KR100510084B1 - watersoluble Calcium complex and manufacturing method thereof - Google Patents

watersoluble Calcium complex and manufacturing method thereof Download PDF

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KR100510084B1
KR100510084B1 KR10-2003-0002501A KR20030002501A KR100510084B1 KR 100510084 B1 KR100510084 B1 KR 100510084B1 KR 20030002501 A KR20030002501 A KR 20030002501A KR 100510084 B1 KR100510084 B1 KR 100510084B1
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calcium
potassium
water
phosphate
magnesium
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KR20040065507A (en
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고재만
최호근
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(주)칼테크
최호근
고재만
류필조
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    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05DINORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00Other inorganic fertilisers
    • C05D9/02Other inorganic fertilisers containing trace elements
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05DINORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D3/00Calcareous fertilisers
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Fertilizers (AREA)

Abstract

본 발명은 물에 완전히 녹는 분말상의 수용성 복합칼슘 조성물 및 그 제조방법에 관한 것으로서 이를 구체적으로 설명하면 물 30∼40중량%에 칼슘화합물로서 탄산칼슘, 수산화칼슘, 염화칼슘, 황산칼슘, 3종의 인산칼슘(Ⅰ,Ⅱ,Ⅲ), 시안화칼슘, 질산칼슘, 플루오르화칼슘과 산화마그네슘, 황산마그네슘, 인산마그네슘, 수산화마그네슘, 황산칼륨, 인산칼륨, 탄산칼륨, 염화칼륨, 수산화칼륨, 인산암모늄, 황산, 염산이 3종 이상으로 이루어지며, 그 중 하나 이상이 칼슘화합물이 되도록 혼합된 혼합물 5∼60중량%와 구연산 또는 구연산나트륨 10∼55중량%를 혼합하는 공정, 상기 혼합물을 70∼150℃의 온도를 유지하고 100∼150rpm으로 약20분∼90분 회전시키는 교반공정, 상기 교반된 혼합물의 수분을 필터프레스 또는 진공탈수기를 사용하여 50%이상 탈수시키는 탈수공정, 상기 탈수된 혼합물을 전기로 또는 열풍건조기를 사용하여 잔여수분을 제거시키는 건조공정으로 이루어져서, 이를 물에 용해시켜 농작물에 신속한 영양을 공급을 함으로써 품질이 우수한 농작물 생산을 가능하게 할 뿐 아니라 인건비 절감, 노동시간 단축을 통한 경제적 이익과 농약의 과다사용을 경감시켜 토양을 개선하는 효과가 있다.  The present invention relates to a powdery water-soluble complex calcium composition and a method for producing the same, which are completely soluble in water. Specifically, the present invention relates to calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, and three kinds of calcium phosphate as calcium compounds in 30 to 40% by weight of water. (I, II, III), calcium cyanide, calcium nitrate, calcium fluoride and magnesium oxide, magnesium sulfate, magnesium phosphate, magnesium hydroxide, potassium sulfate, potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide, ammonium phosphate, sulfuric acid, hydrochloric acid A mixture of 5 to 60% by weight and 10 to 55% by weight of citric acid or sodium citrate, the mixture being mixed so that at least one of them is a calcium compound; Stirring process to maintain and rotate about 20 to 90 minutes at 100-150rpm, to dehydrate more than 50% of the water in the stirred mixture using a filter press or a vacuum dehydrator It consists of a dehydration process and a drying process that removes the residual moisture by using an electric furnace or a hot air dryer, and dissolves it in water to supply nutrients to the crops quickly, thereby enabling the production of high-quality crops. It has the effect of improving the soil by reducing labor costs and reducing labor time and reducing economic benefits and excessive use of pesticides.

Description

수용성 복합칼슘 조성물 및 그 제조방법{watersoluble Calcium complex and manufacturing method thereof}Water-soluble Calcium Complex and manufacturing method

본 발명은 물에 쉽게 녹는 수용성 복합칼슘 조성물 및 그 제조방법에 관한 것으로서, 이를 좀더 구체적으로 설명하면 칼슘화합물, 마그네슘화합물, 칼륨화합물, 인산암모늄, 황산, 염산과 구연산 또는 구연산나트륨과 물을 혼합하여 제조함으로써, pH 5.7∼7.5사이의 범위이고 주성분 칼슘함량이 18∼40%를 유지하는 분말상의 고순도 수용성 복합칼슘 조성물 및 그 제조방법에 관한 것이다.The present invention relates to a water-soluble complex calcium composition and a method for preparing the same, which are easily dissolved in water, and more specifically, to a calcium compound, a magnesium compound, a potassium compound, ammonium phosphate, sulfuric acid, hydrochloric acid and citric acid, or sodium citrate and water. The present invention relates to a powdery high purity water-soluble complex calcium composition having a pH in the range of 5.7 to 7.5 and having a main component calcium content of 18 to 40%, and a method for producing the same.

수용성 복합칼슘은 분말상태의 칼슘을 물에 녹인 후 농작물 등에 살포하여 채소나 과일의 생리장해를 치유하고 신속한 영양공급을 위한 비료로서 사용하거나, 다종의 혼합유해가스를 흡착, 탈취, 흡습 등의 용도로 쓰이는 등 다양하게 사용되고 있다. 이와 같은 다양한 용도로 사용되는 칼슘은 그 주성분 함량이 높을수록 원하는 효과를 크게 얻을 수 있다.Water-soluble complex calcium is used as a fertilizer for dissolving the physiological disorders of vegetables and fruits by dissolving powdered calcium in water and spraying it on crops, etc., or for adsorbing, deodorizing and absorbing various mixed harmful gases. It is used in various ways. Calcium used for such various uses can obtain a desired effect as the main component content is higher.

그러나, 칼슘은 물에 거의 녹지 않는 특성이 있어 수용액으로 만들기 곤란하였으며 또 종래 일반적으로 사용되는 칼슘의 제조방법으로서 조개껍질 등 패각류를 산에 녹인 후 칼슘성분을 추출하는 방법이 있으나 이런 방법으로 제조된 제조물은 형태가 액상이며 일정함량 이상으로 주성분의 칼슘 함량을 높일 수 없었다.However, calcium is hardly dissolved in water, making it difficult to form an aqueous solution. As a method of preparing calcium, which is commonly used in the art, there is a method of extracting a calcium component after dissolving shellfish such as shellfish in an acid. The prepared product was liquid in form and could not increase the calcium content of the main component above a certain content.

상술된 바와 같이 현재 수용성 복합칼슘의 제조기술이 확립되어 있지 않기 때문에 칼슘성분이 20%이상 함유된 고순도 수용성 칼슘을 제조할 수 없었다.As described above, since the current technology for producing water-soluble complex calcium has not been established, high purity water-soluble calcium containing 20% or more of calcium components could not be produced.

따라서 종래 사용자는 저농도의 칼슘 수용액으로 된 비료를 사용하여야 했으며 일정 농도의 칼슘을 공급하여 농작물의 생리장해 치유 및 충분한 영양공급이 이루어지도록 농작물에 살포하는 작업을 수회에 걸쳐 반복하여야 하므로 인건비 상승의 문제점은 물론 농작물의 품질저하 문제가 발생하였으며 이를 개선하고자 고활성 기능을 가진 수용성 복합칼슘은 주성분인 칼슘의 함량이 매우 높고 다수의 유효성분이 함유되어 있어 농작물의 세포벽을 튼튼히 하여 병해충발생을 현저히 줄여주며, 기타 장해에 대한 저항력을 키워준다. Therefore, conventional users had to use fertilizers with low concentration of calcium aqueous solution, and the problem of rising labor cost because it has to be repeated several times to spray the crops so that the physiological disorders of the crops are supplied and sufficient nutrition is supplied by supplying a certain concentration of calcium. Of course, there was a problem of deterioration of crop quality, and in order to improve it, the water-soluble complex calcium with high activity has a very high content of calcium as the main ingredient and contains a large number of active ingredients. Increases resistance to other obstacles.

본 발명은 이상과 같은 문제점을 효과적으로 해소하기 위하여 연구 개발된 것으로서, 본 발명의 목적은 수용성 복합칼슘 조성물의 칼슘 성분함량을 18∼40%까지 높인 분말상의 고순도 수용성 복합칼슘 조성물을 제공하는 것이다. The present invention has been researched and developed to effectively solve the above problems, and an object of the present invention is to provide a powdery high purity water-soluble composite calcium composition having a calcium content of the water-soluble composite calcium composition increased by 18 to 40%.

본 발명의 또 다른 목적은 칼슘의 성분함량이 높은 고순도 수용성 복합칼슘의 제조방법을 제공하는 것이다. Still another object of the present invention is to provide a method for producing a high purity water-soluble complex calcium having a high content of calcium.

상기와 같은 목적을 달성하기 위하여 본 발명의 수용성 복합칼슘 조성물은 칼슘화합물로서 탄산칼슘, 수산화칼슘, 염화칼슘, 황산칼슘, 3종의 인산칼슘(ⅠⅡⅢ), 시안화칼슘, 질산칼슘, 플루오르화칼슘과 산화마그네슘, 황산마그네슘, 인산마그네슘, 수산화마그네슘, 황산칼륨, 인산칼륨, 탄산칼륨, 염화칼륨, 수산화칼륨, 인산암모늄, 황산, 염산이 3종 이상으로 이루어지며, 그 중 하나 이상이 칼슘화합물이 되도록 혼합된 혼합물 5∼60중량%, 구연산 또는 구연산나트륨 10∼55중량% 및 물 30∼40중량%로 이루어진다. In order to achieve the above object, the water-soluble composite calcium composition of the present invention is a calcium compound as calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (ⅠIIIII), calcium cyanide, calcium nitrate, calcium fluoride and magnesium oxide Magnesium sulphate, magnesium phosphate, magnesium hydroxide, potassium sulphate, potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide, ammonium phosphate, sulfuric acid, hydrochloric acid, a mixture of at least one of which is a calcium compound It consists of 5 to 60 weight%, 10 to 55 weight% of citric acid or sodium citrate, and 30 to 40 weight% of water.

또 본 발명의 수용성 복합칼슘 조성물에 따르면 상기 합성된 수용성 복합칼슘 조성물이 pH 5.7∼7.5사이의 범위이고 주성분 함량이 18∼40%를 유지하는 것을 특징으로 한다.In addition, the water-soluble composite calcium composition of the present invention is characterized in that the synthesized water-soluble composite calcium composition is in the range of pH 5.7 to 7.5 and the main component content is 18 to 40%.

본 발명에 따른 수용성 복합칼슘 조성물은 물 30∼40중량%에 칼슘화합물로서 탄산칼슘, 수산화칼슘, 염화칼슘, 황산칼슘, 3종의 인산칼슘(ⅠⅡⅢ), 시안화칼슘, 질산칼슘, 플루오르화칼슘과 산화마그네슘, 황산마그네슘, 인산마그네슘, 수산화마그네슘, 황산칼륨, 인산칼륨, 탄산칼륨, 염화칼륨, 수산화칼륨, 인산암모늄, 황산, 염산이 3종 이상으로 이루어지며, 그 중 하나 이상이 칼슘화합물이 되도록 혼합된 혼합물 5∼60중량%와 구연산 또는 구연산나트륨 10∼55중량%를 혼합하는 공정, 상기 혼합물을 70∼150℃의 온도를 유지하고 100∼150rpm으로 약20분∼90분 회전시키는 교반공정, 상기 교반된 혼합물을 필터프레스 또는 진공탈수기를 사용하여 수분을 50%이상 탈수시키는 탈수공정 및 상기 탈수된 혼합물의 잔여수분을 전기로 또는 열풍건조기로 98%이상 제거시키는 건조공정을 통하여 완성된다.The water-soluble composite calcium composition according to the present invention is calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (IIIIII), calcium cyanide, calcium nitrate, calcium fluoride and magnesium oxide in 30 to 40% by weight of water. Magnesium sulphate, magnesium phosphate, magnesium hydroxide, potassium sulphate, potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide, ammonium phosphate, sulfuric acid, hydrochloric acid, a mixture of at least one of which is a calcium compound Mixing 5 to 60% by weight with 10 to 55% by weight of citric acid or sodium citrate; stirring the mixture to maintain a temperature of 70 to 150 ° C. and rotating about 20 to 90 minutes at 100 to 150 rpm; Dehydration process that dehydrates the mixture by 50% or more by using filter press or vacuum dehydrator and 98% or more of the remaining moisture of the dehydrated mixture by electric or hot air dryer Completed through a drying process to remove.

상기의 제조공정을 좀 더 상세히 설명하면 다음과 같다.The above manufacturing process will be described in more detail as follows.

먼저, 칼슘화합물로서 탄산칼슘, 수산화칼슘, 염화칼슘, 황산칼슘, 3종의 인산칼슘(ⅠⅡⅢ), 시안화칼슘, 질산칼슘, 플루오르화칼슘을 준비하고 산화마그네슘, 황산마그네슘, 인산마그네슘, 수산화마그네슘의 마그네슘화합물, 황산칼륨, 인산칼륨, 탄산칼륨, 염화칼륨, 수산화칼륨의 칼륨화합물, 인산암모늄, 황산, 염산을 준비한다.First, as calcium compounds, calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (IIIIII), calcium cyanide, calcium nitrate and calcium fluoride were prepared, and magnesium compounds of magnesium oxide, magnesium sulfate, magnesium phosphate and magnesium hydroxide Prepare potassium sulfate, potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide potassium compound, ammonium phosphate, sulfuric acid, hydrochloric acid.

본 발명의 주원료로 사용되는 상기 탄산칼슘은 그 순도가 98%이상인 원료를 사용하며, 수산화칼슘, 염화칼슘, 황산칼슘, 3종의 인산칼슘(Ⅰ,Ⅱ,Ⅲ), 시안화칼슘, 질산칼슘, 플루오르화칼슘, 산화마그네슘, 황산마그네슘, 인산마그네슘, 수산화마그네슘, 황산칼륨, 인산칼륨, 탄산칼륨, 염화칼륨, 수산화칼륨, 인산암모늄, 황산은 그 순도가 95%인 원료를 사용하며 염산은 그 순도가 35%인 원료를 사용하는 것이 바람직하다.The calcium carbonate used as the main raw material of the present invention is a raw material having a purity of 98% or more, and calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (I, II, III), calcium cyanide, calcium nitrate, fluorinated Calcium, magnesium oxide, magnesium sulfate, magnesium phosphate, magnesium hydroxide, potassium sulfate, potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide, ammonium phosphate and sulfuric acid use raw materials with 95% purity. Preference is given to using phosphorus raw materials.

상기 화합물들 중 선택하여 원료혼합물을 준비하는데, 3종 이상의 화합물을 선택·혼합하며 상기 원료혼합물에는 칼슘화합물이 반드시 하나 이상 포함되도록 한다.To prepare a raw material mixture by selecting from the above compounds, three or more compounds are selected and mixed so that the raw material mixture contains at least one calcium compound.

예를 들면, 탄산칼슘, 염화칼슘, 수산화칼슘, 3종의 인산칼슘(Ⅰ,Ⅱ,Ⅲ), 황산칼슘 등 칼슘화합물만을 선택하여 혼합물을 만들 수 있고, 칼슘화합물로서 탄산칼슘과 염화칼슘을 선택하고 황산, 염산, 수산화칼륨, 인산마그네슘, 수산화마그네슘을 선택하여 혼합물을 만들 수 있다. 또 칼슘화합물로서 플루오르화칼슘을 선택하고 산화마그네슘, 황산마그네슘, 황산칼륨, 인산암모늄, 인산칼륨을 선택하여 혼합할 수도 있다. For example, a mixture can be made by selecting only calcium compounds such as calcium carbonate, calcium chloride, calcium hydroxide, three kinds of calcium phosphate (I, II, III), calcium sulfate, and calcium carbonate and calcium chloride as the calcium compound. Hydrochloric acid, potassium hydroxide, magnesium phosphate and magnesium hydroxide can be selected to form a mixture. Moreover, calcium fluoride can be selected as a calcium compound, and magnesium oxide, magnesium sulfate, potassium sulfate, ammonium phosphate, and potassium phosphate can also be selected and mixed.

본 발명의 수용성 복합칼슘 조성물에 따르면 상기 원료혼합물로서 탄산칼슘, 염화칼슘, 수산화칼슘, 질산칼슘, 3종의 인산칼슘(Ⅰ,Ⅱ,Ⅲ), 시안화칼슘, 플루오르화칼슘 및 황산칼슘을 선택·혼합하는 것이 가장 바람직하다.According to the water-soluble composite calcium composition of the present invention, the raw material mixture is selected and mixed with calcium carbonate, calcium chloride, calcium hydroxide, calcium nitrate, three kinds of calcium phosphate (I, II, III), calcium cyanide, calcium fluoride and calcium sulfate. Most preferred.

상기와 같이 선택된 원료를 적정한 양으로 혼합한 원료혼합물을 준비한다. 이때, 혼합되는 원료들은 완성되는 수용성 복합칼슘 조성물의 pH가 5.7∼7.5, 칼슘함량이 18∼40%되도록 상호 혼합량을 조절할 수 있다.A raw material mixture prepared by mixing the raw materials selected as described above in an appropriate amount is prepared. At this time, the raw materials to be mixed can adjust the amount of mutual mixing so that the pH of the finished water-soluble composite calcium composition is 5.7 to 7.5, calcium content 18 to 40%.

또한 상기 혼합물에 첨가될 구연산(Citric acid) 또는 구연산나트륨을 준비한다.Also prepare citric acid or sodium citrate to be added to the mixture.

구연산(C6H8O7)은 히드록시기를 가지는 다염기(多鹽基) 카르복실산의 하나로 시트르산 (citric acid)이라고도 하며 많은 식물의 씨나 과즙 속에 유리상태의 산으로 함유되어 있고 물과 에탄올에 잘 녹는 특징을 가지고 있다.Citric acid (C 6 H 8 O 7 ) is a hydroxyl-based polybasic carboxylic acid, also known as citric acid. It has good melting characteristics.

구연산나트륨(Sodium Citrate)은 백색결정의 입상분말로서 물에는 쉽게 녹으며 식품 제조시 pH를 정확하게 조절하는 pH조정제로 사용된다.Sodium citrate is a granular powder of white crystals, easily soluble in water and used as a pH adjuster to precisely control pH in food production.

이 밖에 상기 구연산 또는 구연산나트륨은 제조되는 수용성 복합칼슘 조성물의 pH 범위를 조절하도록 그 양을 10∼55중량%로 혼합하는 것이 바람직하다.In addition, the citric acid or sodium citrate is preferably mixed in an amount of 10 to 55% by weight so as to adjust the pH range of the water-soluble composite calcium composition prepared.

교반기에 물 30∼40중량%, 상기 혼합된 원료화합물 5∼60중량%와 구연산 또는 구연산나트륨 10∼55중량%를 투입하여 혼합시킨다. 이때, 상기 교반기에서의 혼합속도는 100∼150rpm으로 조정하고 반응온도는 70∼150℃로 유지하면서 20∼90분 동안 교반시킨다. 상기 교반기에서의 혼합속도와 반응온도 및 반응시간은 칼슘과 구연산의 중량차로 인한 혼합의 곤란성을 해결할 수 있도록 설정된 것이며, 상기의 원료물질 상호간의 배합조성비 및 합성 조건이 맞지 않을 경우 고순도의 수용성 복합칼슘 조성물의 제조가 어렵고 부수적인 효과를 주는 pH문제를 해결할 수 없으므로 상기 조건들을 맞춰주는 것이 바람직하다.30 to 40% by weight of water, 5 to 60% by weight of the mixed raw compound and 10 to 55% by weight of citric acid or sodium citrate are added to the stirrer and mixed. At this time, the mixing speed in the stirrer is adjusted to 100 ~ 150rpm and the reaction temperature is stirred for 20 to 90 minutes while maintaining at 70 ~ 150 ℃. The mixing speed, reaction temperature, and reaction time in the stirrer are set to solve the difficulty of mixing due to the weight difference between calcium and citric acid, and high purity water-soluble complex calcium when the mixing composition ratio and synthesis conditions of the raw materials do not match. It is desirable to meet the above conditions because the preparation of the composition is difficult and can not solve the pH problem of the side effect.

상기 교반공정을 거친 혼합물을 필터프레스 또는 진공탈수기를 사용하여 수분을 50%이상 탈수시킨 다음 전기로 또는 열풍건조기를 사용하여 나머지 잔여수분을 98%이상 제거시킨다. The mixture was subjected to the stirring process to dehydrate water by 50% or more using a filter press or a vacuum dehydrator, and then removes the remaining residual water by 98% or more using an electric furnace or a hot air dryer.

상기 필터프레스 또는 진공탈수기에서 수분을 50%이상 탈수시키는 이유는 다음공정인 전기로와 열풍건조기에서의 건조시간이 길어지지 않게 하기 위함이며 전기로와 열풍건조기에서 수분을 98%이상 제거시키는 이유는 완성된 수용성 복합칼슘 조성물이 덩어리로 뭉쳐지지 않고 분말화가 잘 되어 제품의 품질이 우수하며 이를 사용하고자 계량할 때 편리하게 하기 위함이다.The reason for dehydrating more than 50% of the moisture in the filter press or vacuum dehydrator is to prevent the drying time in the electric furnace and the hot air dryer, which is the next process, and to remove 98% or more of the moisture in the electric furnace and the hot air dryer. The water-soluble complex calcium composition does not aggregate into agglomerates and is well powdered so that the quality of the product is excellent and it is for convenience when weighing to use it.

이렇게 하여 완성된 본 발명의 수용성 복합칼슘 조성물은 주성분 함량이 18∼40%인 고순도 칼슘으로서 물에 완전히 녹기 때문에 비료로서 사용될 때 농작물에 매우 높은 흡수력을 갖게 한다. 따라서 신속한 영양공급을 통해 농작물의 세포벽을 튼튼히 하고 영양결핍과 이로 인한 각종 생리장해 및 병충해의 발생을 예방 및 치유할 수 있다. 나아가, 본 발명의 수용성 복합칼슘 조성물은 환경오염 원인중의 하나인 농약의 과다사용을 경감시키고 토양의 산성화를 방지시켜 중성토양으로 서서히 바꿔주는 역할을 할 수 있다.The water-soluble composite calcium composition of the present invention thus completed has a very high absorption power to the crop when used as a fertilizer because it is completely dissolved in water as high purity calcium having a main component content of 18 to 40%. Therefore, it is possible to strengthen the cell walls of crops through rapid nutrition, and to prevent and cure the occurrence of malnutrition and various physiological disorders and pests. Furthermore, the water-soluble complex calcium composition of the present invention may serve to reduce overuse of pesticides, which is one of the causes of environmental pollution, and to gradually convert the soil into neutral soil by preventing acidification of the soil.

이하 본 발명의 실시예와 본 발명의 주원료로 사용되는 칼슘화합물, 마그네슘화합물, 칼륨화합물, 인산암모늄, 황산, 염산 및 구연산 또는 구연산나트륨의 최적 혼합비율을 알아보기 위한 실험예를 나타내도록 하겠으나, 본 발명의 보호범위는 이에 한정되는 것이 아니다.Examples of the present invention and calcium compounds, magnesium compounds, potassium compounds, ammonium phosphate, sulfuric acid, hydrochloric acid and citric acid or sodium citrate to be used as the main raw material of the present invention will be shown an experimental example to find the optimum mixing ratio, but The protection scope of the invention is not limited thereto.

〈실시예1〉<Example 1>

용매제인 물 35중량%에 구연산 30중량%와 탄산칼슘, 수산화칼슘, 염화칼슘, 황산칼슘, 3종의 인산칼슘(Ⅰ,Ⅱ,Ⅲ), 황산, 염산, 수산화칼륨, 인산마그네슘, 수산화마그네슘을 혼합한 혼합물 35중량%를 첨가하였다.35% by weight of the solvent, water, 30% by weight citric acid and calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (I, II, III), sulfuric acid, hydrochloric acid, potassium hydroxide, magnesium phosphate, magnesium hydroxide 35% by weight of the mixture was added.

상기 혼합물을 교반기에 넣고 교반기의 온도를 100℃로 유지하면서 60분간 120rpm의 속도로 회전시키면서 교반하였다. 교반공정 동안 용매로 사용된 물이 다소 제거되었다.The mixture was placed in a stirrer and stirred while rotating at a speed of 120 rpm for 60 minutes while maintaining the temperature of the stirrer at 100 ° C. The water used as solvent during the stirring process was somewhat removed.

상기 교반된 혼합물을 진공탈수기에 넣어 50%이상의 수분을 탈수시켰다. 탈수공정 후에도 여전히 남아있는 수분을 제거시키기 위해 상기 혼합물을 열풍건조기에 의해 일정량의 열풍이 연속 공급되는 벨트로 통과시켜 98%이상의 수분을 제거시켰다. The stirred mixture was put in a vacuum dehydrator to dehydrate more than 50% of water. In order to remove the water remaining even after the dehydration process, the mixture was passed through a belt through which a constant amount of hot air was continuously supplied by a hot air dryer to remove more than 98% of water.

이렇게 하여 완성된 수용성 복합칼슘 조성물은 칼슘성분의 함량이 18∼40%인 분말상의 고순도 제품으로서 물에 완전히 녹는 수용성 복합칼슘 조성물이기 때문에 농작물 또는 토양의 비료로서 사용될 때 매우 높은 흡수력을 갖게 하고 신속한 영양공급을 통해 농작물의 영양결핍 및 각종 병해충의 발생을 억제/최소화하는 역할은 물론 산성화가 진행된 토양을 중성토양으로 서서히 바꿔주는 역할을 하였다. The water-soluble composite calcium composition thus obtained is a powdery high purity product having a calcium content of 18 to 40%, which is completely soluble in water, and thus has very high absorption ability and rapid nutrition when used as a fertilizer for crops or soil. Through the supply, the role of suppressing / minimizing the crop's nutritional deficiency and the occurrence of various pests, as well as gradually changing the acidified soil into neutral soils.

〈실험예1〉Experimental Example 1

탄산칼슘, 염화칼슘, 수산화칼슘, 인산칼슘(Ⅰ,Ⅱ,Ⅲ) 및 황산칼슘과 구연산 또는 구연산나트륨을 아래와 같은 중량으로 혼합하여 수용성 복합칼슘 조성물을 제조하였다.Calcium carbonate, calcium chloride, calcium hydroxide, calcium phosphate (I, II, III) and calcium sulfate and citric acid or sodium citrate were mixed in the following weight to prepare a water-soluble composite calcium composition.

NO.원료명      NO. 1One 22 33 44 55 66 77 88 99 1010 1111 탄산칼슘Calcium carbonate 40.240.2 35.635.6 35.635.6 32.932.9 21.421.4 24.024.0 18.618.6 24.624.6 27.527.5 27.827.8 27.927.9 염화칼슘Calcium chloride 15.715.7 13.913.9 13.913.9 16.516.5 21.421.4 19.219.2 18.618.6 19.719.7 18.318.3 16.616.6 16.716.7 수산화칼슘Calcium hydroxide 2.82.8 2.52.5 2.52.5 5.55.5 5.35.3 4.84.8 4.74.7 4.94.9 4.64.6 5.65.6 5.65.6 인산칼슘Calcium phosphate -- -- 1.01.0 1.11.1 5.95.9 10.610.6 4.74.7 5.45.4 10.110.1 3.33.3 3.43.4 황산칼슘Calcium sulfate 1.11.1 1.01.0 -- -- 3.23.2 2.92.9 2.82.8 2.92.9 2.82.8 2.02.0 1.71.7 구연산/구연산나트륨Citric Acid / Sodium Citrate 40.240.2 47.047.0 47.047.0 44.044.0 42.842.8 38.538.5 50.650.6 42.542.5 36.736.7 44.744.7 44.744.7 총량(g)Gross weight (g) 100100 100100 100100 100100 100100 100100 100100 100100 100100 100100 100100 pHpH 7.417.41 6.886.88 6.666.66 7.027.02 6.586.58 6.956.95 6.846.84 7.287.28 7.197.19 6.736.73 6.716.71 용해 상태Dissolution state 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good

본 실험은 탄산칼슘, 염화칼슘, 수산화칼슘, 인산칼슘(Ⅰ,Ⅱ,Ⅲ) 및 황산칼슘과 구연산 또는 구연산나트륨의 총 혼합양이 100g이 되도록 혼합하여 물에 용해시켰을 때 pH와 용해상태를 알아본 시험이다. This experiment was carried out to determine the pH and dissolution of calcium carbonate, calcium chloride, calcium hydroxide, calcium phosphate (I, II, III), and when dissolved in water by mixing the total amount of calcium sulfate and citric acid or sodium citrate to 100g. to be.

상기 용해상태의 표시에서 양호라 함은 상기 혼합물을 용해시켰을 때 잘 녹고 수용액에 함유된 칼슘성분이 18∼40% 내로 조절가능하며 투명도 또한 높은 상태를 의미하는 것이다.Good in the display of the dissolved state means that the calcium component in the aqueous solution is dissolved well when dissolved in the mixture is adjustable within 18 to 40% and the transparency is also high.

표1에서 시험번호 1∼4는 주성분 함량이 높은 계통이며, 시험번호 5∼11은 주성분 함량이 낮은 계통을 나타낸다.In Table 1, Test Nos. 1 to 4 are strains having a high main ingredient content, and Test Nos. 5 to 11 are strains having a low main ingredient content.

〈실험예2〉Experimental Example 2

탄산칼슘, 염화칼슘, 수산화칼슘, 인산칼슘(Ⅰ,Ⅱ,Ⅲ), 황산칼슘 및 질산칼슘과 구연산 또는 구연산나트륨을 아래와 같은 중량으로 혼합하여 수용성 복합칼슘 조성물을 제조하였다.Water-soluble complex calcium compositions were prepared by mixing calcium carbonate, calcium chloride, calcium hydroxide, calcium phosphate (I, II, III), calcium sulfate and calcium nitrate with citric acid or sodium citrate in the following weights.

NO.원료명      NO. 1One 22 33 44 55 66 77 탄산칼슘Calcium carbonate 27.427.4 27.427.4 27.427.4 27.427.4 27.427.4 27.427.4 27.427.4 염화칼슘Calcium chloride 4.54.5 4.54.5 4.54.5 4.54.5 13.613.6 9.19.1 4.54.5 수산화칼슘Calcium hydroxide 18.218.2 13.613.6 9.19.1 4.54.5 -- -- -- 인산칼슘Calcium phosphate -- 4.54.5 4.54.5 4.54.5 6.46.4 11.811.8 13.613.6 황산칼슘Calcium sulfate -- -- 4.54.5 3.63.6 2.72.7 1.81.8 2.72.7 질산칼슘Calcium nitrate -- -- -- -- -- -- 1.81.8 구연산/구연산나트륨Citric Acid / Sodium Citrate 49.949.9 50.050.0 50.050.0 55.555.5 49.949.9 49.949.9 50.050.0 총량(g)Gross weight (g) 100100 100100 100100 100100 100100 100100 100100 pHpH 6.266.26 6.286.28 6.076.07 6.296.29 5.695.69 5.915.91 6.306.30 용해 상태Dissolution state 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good

본 실험은 탄산칼슘, 염화칼슘, 수산화칼슘, 인산칼슘(Ⅰ,Ⅱ,Ⅲ), 황산칼슘 및 질산칼슘과 구연산 또는 구연산나트륨의 총 혼합양이 100g이 되도록 혼합하여 물에 용해시켰을 때 pH와 용해상태를 알아본 시험이다. In this experiment, the total mixing amount of calcium carbonate, calcium chloride, calcium hydroxide, calcium phosphate (I, II, III), calcium sulfate and calcium nitrate with 100 g of citric acid or sodium citrate was mixed to dissolve in water. This is the test I saw.

상기 용해상태의 표시에서 양호라 함은 상기 혼합물을 용해시켰을 때 잘 녹고 수용액에 함유된 칼슘성분이 18∼40% 내로 조절가능하며 투명도 또한 높은 상태를 의미하는 것이다.Good in the display of the dissolved state means that the calcium component in the aqueous solution is dissolved well when dissolved in the mixture is adjustable within 18 to 40% and the transparency is also high.

표2에서 시험번호 1∼7은 pH 5.7∼6.3사이의 약산성을 갖는 계통을 나타낸다.In Table 2, Test Nos. 1 to 7 indicate strains having a weak acidity between pH 5.7 and 6.3.

〈실험예3〉Experimental Example 3

플루오르화칼슘, 산화마그네슘, 황산마그네슘, 황산칼륨, 인산암모늄 및 인산칼륨과 구연산 또는 구연산나트륨을 아래와 같은 중량으로 혼합하여 수용성 복합칼슘 조성물을 제조하였다.Water-soluble complex calcium compositions were prepared by mixing calcium fluoride, magnesium oxide, magnesium sulfate, potassium sulfate, ammonium phosphate and potassium phosphate with citric acid or sodium citrate in the following weights.

No.원료명     No. Raw Material Name 1One 22 33 44 55 66 77 플루오르화칼슘Calcium fluoride 27.427.4 27.427.4 27.427.4 27.427.4 27.427.4 27.427.4 27.427.4 산화마그네슘Magnesium oxide 18.218.2 13.613.6 9.19.1 4.54.5 -- -- -- 황산마그네슘Magnesium sulfate 4.54.5 4.54.5 4.54.5 4.54.5 13.613.6 9.19.1 4.54.5 황산칼륨Potassium sulfate -- 4.54.5 4.54.5 4.54.5 6.46.4 11.811.8 13.613.6 인산암모늄Ammonium Phosphate -- -- 4.54.5 3.63.6 2.72.7 1.81.8 2.72.7 인산칼륨Potassium phosphate -- -- -- -- -- -- 1.81.8 구연산/구연산나트륨Citric Acid / Sodium Citrate 49.949.9 50.050.0 50.050.0 55.555.5 49.949.9 49.949.9 50.050.0 총량(g)Gross weight (g) 100100 100100 100100 100100 100100 100100 100100 pHpH 6.016.01 6.116.11 5.845.84 6.086.08 6.116.11 6.086.08 6.356.35 용해 상태Dissolution state 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good

본 실험은 플루오르화칼슘, 산화마그네슘, 황산마그네슘, 황산칼륨, 인산암모늄 및 인산칼륨과 구연산 또는 구연산나트륨의 총 혼합양이 100g이 되도록 혼합하여 물에 용해시켰을 때 pH와 용해상태를 알아본 시험이다. This experiment is to check the pH and dissolution of calcium fluoride, magnesium oxide, magnesium sulfate, potassium sulfate, ammonium phosphate, potassium phosphate, potassium phosphate and citric acid or sodium citrate in a total amount of 100g. .

상기 용해상태의 표시에서 양호라 함은 상기 혼합물을 용해시켰을 때 잘 녹고 수용액에 함유된 칼슘성분이 18∼40% 내로 조절가능하며 투명도 또한 높은 상태를 의미하는 것이다.Good in the display of the dissolved state means that the calcium component in the aqueous solution is dissolved well when dissolved in the mixture is adjustable within 18 to 40% and the transparency is also high.

표3에서 시험번호 1∼7은 구연산 비율이 높은 계통을 나타낸다.In Table 3, Test No. 1-7 shows the system with high citric acid ratio.

〈실험예4〉Experimental Example 4

탄산칼슘, 염화칼슘, 수산화칼슘, 염산, 인산마그네슘, 수산화마그네슘 및 황산과 구연산 또는 구연산나트륨을 아래와 같은 중량으로 혼합하여 수용성 복합칼슘 조성물을 제조하였다.Water-soluble complex calcium compositions were prepared by mixing calcium carbonate, calcium chloride, calcium hydroxide, hydrochloric acid, magnesium phosphate, magnesium hydroxide and sulfuric acid with citric acid or sodium citrate in the following weights.

No.원료명            No. Raw Material Name 1One 22 33 44 55 66 77 88 탄산칼슘Calcium carbonate 27.427.4 27.427.4 27.427.4 27.427.4 27.427.4 27.427.4 27.427.4 27.427.4 염화칼슘Calcium chloride 18.218.2 13.613.6 9.19.1 4.54.5 -- -- -- 4.54.5 수산화칼슘Calcium hydroxide 4.54.5 4.54.5 4.54.5 4.54.5 13.613.6 9.19.1 1.81.8 3.63.6 염산Hydrochloric acid -- -- -- -- -- -- -- 4.54.5 인산마그네슘Magnesium phosphate -- 4.54.5 4.54.5 4.54.5 6.46.4 11.811.8 13.613.6 2.72.7 수산화마그네슘Magnesium hydroxide -- -- 4.54.5 3.63.6 2.72.7 1.81.8 2.72.7 2.72.7 황산Sulfuric acid -- -- -- -- -- -- 4.54.5 4.54.5 구연산/구연산나트륨Citric Acid / Sodium Citrate 49.949.9 50.050.0 50.050.0 55.555.5 49.949.9 49.949.9 50.050.0 50.150.1 총량(g)Gross weight (g) 100100 100100 100100 100100 100100 100100 100100 100100 pHpH 6.096.09 5.975.97 5.775.77 6.286.28 6.656.65 6.846.84 6.356.35 6.106.10 용해 상태Dissolution state 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good 양호Good

본 실험은 탄산칼슘, 염화칼슘, 수산화칼슘, 염산, 인산마그네슘, 수산화마그네슘 및 황산과 구연산 또는 구연산나트륨의 총 혼합양이 100g이 되도록 혼합하여 물에 용해시켰을 때 pH와 용해상태를 알아본 시험이다. This experiment is to check the pH and dissolution of calcium carbonate, calcium chloride, calcium hydroxide, hydrochloric acid, magnesium phosphate, magnesium hydroxide, sulfuric acid and citric acid or sodium citrate in a total mixing amount of 100g and dissolved in water.

상기 용해상태의 표시에서 양호라 함은 상기 혼합물을 용해시켰을 때 잘 녹고 수용액에 함유된 칼슘성분이 18∼40% 내로 조절가능하며 투명도 또한 높은 상태를 의미하는 것이다.Good in the display of the dissolved state means that the calcium component in the aqueous solution is dissolved well when dissolved in the mixture is adjustable within 18 to 40% and the transparency is also high.

표4에서 시험번호 1∼8은 pH가 5.7∼6.8사이를 갖는 계통을 나타낸다.In Table 4, Test Nos. 1 to 8 indicate strains having a pH between 5.7 and 6.8.

상술한 바와 같은 본 발명의 수용성 복합칼슘 조성물은 고활성기능을 가진 분말상의 수용성 복합칼슘 조성물로서, 농작물에 신속하게 영양을 공급할 수 있어 품질이 우수한 농작물 생산을 가능하게 할 뿐 아니라 인건비 절감, 노동시간 단축을 통해 사용자가 경제적 이익을 얻을 수 있고 나아가 농약의 과다사용을 경감시켜 토양을 개선하는 효과가 있어서 환경개선제로서도 그 일익을 담당할 수 있다.As described above, the water-soluble complex calcium composition of the present invention is a powdered water-soluble complex calcium composition having a high activity function, which can quickly supply nutrition to crops, thereby producing crops of high quality, as well as reducing labor costs and working hours. By shortening the user's economic benefits and further reducing the overuse of pesticides, it is effective in improving the soil, which can serve as an environmental improvement agent.

또한 본 발명에 따라 제조된 수용성 복합칼슘 조성물은 다종의 혼합유해가스나 악취 등의 흡착, 탈취, 흡습에도 효과가 우수하여 다양한 용도로 사용될 수 있다. In addition, the water-soluble composite calcium composition prepared according to the present invention is excellent in the effects of adsorption, deodorization, and moisture absorption of various types of mixed harmful gases and odors, and thus can be used in various applications.

Claims (3)

칼슘화합물로서 탄산칼슘, 수산화칼슘, 염화칼슘, 황산칼슘, 3종의 인산칼슘(Ⅰ,Ⅱ,Ⅲ), 시안화칼슘, 질산칼슘, 플루오르화칼슘과 산화마그네슘, 황산마그네슘, 인산마그네슘, 수산화마그네슘, 황산칼륨, 인산칼륨, 탄산칼륨, 염화칼륨, 수산화칼륨, 인산암모늄, 황산, 염산이 3종 이상으로 이루어지며, 그 중 하나 이상이 칼슘화합물이 되도록 혼합된 원료혼합물 5∼60중량%, 구연산 또는 구연산나트륨 10∼55중량% 및 물 30∼40중량%로 이루어지며, Calcium compounds include calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, three types of calcium phosphate (I, II, III), calcium cyanide, calcium nitrate, calcium fluoride and magnesium oxide, magnesium sulfate, magnesium phosphate, magnesium hydroxide, potassium sulfate , Consisting of three or more kinds of potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide, ammonium phosphate, sulfuric acid, and hydrochloric acid, at least one of which is mixed with 5 to 60 wt% of citric acid, citric acid or sodium citrate It consists of -55 weight% and 30-40 weight% of water, 수소이온농도범위가 pH 5.7∼7.5이고 칼슘의 주성분 함량이 18∼40%를 유지하는 것을 특징으로 하는 수용성 복합칼슘 조성물.A water-soluble composite calcium composition characterized in that the hydrogen ion concentration ranges from pH 5.7 to 7.5 and maintains the main component content of calcium at 18 to 40%. 삭제delete 물 30∼40중량%에 칼슘화합물로서 탄산칼슘, 수산화칼슘, 염화칼슘, 황산칼슘, 3종의 인산칼슘(Ⅰ,Ⅱ,Ⅲ), 시안화칼슘, 질산칼슘, 플루오르화칼슘과 산화마그네슘, 황산마그네슘, 인산마그네슘, 수산화마그네슘, 황산칼륨, 인산칼륨, 탄산칼륨, 염화칼륨, 수산화칼륨, 인산암모늄, 황산, 염산이 3종 이상으로 이루어지며, 그 중 하나 이상이 칼슘화합물이 되도록 혼합된 혼합물 5∼60중량%와 구연산 또는 구연산나트륨 10∼55중량%를 혼합하는 공정; Calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (I, II, III), calcium cyanide, calcium nitrate, calcium fluoride and magnesium oxide, magnesium sulfate, phosphoric acid 5 to 60% by weight of a mixture of magnesium, magnesium hydroxide, potassium sulfate, potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide, ammonium phosphate, sulfuric acid and hydrochloric acid, so that at least one of them is a calcium compound Mixing 10 to 55% by weight of citric acid or sodium citrate; 상기 혼합물을 70∼150℃의 온도를 유지하고 100∼150rpm으로 약20분∼90분 회전시키는 교반공정;Stirring the mixture for about 20 to 90 minutes at 100 to 150 rpm while maintaining the temperature of 70 to 150 ° C; 상기 교반된 혼합물을 필터프레스 또는 진공탈수기를 사용하여 수분을 50%이상 탈수시키는 탈수공정;A dehydration step of dehydrating the stirred mixture by 50% or more of water using a filter press or a vacuum dehydrator; 상기 탈수된 혼합물의 잔여수분을 전기로 또는 열풍건조기로 98%이상 제거시키는 건조공정으로 이루어지는 것을 특징으로 하는 수용성 복합칼슘 조성물의 제조방법.Method for producing a water-soluble composite calcium composition, characterized in that the drying step of removing the excess water of the dehydrated mixture of 98% or more by an electric furnace or a hot air dryer.
KR10-2003-0002501A 2003-01-14 2003-01-14 watersoluble Calcium complex and manufacturing method thereof KR100510084B1 (en)

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