddish brown transparent liquid having a strong alkalinity of pH 12.5 or more and specific gravity of 1.29 (32 to 33 Be). In addition, the lime sulfur mixture prepared as described above is easy to be decomposed in the air, so the air should be stored in a blocked state.
그런데 기존의 석회유황합제는 생석회(순도: 98%이상), 유황(99.5%이상) 및 물을 혼합하여 제조하는데 기존의 석회유황합제 원료성분 중에서 생석회는 취급이불편하며, 생석회가 유황 및 물과 반응할 때 열이 발생할 뿐만 아니라 유독성가스인 H2S, SO2, SO3등이 생성되므로 상기와 같은 유독성가스를 제거하기 위한 별도의 제거장치가 필요하며, 생석회와 유황을 반응시킨 후에는 슬러지와 폐수가 다량 발생하기 때문에 기존의 석회유황합제를 제조하는 방법은 제조시 생성되는 슬러지와 폐수를 처리하기 위한 환경관리비가 많이 들어가는 문제점이 있었다.However, the conventional lime sulfur mixture is prepared by mixing quicklime (purity: 98%), sulfur (99.5%) and water. Among the raw materials of the conventional lime sulfur mixture, quicklime is not easy to handle. When the reaction not only generates heat but also generates toxic gases such as H 2 S, SO 2 , and SO 3 , a separate removal device for removing such toxic gases is required, and after reacting quicklime with sulfur, sludge Since a large amount of wastewater and wastewater is generated, the conventional method for preparing lime sulfur mixture has a problem in that a lot of environmental management costs for treating sludge and wastewater generated during manufacture are required.
또한 기존의 석회유황합제를 제조할 때 사용되는 원료로서 분말유황을 사용하는데 분말유황은 융점이 115℃이상이므로 기존의 석회유황합제를 제조할 때 분말유황의 융점 이하에서는 분말유황의 형태변화가 전혀 없다.In addition, powder sulfur is used as a raw material for the production of the conventional lime sulfur mixture. Since the powder sulfur has a melting point of 115 ° C. or higher, the shape change of the powder sulfur does not change at all below the melting point of the powder sulfur. none.
또한 기존의 석회유황합제를 제조할 때 고상 유황을 액상 수산화칼슘으로 처리하는 경우 고상 유황이 용해되기 전에 고상 유황이 물을 일시적으로 흡수하여 온도 및 압력이 불규칙적으로 급상승하므로 기존의 석회유황합제 제조방법은 제조 반응기가 폭발할 수 있는 위험성이 따르게 된다.In addition, when the solid sulfur is treated with liquid calcium hydroxide in the production of the conventional lime sulfur mixture, the solid sulfur absorbs water temporarily before the solid sulfur is dissolved, so that the temperature and the pressure increase irregularly. There is a risk that the production reactor may explode.
기존의 석회유황합제 제조시 제조 반응기가 폭발할 수 있는 위험성이 있기 때문에 일반적으로 생석회를 사용하는데 이 경우 생석회의 순도를 아무리 순수하게 유지시킨다 할지라도 약 20% 이상의 슬러지가 생성되며 H2S, SO2, SO3등과 같은 유해가스가 생성되는 문제점이 발생한다.Because of the risk of explosion of the manufacturing reactor in the manufacture of conventional lime sulfur mixtures, quick lime is generally used.In this case, no matter how pure the purity of the quick lime is maintained, more than 20% of sludge is produced and H 2 S, SO 2 , there is a problem that generates harmful gases such as SO 3 .
본 발명의 목적은 생석회를 물과 반응시킨 후 여과하여 생성된 액상수산화칼슘과 액상유황을 적정량 혼합하여 반응시켜 석회유황합제를 제조하는 방법을 제공한다. 또한 본 발명은 기존의 석회유황합제 제조방법에 비하여 슬러지와 폐수발생이 거의 없고 유독성가스가 거의 없을 뿐만 아니라 생석회에서 발생하는 슬러지, 폐수 및 유독성 가스를 제거하기 위한 별도의 제거장치를 설치할 필요가 없는 석회유황합제의 제조방법을 제공하는 것이다. 또한 본 발명은 기존의 석회유황합제 제조방법에서 원료로서 사용하던 분말유황 대신에 액상유황을 사용함으로서 반응시 직화에 의한 폭발 위험성과 슬러지의 발생을 극소화시킬 수 있는 석회유황합제의 제조방법을 제공한다.It is an object of the present invention to provide a method for preparing a lime sulfur mixture by reacting quicklime with water and then reacting by mixing an appropriate amount of liquid calcium hydroxide and liquid sulfur produced by filtration. In addition, the present invention has little sludge and wastewater generation and little toxic gas as compared to the conventional method for preparing lime sulfur mixture, and does not need to install a separate removal device for removing sludge, wastewater and toxic gas generated from quicklime. It is to provide a method for producing a lime sulfur mixture. In addition, the present invention provides a method for producing a lime sulfur mixture that can minimize the explosion risk and the generation of sludge during the reaction by using liquid sulfur instead of the powder sulfur used as a raw material in the conventional lime sulfur mixture manufacturing method. .
본 발명의 석회유황합제 제조방법은 고순도의 수산화칼슘 수용액을 사용하기 때문에 기존의 석회유황합제를 제조하기 위한 반응시 발생할 수 있는 H2S, SO2, SO3등과 같은 유해가스는 고순도의 수산화칼슘 수용액에 의하여 제거되고 반응 원료인 20% 수산화칼슘 수용액 제조시 공정상 3차례의 여과과정을 통하여 슬러지가 먼저 제거되기 때문에 본 발명의 석회유황합제를 제조하기 위한 반응시 슬러지의 발생이 거의 없다. 따라서 본발명은 기존의 석회유황합제 제조방법에서 야기되는 유해가스의 발생 제거에 관한 문제점 및 슬러지의 발생 제거에 관한 문제점을 동시에 해결할 수 있는 획기적인 석회유황합제의 제조방법을 제공한다.Since the method for preparing lime sulfur mixture of the present invention uses a high purity calcium hydroxide aqueous solution, harmful gases such as H 2 S, SO 2 , and SO 3 , which may occur during the reaction for preparing a conventional lime sulfur mixture, may be added to a high purity calcium hydroxide aqueous solution. And sludge is first removed through three filtration steps in the process of preparing a 20% calcium hydroxide aqueous solution as a reaction raw material, and thus little sludge is generated during the reaction for preparing the lime sulfur mixture of the present invention. Accordingly, the present invention provides a breakthrough method for producing a lime sulfur mixture that can simultaneously solve the problem of elimination of harmful gases and sludge generation caused by the conventional lime sulfur mixture manufacturing method.
도 1은 생석회와 유황분말을 사용한 기존의 석회유황합제의 제조방법을 설명한 공정의 개략적인 흐름도이다.1 is a schematic flowchart illustrating a process for preparing a conventional lime sulfur mixture using quicklime and sulfur powder.
도 2는 수산화칼슘 수용액과 액상유황을 사용한 본 발명의 석회유황합제의 제조방법을 설명한 공정의 개략적인 흐름도이다.2 is a schematic flowchart of a process for explaining a method for preparing a lime sulfur mixture of the present invention using an aqueous calcium hydroxide solution and liquid sulfur.
상기 목적을 달성하기 위하여, 본 발명은 기존의 석회유황합제 제조방법에서원료로서 사용하였던 생석회 대신에 20 내지 50%의 수산화칼슘 수용액을 사용하고 유황분말 대신에 액상유황을 사용한다.In order to achieve the above object, the present invention uses a 20 to 50% calcium hydroxide aqueous solution instead of quick lime used as a raw material in the conventional lime sulfur preparation method, and uses liquid sulfur instead of sulfur powder.
3Ca(OH)2+ 12S(액상) →2CaS5+ CaS2O5+ 3H2O3Ca (OH) 2 + 12S (liquid) → 2CaS 5 + CaS 2 O 5 + 3H 2 O
본 발명의 석회유황합제 제조방법은 90 내지 110℃로 유지시킨 20 내지 50% 수산화칼슘 수용액에 120 내지 130℃로 유지시킨 액상유황을 서서히 교반하면서 첨가 반응시켜 CaS5, CaS2O5및 물로 구성되어 있는 석회유황합제를 제조한다. 본 발명의 석회유황합제 제조방법에서 20% 수산화칼슘 수용액을 사용하는 경우 순도 99% 이상인 20% 수산화칼슘 수용액 76.5중량%에 순도 99.5% 이상인 액상유황 23.5중량%를 서서히 교반하면서 첨가하여 40분간 반응시킨다. 본 발명의 석회유황합제 제조방법에서 25% 수산화칼슘 수용액을 사용하는 경우 25% 수산화칼슘 수용액 80중량부에 물 20중량부를 가하여 20% 수산화칼슘 수용액이 되도록 하여 사용한다. 또한 본 발명의 석회유황합제 제조방법에서 50% 수산화칼슘 수용액을 사용하는 경우 50% 수산화칼슘 수용액 40중량부에 물 60중량부를 가하여 20% 수산화칼슘 수용액이 되도록 하여 사용한다.The method for preparing lime sulfur mixture of the present invention is composed of CaS 5 , CaS 2 O 5, and water by slowly adding and stirring liquid sulfur maintained at 120 to 130 ° C. to 20 to 50% aqueous calcium hydroxide solution maintained at 90 to 110 ° C. To prepare a lime sulfur mixture. When the 20% calcium hydroxide aqueous solution is used in the method for preparing lime sulfur mixture of the present invention, 23.5% by weight of liquid sulfur having a purity of 99.5% or more is added to 76.5% by weight of a 20% calcium hydroxide aqueous solution having a purity of 99% or more, and then reacted for 40 minutes. When the 25% calcium hydroxide aqueous solution is used in the method of preparing the lime sulfur mixture of the present invention, 20 parts by weight of water is added to 80 parts by weight of the 25% calcium hydroxide aqueous solution so that the 20% calcium hydroxide aqueous solution is used. In addition, when the 50% calcium hydroxide aqueous solution is used in the method for preparing lime sulfur mixture of the present invention, 60 parts by weight of water is added to 40 parts by weight of the 50% calcium hydroxide aqueous solution so that the 20% calcium hydroxide aqueous solution is used.
본 발명의 석회유황합제 제조방법에서 반응시 수산화칼슘 수용액의 온도는 90 내지 110℃로 유지시킨 상태에서 반응시키는 것이 바람직하다. 반응시 수산화칼슘 수용액의 온도가 90℃ 이하가 되면 수산화칼슘 수용액과 액상유황의 혼합 과정에서 그 온도차에 의하여 수분의 증발량이 증대되어 물의 소비량이 많고 이 때 급속하게 액상유황의 온도가 변화하는 경우 액상유황의 고결화 현상이 일어나며 보온탱크에서 간접열을 이용하여 상승시킬 수 있는 온도가 90℃로 한정되어 있기 때문에 본 발명의 석회유황합제 제조방법에서 반응시 수산화칼슘 수용액의 온도는 90℃ 이상으로 유지시킨 상태에서 반응시키는 것이 바람직하다. 본 발명의 석회유황합제 제조방법에서 반응시 수산화칼슘 수용액의 온도가 110℃ 이상 경우는 반응이 급격하게 일어나므로 110℃ 이하로 유지시킨 상태에서 반응시키는 것이 바람직하다.In the method of preparing a lime sulfur mixture of the present invention, the temperature of the calcium hydroxide aqueous solution is preferably reacted in a state maintained at 90 to 110 ° C. When the temperature of the aqueous solution of calcium hydroxide is less than 90 ℃ during the reaction, the evaporation amount of water increases due to the temperature difference during the mixing of the aqueous solution of calcium hydroxide and liquid sulfur, and the consumption of water is large. The solidification phenomenon occurs and the temperature which can be raised by using indirect heat in the thermal insulation tank is limited to 90 ° C. In the lime sulfur mixture manufacturing method of the present invention, the temperature of the calcium hydroxide aqueous solution is maintained at 90 ° C. or higher. It is preferable to make it react. When the temperature of the calcium hydroxide aqueous solution is 110 ° C. or more during the reaction in the method for preparing lime sulfur mixture of the present invention, the reaction occurs rapidly, and the reaction is preferably performed at a state of 110 ° C. or less.
본 발명의 석회유황합제 제조방법에서 반응시 액상유황의 온도는 120 내지 130℃로 유지시킨 상태에서 반응시키는 것이 바람직하다. 유황의 용융점은 115℃이기 때문에 액상유황을 액상 상태로 유지시키기 위해서는 본 발명의 석회유황합제 제조방법에서 반응시 액상유황의 온도는 120℃ 이상으로 유지시키는 것이 바람직하다. 본 발명의 석회유황합제 제조방법에서 반응시 액상유황의 온도가 130℃ 이상 경우는 반응이 급격하게 일어나므로 130℃ 이하로 유지시킨 상태에서 반응시키는 것이 바람직하다.In the lime sulfur mixture production method of the present invention, the reaction temperature of the liquid sulfur is preferably maintained at 120 to 130 ° C. Since the melting point of sulfur is 115 ° C., in order to maintain the liquid sulfur in the liquid state, it is preferable to maintain the temperature of the liquid sulfur at 120 ° C. or higher during the reaction in the lime sulfur mixture manufacturing method of the present invention. In the method of preparing a lime sulfur mixture of the present invention, when the temperature of the liquid sulfur is 130 ° C. or higher during the reaction, the reaction occurs rapidly, and the reaction is preferably performed at a temperature of 130 ° C. or lower.
이하, 본 발명을 실시예에 의해 상세히 설명한다. 다만, 하기 실시예는 본 발명의 이해를 위해 제공되는 예시일 뿐이며, 본 발명의 보호범위 내에서 다양한 변형 및 보완이 가능하다는 것은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 명확할 것이다.Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are only examples provided for understanding the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the protection scope of the present invention. .
<실시예 1><Example 1>
생석회와 유황분말을 사용한 석회유황합제의 제조Preparation of Lime Sulfur Mixture Using Quick Lime and Sulfur Powder
99.5% 이상인 분말유황 1,500Kg, 98% 이상인 생석회 1,000Kg 및 물 3,800Kg를 회전용 반응기(10,000Kg)에 투입한 후 경유버너를 이용하여 직화로 가열 반응시켜 120∼130℃, 3기압으로 2시간 동안 유지시켜 반응이 종료되면 열교환기를 통과하고 가압여과기를 통과시킨 후 슬러지를 제거하고 30분간 숙성시킨 후 생성된 석회유황합제 4,800Kg(수율: 76.2%)을 저장탱크에 저장한다. 상기 제조 방법에 의하여 생성된 석회유황합제를 석회유황합제의 분석법인 AOAC Official Method 920.33에 따라서 분석한 결과 상기 제조 방법에 의하여 생성된 석회유황합제의 품위는 황(S)을 기준으로 할 때 22.75∼22.95(비중 1.265)로 확인되었다.1,500Kg of powdered sulfur of more than 99.5%, 1,000Kg of quicklime of more than 98% and 3,800Kg of water were added to a rotary reactor (10,000Kg), and then heated and reacted by direct combustion using a diesel oil burner. When the reaction is completed by passing through the heat exchanger, the pressure filter was passed through, the sludge is removed, aged for 30 minutes and the resulting lime sulfur mixture 4,800Kg (yield: 76.2%) is stored in the storage tank. As a result of analyzing the lime sulfur mixture produced by the manufacturing method according to AOAC Official Method 920.33, which is an analysis method of the lime sulfur mixture, the quality of the lime sulfur mixture produced by the manufacturing method is 22.75 to 22% based on sulfur (S). 22.95 (specific gravity 1.265).
<실시예 2><Example 2>
수산화칼슘 수용액과 액상유황을 사용한 석회유황합제의 제조Preparation of Lime Sulfur Mixture Using Calcium Hydroxide Solution and Liquid Sulfur
90℃로 유지시킨 순도 99% 이상인 20% 수산화칼슘 수용액 76,500Kg에 130℃로 유지시킨 순도 99.5% 이상인 액상유황 23,500Kg을 교반하면서 서서히 첨가하면서 120℃에서 40분간 반응시킨 후 여과하여 고체상의 불순물을 제거하고 석회유황합제 95,000Kg(수율: 95.0%)을 얻는다. 상기 제조 방법에 의하여 생성된 석회유황합제를 석회유황합제의 분석법인 AOAC Official Method 920.33에 따라서 분석한 결과 상기 제조 방법에 의하여 생성된 석회유황합제의 품위는 황(S)을 기준으로 할 때 22.75∼22.95(비중 1.265)로서 실시예1의 생석회와 유황분말을 사용하여 제조한 석회유황합제의 품위와 거의 동일하였다.23,500 Kg of liquid sulfur having a purity of 99.5% or higher maintained at 130 ° C. was slowly added with stirring to 76,500 Kg of an aqueous 20% calcium hydroxide solution having a purity of 99% or higher maintained at 90 ° C. for 40 minutes at 120 ° C., followed by filtration to remove solid impurities. 95,000 Kg (yield: 95.0%) of lime sulfur mixture is obtained. As a result of analyzing the lime sulfur mixture produced by the manufacturing method according to AOAC Official Method 920.33, which is an analysis method of the lime sulfur mixture, the quality of the lime sulfur mixture produced by the manufacturing method is 22.75 to 22% based on sulfur (S). 22.95 (specific gravity 1.265), which was almost the same quality as the lime sulfur mixture prepared using the quicklime and sulfur powder of Example 1.
상기에서 알 수 있는 바와 같이, 본 발명의 석회유황합제 제조방법은 고순도의 수산화칼슘 수용액을 사용하기 때문에 반응시 발생할 수 있는 H2S, SO2, SO3등과 같은 유해가스는 고순도의 수산화칼슘 수용액에 의하여 제거되고 반응 원료인 20% 수산화칼슘 수용액 제조시 공정상 3차례의 여과과정을 통하여 슬러지가 먼저 제거되기 때문에 본 발명의 반응시 슬러지의 발생이 거의 없어서 기존의 석회유황합제 제조방법에서 야기되는 유해가스의 발생 제거 및 슬러지의 발생 제거에 관한 문제점을 동시에 해결할 수 있는 획기적인 석회유황합제의 제조방법을 제공한다.As can be seen from the above, since the method for preparing lime sulfur mixture of the present invention uses a high-purity calcium hydroxide solution, harmful gases such as H 2 S, SO 2 , and SO 3 generated during the reaction may be generated by a high-purity calcium hydroxide solution. Since sludge is first removed through three filtration processes in the process of preparing a 20% calcium hydroxide aqueous solution, which is a reaction raw material, there is almost no generation of sludge during the reaction of the present invention. Provided is a breakthrough method for producing a lime sulfur mixture that can simultaneously solve the problem of elimination of generation and sludge generation.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100443406B1 (en) * | 2002-01-31 | 2004-08-09 | 김진철 | Manufacturing Method of Composite Fertilizer |
| KR20050083584A (en) * | 2005-07-22 | 2005-08-26 | (주)보원헬텍 | Base manure and diluted solution to produce agricultural products (fruit, vegetables, etc.) containing dimethyl sulfone(methyl sulfonyl methane) supplied with, the method of manufacturing the same, the method of spreading the same, and agricultural products containing dimethyl sulfone(methyl sulfonyl methane) cultivated and produced with the method of the same |
| KR100761889B1 (en) * | 2006-04-05 | 2007-10-04 | 김진철 | Pro-environmental disinfection, insecticide, fertilizer liquid hydrate sulfur, its manufacturing methods and its using methods |
| KR101053186B1 (en) * | 2010-09-09 | 2011-08-01 | 정두희 | Method of producing polysulfide solution, and method of producing precipitated sulfur employing the same |
| KR101373028B1 (en) * | 2012-03-30 | 2014-03-11 | 고재칠 | Manufacturing Method for High Concentrated Basic Sulfur Sol Using Waste Sulfur |
| CN105265481A (en) * | 2015-11-23 | 2016-01-27 | 袁仓绪 | Decocting process and using method for high-concentration lime sulphur for kiwi fruit trees |
| KR20190030205A (en) * | 2019-03-13 | 2019-03-21 | 재단법인 포항산업과학연구원 | Method for preparing the lime sulfur with steel industry by-product and lime sulfur prepared therefrom |
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| KR101446208B1 (en) * | 2014-01-23 | 2014-10-01 | 김근호 | A method of manufacturing sulfur bordeaux mixture and sulfur bordeaux mixture manufactured by using the method |
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| JPS53133630A (en) * | 1977-04-22 | 1978-11-21 | Matsuo Kasei Kk | Production of crystalline lime and sulphur composite agent |
| JPS5543038A (en) * | 1978-09-25 | 1980-03-26 | Nisshinbo Ind Inc | Concentrated lime sulfur mixture |
| KR910019498A (en) * | 1990-05-19 | 1991-12-19 | 한기삼 | Method and apparatus for producing crystalline lime sulfur mixture |
| KR920008347A (en) * | 1990-10-15 | 1992-05-27 | 성갑제 | Head of seat integrated air compressor |
| EP0732877A4 (en) * | 1993-12-10 | 1998-04-29 | Punto Quimica Ltda | Nonphytotoxic aqueous polysulfide contact fungicides and their use |
| KR101039701B1 (en) * | 2010-11-29 | 2011-06-08 | 주식회사 유성엔지니어링 | Sludge collecting apparatus |
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|---|---|---|---|---|
| KR100443406B1 (en) * | 2002-01-31 | 2004-08-09 | 김진철 | Manufacturing Method of Composite Fertilizer |
| KR20050083584A (en) * | 2005-07-22 | 2005-08-26 | (주)보원헬텍 | Base manure and diluted solution to produce agricultural products (fruit, vegetables, etc.) containing dimethyl sulfone(methyl sulfonyl methane) supplied with, the method of manufacturing the same, the method of spreading the same, and agricultural products containing dimethyl sulfone(methyl sulfonyl methane) cultivated and produced with the method of the same |
| KR100761889B1 (en) * | 2006-04-05 | 2007-10-04 | 김진철 | Pro-environmental disinfection, insecticide, fertilizer liquid hydrate sulfur, its manufacturing methods and its using methods |
| KR101053186B1 (en) * | 2010-09-09 | 2011-08-01 | 정두희 | Method of producing polysulfide solution, and method of producing precipitated sulfur employing the same |
| KR101373028B1 (en) * | 2012-03-30 | 2014-03-11 | 고재칠 | Manufacturing Method for High Concentrated Basic Sulfur Sol Using Waste Sulfur |
| CN105265481A (en) * | 2015-11-23 | 2016-01-27 | 袁仓绪 | Decocting process and using method for high-concentration lime sulphur for kiwi fruit trees |
| KR20190030205A (en) * | 2019-03-13 | 2019-03-21 | 재단법인 포항산업과학연구원 | Method for preparing the lime sulfur with steel industry by-product and lime sulfur prepared therefrom |
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