KR101288554B1 - Nitrate production method for deodorization using shell - Google Patents

Nitrate production method for deodorization using shell Download PDF

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KR101288554B1
KR101288554B1 KR1020120015375A KR20120015375A KR101288554B1 KR 101288554 B1 KR101288554 B1 KR 101288554B1 KR 1020120015375 A KR1020120015375 A KR 1020120015375A KR 20120015375 A KR20120015375 A KR 20120015375A KR 101288554 B1 KR101288554 B1 KR 101288554B1
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nitrate
shell
aqueous solution
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deodorizing
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송호면
우달식
이학수
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한국건설기술연구원
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/36Nitrates
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/01Deodorant compositions
    • A61L9/013Deodorant compositions containing animal or plant extracts, or vegetable material
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2209/00Aspects relating to disinfection, sterilisation or deodorisation of air
    • A61L2209/20Method-related aspects
    • A61L2209/21Use of chemical compounds for treating air or the like

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Inorganic Chemistry (AREA)
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  • Treating Waste Gases (AREA)

Abstract

PURPOSE: A manufacturing method of nitrate for deodorization using shells is provided to present an effective treatment by reusing the disposed oyster shell at the seashore. CONSTITUTION: The manufacturing method of nitrate using shells is to remove bad smell of the sewer pipe. The manufacturing method of nitrate using shells comprises preconditioning progress which removes impurity by washing the shell and processing plasticity with the shell; a generating process of nitrate aqueous solution that reacts the shell which removed the impurity by the preconditioning progress; a generating progress of nitrate crystalline powder which collects nitrate crystalline powder by cooling after concentrating the nitrate aqueous solution.

Description

패각을 이용한 탈취용 질산염 제조방법{NITRATE PRODUCTION METHOD FOR DEODORIZATION USING SHELL}Nitrate for deodorization using shells {NITRATE PRODUCTION METHOD FOR DEODORIZATION USING SHELL}

본 발명은 패각을 이용하여 탈취용 질산염을 제조하는 방법에 관한 것으로, 더욱 상세하게는 패각을 이용하여 하수관거에서 발생하는 퇴적물 및 생물막에서 황산염-환원세균에 의해 발생되는 황화수소를 제거하기 위한 탈취용 질산염을 제조하는 방법에 관한 것이다.
The present invention relates to a method for producing a deodorizing nitrate using a shell, more specifically, a deodorizing nitrate for removing hydrogen sulfide generated by sulfate-reducing bacteria in sediments and biofilms generated in sewage pipe using the shell. It relates to a method of manufacturing.

굴과 같은 패각류에서 발생되는 패각은 남해안 일대를 중심으로 연간 28~30만여 톤이 발생되고 있다. 하지만, 굴 패각 총 발생량의 약 10%만이 공업용 비료, 토양개량제 및 건축재료 등으로 활용되고 있을 뿐 대부분의 굴 패각은 무단으로 매립되거나 생활주변에 불법적으로 약적 방치되고 있는 실정이다. The shells generated by shells such as oysters generate about 280,000 to 300,000 tons annually in the southern coastal area. However, only about 10% of the total oyster shells are used as industrial fertilizers, soil improvers and building materials. Most of the oyster shells are either landfilled or illegally left unattended.

이처럼 방치되고 있는 굴 패각들은 시간이 경과되면서 표면에 부착되어 있던 유기물질들이 부패되어 고약한 악취를 발생시킬 뿐 아니라 주변경관 훼손 등 지역주민의 생활환경 및 지역 관광산업 등을 저해하는 해양 환경오염원으로써 그 문제성이 매우 심각한 실정이다.These oyster shells that have been left unattended over time have decayed organic substances attached to the surface and cause nasty odors, as well as marine environmental pollution sources that hamper the local people's living environment and local tourism such as damage to surrounding landscapes. The problem is very serious.

한편, 산업문명의 발달로 인한 국민들의 생활수준 향상으로 환경공해에 대한 관심이 급증하게 되면서 악취에 대한 민원이 매년 급증하고 있다. 그 중 도시의 정맥과 같은 기능을 가진 하수관거에서 발생되는 악취는 최근 생활환경을 저해하는 중요한 요인으로 많은 민원을 야기하고 있는 실정이다.Meanwhile, as the interest in environmental pollution has increased due to the improvement of people's living standards due to the development of industrial civilization, complaints about odor are increasing every year. Among them, odor generated from sewage pipes having the same function as urban veins is causing a lot of complaints as an important factor that hinders the living environment in recent years.

악취에 대한 일반적 정의는 황화수소, 메르캅탄류, 아민류 그 밖에 자극성이 있는 기체상태의 물질로 사람의 후각을 자극하는 불쾌감과 혐오감을 주는 냄새로 정의되어 있다. 하수의 경우 전체 황화물의 대부분(70~90%)은 용존 황화물이 차지하고 있다.The general definition of odor is hydrogen sulfide, mercaptans, amines, and other irritating gaseous substances that are defined as an unpleasant and disgusting odor that stimulates the human sense of smell. In sewage, most of the total sulfides (70-90%) are made up of dissolved sulfides.

하수관거의 내 악취발생의 최대 원인 물질은 황화합물 중 황화수소이다. 이러한 황화수소가 발생되는 메카니즘은 하수가 혐기 상태로 되면서 관거의 퇴적물이나 관벽에 부착된 생물막중에 서식하는 황산염 환원세균이 활성화되고, 하수 중의 황산이온이 황화물로 환원됨으로써 이루어진다.The main cause of odor in sewage pipes is hydrogen sulfide among sulfur compounds. The mechanism by which hydrogen sulfide is generated is achieved by the activation of sulfate reducing bacteria in the sediments of conduits and biofilms attached to the pipe walls while the sewage is anaerobic, and the reduction of sulfate ions in the sewage into sulfides.

이러한 악취 물질을 제거하는 방법으로서, 크게 액상처리 방법과 기상처리 방법 두 가지로 구분할 수 있다. 액상처리 방법은 일반적으로 순산소(Pure oxygen)나 공기를 압력하수관에 고압으로 주입하는 방법, 철염(Iron salts)으로 처리하는 방법, 산화제 약품을 투입하는 방법, pH를 조절하는 방법, 질산염을 사용하는 방법, 미생물제나 효소를 주입하는 방법 등으로 처리되고 있으며, 기상처리 방법은 환기, 약품중화제 살포 등의 방법으로 처리되고 있다. 이외에도 펌프장 구조개선, 세정탑, 바이오필터를 설치하는 방법 등이 있다.As a method of removing such odorous substances, it can be largely divided into a liquid treatment method and a gas phase treatment method. Liquid treatment methods generally involve pure oxygen or air at high pressure into the pressure sewer, treatment with iron salts, oxidizing agents, pH adjustment, and nitrates. It is processed by the method of injecting | pouring, the method of injecting a microbial agent, an enzyme, etc., and the vapor phase processing method is processed by methods, such as ventilation and spraying a chemical neutralizer. In addition, there is a method for improving the structure of a pumping station, a washing tower, and installing a biofilter.

상기의 악취 물질 제거방법 중 질산염을 사용하는 방법은 상기에서 설명한 황화수소와 반응하지 않고 오히려 황화수소의 형성을 방해하는 방법이다. 질산염을 사용하기 위하여 사용되는 화합물은 질산나트륨, 질산철, 질산칼슘 등이 있으며, 이중 질산칼슘이 가장 우수한 화합물로 인정되고 있으나, 국내에서는 고가의 약품에 해당하므로 현장 적용에는 한계가 있는 문제점이 있다. The method of using nitrate in the method of removing odorous substances is a method of not reacting with hydrogen sulfide as described above but rather preventing formation of hydrogen sulfide. Compounds used to use nitrates include sodium nitrate, iron nitrate, calcium nitrate, etc. Among these, calcium nitrate is recognized as the most excellent compound, but it is expensive in Korea, so there is a problem in the field application. .

따라서, 고가의 화합물을 이용하지 않으면서도 악취를 제거할 수 있는 질산염을 수득할 수 있는 현실적인 제조방법이 부존하는 것이 문제이다.
Therefore, there is a problem that a realistic manufacturing method for obtaining nitrates capable of removing odors without using expensive compounds is lacking.

본 발명은 이와 같은 종래의 문제점을 해결하기 위한 것으로, 본 발명의 목적은 해안에서 폐기되는 굴 패각을 재활용하여 효과적으로 처리할 수 있는 방안을 제시하는 것이다.The present invention is to solve such a conventional problem, the object of the present invention is to propose a method that can be effectively treated by recycling the oyster shell discarded from the coast.

본 발명의 다른 목적은 악취를 제거하기 위한 질산염을 제조하기 위하여 굴 패각을 이용하는 것이다.
Another object of the present invention is to use oyster shells to produce nitrates for removing odors.

이와 같은 목적을 달성하기 위한 본 발명의 특징에 의하면, 본 발명의 패각을 이용한 탈취용 질산염 제조방법은 패각을 이용하여 하수관거의 악취물질을 제거하기 위한 질산염을 제조하는 방법에 있어서, 패각을 세정하고 소성시킴으로써 불순물을 제거하는 전처리 공정; 상기 전처리 공정에 의해 불순물이 제거된 패각을 질산수용액에 반응시킴으로써 질산염 수용액을 얻는 질산염 수용액 생성 공정;및 상기 질산염 수용액을 농축시킨 후 냉각시킴으로써 질산염 결정분말을 회수하는 질산염 결정분말 생성 공정을 포함하는 것이 바람직하다.According to a feature of the present invention for achieving the above object, the deodorizing nitrate manufacturing method using the shell of the present invention in the method for producing a nitrate for removing odorous substances in the sewage pipe using the shell, washing the shell A pretreatment step of removing impurities by firing; A nitrate solution generation step of obtaining an nitrate aqueous solution by reacting the shell from which impurities are removed by the pretreatment step with an aqueous solution of nitrate; and a nitrate crystal powder generation step of recovering the nitrate crystal powder by concentrating and cooling the nitrate solution. desirable.

본 발명의 전처리 공정은 상기 소성과정에 의해 불순물이 제거된 패각을 분쇄하여 패각 분말을 생성하는 분쇄공정을 포함하는 것이 바람직하다.The pretreatment process of the present invention preferably includes a crushing step of pulverizing the shell from which impurities are removed by the calcination process to produce shell powder.

본 발명의 분쇄공정은 상기 패각 분말의 입도가 2 ~ 300 ㎛가 되도록 상기 패각을 분쇄하는 것이 바람직하다.In the grinding step of the present invention, it is preferable to grind the shell so that the particle size of the shell powder is 2 ~ 300 ㎛.

본 발명의 전처리공정은 상기 패각을 세정한 후, 400 ~ 500℃의 온도로 소성처리하는 것이 바람직하다.In the pretreatment step of the present invention, the shell is washed, and then calcined at a temperature of 400 to 500 ° C.

본 발명의 질산염 수용액 생성공정은 상기 패각에 7 ~ 12N의 질산수용액을 10 ~ 55 mL/min의 속도로 투입하여 20 ~ 60분간 교반하는 것이 바람직하다.In the nitrate aqueous solution generation process of the present invention, it is preferable to add 7 to 12N of nitric acid solution to the shell at a rate of 10 to 55 mL / min and stir for 20 to 60 minutes.

본 발명의 질산염 수용액 생성공정은 상온에서 실시되는 것이 바람직하다.The nitrate aqueous solution generation process of the present invention is preferably carried out at room temperature.

본 발명의 질산염 수용액 생성공정은 생성된 질산염 수용액과 염기성 수용액을 서로 중화반응시키는 것이 바람직하다.In the nitrate aqueous solution generation process of the present invention, it is preferable to neutralize the generated nitrate aqueous solution and the basic aqueous solution.

본 발명의 질산염 수용액은 상기 중화반응에 의해 5 ~ 9 pH를 가지는 것이 바람직하다.It is preferable that the nitrate aqueous solution of this invention has a pH of 5-9 by the said neutralization reaction.

본 발명의 염기성 수용액은 수산화칼슘 또는 산화칼슘수용액인 것이 바람직하다.The basic aqueous solution of the present invention is preferably calcium hydroxide or calcium oxide aqueous solution.

본 발명의 질산염 수용액 생성공정은 상기 질산염 수용액 이외의 성분을 여과하는 여과공정을 포함하는 것이 바람직하다.It is preferable that the nitrate aqueous solution production process of this invention includes the filtration process of filtering components other than the said nitrate aqueous solution.

본 발명의 질산염 결정분말 생성 공정은 상기 질산염 수용액을 50 ~ 100℃의 온도로 20 ~ 60분간 가열한 후, 냉각시킴으로써 질산염 결정분말을 회수하는 것이 바람직하다.In the nitrate crystal powder production process of the present invention, it is preferable to recover the nitrate crystal powder by heating the nitrate aqueous solution at a temperature of 50 to 100 ° C. for 20 to 60 minutes and then cooling the same.

본 발명의 질산염 결정분말 생성 공정은 상기 가열 및 냉각 공정을 다수회 반복 실시하는 것이 바람직하다.
In the nitrate crystal powder generation step of the present invention, the heating and cooling steps are preferably repeated a plurality of times.

이와 같은 본 발명에 의한 패각을 이용한 탈취용 질산염 제조방법에 의하면, 기존의 하수관거 악취저감을 위해 사용되는 질산염을 굴 패각을 이용하여 저렴하게 생산할 수 있으므로 비용측면에서 경제적으로 유리하고, 해안에 폐기되는 굴 패각을 재활용할 수 있기 때문에 환경친화적이고 해양오염을 감소시킬 수 있음과 동시에 폐자원을 활용할 수 있고 항구적인 대체 자원으로 활용할 수 있는 이점이 있다.
According to the method for manufacturing deodorizing nitrate using the shell according to the present invention, it is economically advantageous in terms of cost because it can be produced inexpensively using oyster shell to reduce the smell of the existing sewage pipe odor, which is disposed on the coast Oyster shells can be recycled, making them environmentally friendly and reducing marine pollution, while utilizing waste resources as well as permanent alternatives.

이하에서는 본 발명의 바람직한 실시예를 보다 상세하게 설명한다.Hereinafter, a preferred embodiment of the present invention will be described in more detail.

하수관거의 악취발생 원인인 황화수소는 하수가 혐기 상태로 되면서 황산염 - 환원세균(SRB)이 활성화되고, 하수 중의 황산이온이 황화물로 환원됨으로써 이루어지고, 이에 대한 화학식은 아래의 화학식 1과 같다.Hydrogen sulfide, which is the cause of odor of sewage pipes, is made by sulphate-reducing bacteria (SRB) as sewage becomes anaerobic, and by reducing sulfate ions in the sewage to sulfides, the chemical formula of which is represented by the following Chemical Formula 1.

Figure 112012012176947-pat00001
Figure 112012012176947-pat00001

상기 화학식 1에 기재된 바와 같이, 황산염 - 환원세균(SRB)이 황산이온을 이용하여 황화수소를 형성함으로써, 악취의 원인이 되는 황화수소를 발생시킨다. As described in Formula 1, the sulfate-reducing bacterium (SRB) forms hydrogen sulfide using sulfate ions, thereby generating hydrogen sulfide which causes odor.

그리고, 이러한 황화수소의 발생을 억제하기 위한 질산염을 이용하는 방법은 황산염 - 환원세균(SRB)이 황산이온보다는 질산염과 더 반응도가 높은 성질을 이용하는 것이다. 즉, 악취 대상 물질에 질산염을 투여하면, 황산염 - 환원세균은 최종전자수용체로서 황산이온보다 질산이온을 사용하므로 황화수소의 발생을 억제할 수 있다.In addition, the method of using nitrate to suppress the generation of hydrogen sulfide is to use the property that sulfate-reducing bacteria (SRB) is more reactive with nitrate than sulfate ions. In other words, when nitrate is administered to a malodorous substance, the sulfate-reducing bacterium uses nitrate ions rather than sulfate ions as the final electron acceptor, thereby suppressing the generation of hydrogen sulfide.

이러한, 질산이온 수용체인 질산염을 제조하기 위하여 기존의 질산나트륨, 질산철, 질산칼슘을 이용하지 않고, 굴 패각에 포함되어 있는 탄산칼슘(CaCO3)을 이용하여 질산염을 형성함으로써 제조비용을 절감할 수 있다.In order to manufacture the nitrate, which is the nitrate ion receptor, the manufacturing cost can be reduced by forming nitrate using calcium carbonate (CaCO 3 ) included in the oyster shell, without using conventional sodium nitrate, iron nitrate, and calcium nitrate. Can be.

본 발명에 의한 패각을 이용한 탈취용 질산염 제조방법은 패각을 세정하고 소성시킴으로써 불순물을 제거하고 패각을 분쇄하는 전처리 공정; 상기 전처리 공정에 의해 불순물이 제거된 패각을 질산수용액에 의해 반응시킴으로써 질산염 수용액을 얻는 질산염 수용액 생성 공정;및 상기 질산염 수용액을 농축시킨 후 냉각시킴으로써 질산염 결정분말을 회수하는 질산염 결정분말 생성 공정을 포함한다.Deodorizing nitrate manufacturing method using a shell according to the present invention is a pre-treatment step of removing impurities and crushing the shell by washing and firing the shell; A nitrate aqueous solution generation step of obtaining an nitrate aqueous solution by reacting the shell from which impurities are removed by the pretreatment step with an aqueous nitrate solution; and a nitrate crystal powder generation step of recovering the nitrate crystal powder by concentrating and cooling the nitrate aqueous solution. .

먼저, 상기 전처리 공정은 패각을 세정하고 소성시킴으로써 불순물을 제거하는 질산수용액 반응에 필요한 준비과정에 해당한다. 본 발명에 사용되는 패각은 탄산칼슘이 포함된 해양 생물체의 외피를 의미하며, 바람직하게는 해안에서 다량으로 폐기되는 굴 패각으로 구성될 수 있다.First, the pretreatment process corresponds to the preparation process required for the nitric acid solution reaction to remove impurities by washing and firing the shell. Shell used in the present invention refers to the shell of marine organisms containing calcium carbonate, and may preferably be composed of oyster shells that are discarded in large quantities at the coast.

상기 굴 패각은 염분, 유기물 및 각종 불순물이 섞여있기 때문에 질산수용액 반응에 적합하지 않은 상태로 존재한다. 따라서, 상기 전처리 공정은 일반 수돗물과 같은 세정액으로 수세 과정을 거친 후, 특별한 건조 과정없이 반응로에서 400 ~ 500℃의 온도로 60 ~ 120 분간 소성처리하는 것이 바람직하다.The oyster shell is present in a state that is not suitable for the nitric acid solution reaction because the salt, organic matter and various impurities are mixed. Therefore, after the pretreatment process is washed with a washing solution, such as general tap water, it is preferable to bake for 60 to 120 minutes at a temperature of 400 ~ 500 ℃ in a reactor without a special drying process.

이때, 본 발명의 전처리 공정에서는 반응로로서 1000℃ 이상의 가열로를 사용하지 않고 400 ~ 550℃의 전기로를 사용함으로써 굴 패각의 세정과정에서 포함되는 수분에 의한 반응로 내의 폭발현상을 방지할 수 있다. At this time, in the pretreatment process of the present invention, by using an electric furnace of 400 ~ 550 ℃ without using a heating furnace of 1000 ℃ or more as a reaction furnace it is possible to prevent the explosion phenomenon in the reactor by the water included in the oyster shell cleaning process. .

또한, 소성처리과정은 굴 패각에 포함되는 염분을 감소시킴에 있어서 매우 효율적이고, 그 결과는 아래의 표 1에 기재된 X선 형광분석법(X-Ray Flourescence Spectrometry, XRF)에 의한 분석결과에 나타나 있다.In addition, the firing process is very efficient in reducing the salinity contained in the oyster shell, and the results are shown in the analysis results by X-Ray Flourescence Spectrometry (XRF) described in Table 1 below. .

Figure 112012012176947-pat00002
Figure 112012012176947-pat00002

(L.I.* : Loss on Ignition)(LI * : Loss on Ignition)

상기와 같이, 세정 및 소성과정을 거치면, 그라인더를 이용하여 2 ~ 300㎛의 입도 크기로 패각을 분쇄함으로써 이후에서 이루어지는 질산수용액과의 반응이 원활하게 이루어지도록 한다.As described above, after the washing and firing process, the shell is crushed to a particle size of 2 ~ 300㎛ using a grinder to facilitate the reaction with the aqueous nitric acid solution made thereafter.

위와 같은, 전처리과정을 거친 결과, 굴 패각의 염분 및 불순물은 99% 이상 제거되었으며, 400℃ 이하의 온도에서는 소성이 균일하게 이루어지지 않아 차후의 분쇄공정에 어려움이 발생되며, 550℃ 이상의 온도에서는 처리비용을 상승시키므로 본 발명의 목적에 적합하지 않다.As a result of the above, as a result of the pretreatment process, more than 99% of the salinity and impurities of the oyster shell were removed, and since the calcination is not uniform at the temperature below 400 ° C, difficulties occur in the subsequent grinding process. Since the treatment cost is increased, it is not suitable for the purpose of the present invention.

상기 전처리 공정이 완료되면, 분쇄된 패각을 질산수용액에 의해 반응시킴으로써 질산염 수용액을 얻는 질산염 수용액 생성 공정을 실시한다. 상기 질산염 수용액 생성공정에 대한 화학식은 아래의 화학식 2와 같다.When the pretreatment step is completed, the nitrate aqueous solution generation step of obtaining a nitrate aqueous solution is performed by reacting the crushed shell with an aqueous solution of nitric acid. Chemical formula for the nitrate aqueous solution generation process is the same as the formula (2) below.

Figure 112012012176947-pat00003
Figure 112012012176947-pat00003

상기 질산염 수용액 생성공정은 60 ~ 68%의 질산을 7 ~ 12N(노르말농도)로 제조한 질산수용액을 굴 패각 분말에 10 ~ 55 mL/min의 속도로 투입하여 상온(25℃)에서 20 ~ 60분간 교반하여 여과시킴으로써 질산염 수용액을 얻는 것이 바람직하다.The aqueous solution of nitrate is produced by injecting nitric acid solution prepared at 60 to 68% of nitric acid at 7 to 12 N (normal concentration) into the oyster shell powder at a rate of 10 to 55 mL / min at 20 to 60 at room temperature (25 ° C). It is preferable to obtain the nitrate aqueous solution by stirring for a minute and filtering.

상기 공정에서 굴 패각 분말에 포함된 탄산칼슘이 질산 수용액과 반응하는 과정에서 이산화탄소가 발생하기 때문에 폭발의 위험이 있다. 따라서, 질산수용액의 농도를 7 ~ 12N로 제조하고 10 ~ 55 mL/min로 정량 투입하는 것이 바람직하다.In the process, there is a risk of explosion because carbon dioxide is generated during the reaction of calcium carbonate contained in the oyster shell powder with the nitric acid solution. Therefore, it is preferable to prepare the concentration of the aqueous nitric acid solution of 7 ~ 12N and quantitatively 10 ~ 55 mL / min.

질산수용액의 농도가 7N 이하이거나 10 mL/min 이하의 투입속도에서는 공정시간이 느려지게 되어 비경제적이다. 그리고, 질산수용액의 농도가 12N 이상이거나 55 mL/min 이상의 투입속도에서는 급격한 투입으로 인한 폭발의 위험성이 있다.If the concentration of the nitric acid solution is less than 7N or less than 10 mL / min, the process time is uneconomical. In addition, when the concentration of the nitric acid solution is 12N or more or more than 55 mL / min, there is a risk of explosion due to rapid addition.

그리고, 상기 반응공정에 의해 수득된 질산염 수용액은 수산화칼슘 또는 산화칼슘수용액과 같은 염기성 수용액으로 중화반응시켜 상기 질산염 수용액의 pH가 5 ~ 9가 되도록 한다. 상기 질산염 수용액의 5 ~ 9 pH는 하수관거의 악취제거용으로 사용되기 위한 적정 pH에 해당한다.In addition, the nitrate aqueous solution obtained by the reaction process is neutralized with a basic aqueous solution such as calcium hydroxide or calcium oxide aqueous solution so that the pH of the nitrate aqueous solution is 5-9. 5 to 9 pH of the nitrate aqueous solution corresponds to the appropriate pH to be used for odor removal of sewage pipe.

상기 반응공정에 의해 반응이 완료된 질산염 수용액에서 질산염(Ca(NO3)34H2O)을 제외한 나머지 성분을 제거하기 위하여 고액분리에 의해 여과를 시킴으로써 최종적인 질산염 수용액을 얻는다.The final nitrate aqueous solution is obtained by filtration by solid-liquid separation in order to remove the remaining components except nitrate (Ca (NO 3 ) 3 4H 2 O) in the nitrate aqueous solution is completed by the reaction process.

상기 질산염 수용액 생성공정이 완료되면, 수득된 질산염 수용액을 농축시킨 후 냉각시킴으로써 질산염 결정분말을 회수하는 질산염 결정분말 생성 공정을 실시한다.When the nitrate aqueous solution generation process is completed, the nitrate crystal powder production process is performed to recover the nitrate crystal powder by concentrating and cooling the obtained nitrate aqueous solution.

상기 질산염 결정분말을 얻기 위한 공정은 여과된 질산염 수용액을 50 ~ 100 ℃로 20 ~ 60분간 가열을 시킴으로써 농축한 후, 서서히 냉각시켜 결정분말을 회수하는 것이 바람직하다.In the process for obtaining the nitrate crystal powder, the filtered nitrate aqueous solution is concentrated by heating at 50 to 100 ° C. for 20 to 60 minutes, and then gradually cooled to recover the crystal powder.

상기 굴 패각 분말과 질산수용액의 반응으로부터 얻어진 혼합물의 결정화를 위하여 50 ~ 100℃의 열로 20 ~ 60분간 가열시킴으로써 질산염을 제외한 수용액을 기화시켜 농축시키고, 이를 서서히 냉각시킴으로써 결정을 회수한다. 가열온도가 50℃ 이하의 경우에는 결정화가 제대로 이루어지지 않으며, 생산수율도 낮아 효율성이 저하된다.For crystallization of the mixture obtained from the reaction of the oyster shell powder and the aqueous solution of nitric acid, by heating for 20 to 60 minutes with a heat of 50 ~ 100 ℃ by evaporating and concentrating the aqueous solution except nitrate, the crystals are recovered by slowly cooling. If the heating temperature is less than 50 ℃ crystallization is not performed properly, the production yield is low, the efficiency is lowered.

이렇게 1차로 농축시키는 과정을 수행하면, 질산염 농도가 약 76%인 질산염 결정분말을 수득할 수 있다. 농도가 76%인 질산염만으로도 하수관거 악취제거용 반응물로 사용하기에 적절하다.By performing this first concentration, a nitrate crystal powder having a nitrate concentration of about 76% can be obtained. Nitrate with a concentration of 76% alone is suitable for use as a reactant for removing odor from sewage pipes.

그리고, 질산염의 농도를 보다 증가시키기 위해서는 상기의 농축과정 및 냉각과정을 반복할 수 있다. 상기 농축과정 및 냉각과정의 반복에 의해 질산염의 농도를 99%까지 상승시킬 수 있다.In addition, in order to further increase the concentration of nitrate, the above-described concentration and cooling processes may be repeated. By repeating the concentration process and the cooling process, the concentration of nitrate can be increased to 99%.

이와 같은 본 발명의 기본적인 기술적 사상의 범주 내에서, 당업계의 통상의 지식을 가진 자에게 있어서는 다른 많은 변형이 가능함은 물론이고, 본 발명의 권리범위는 후술하는 특허청구범위에 기초하여 해석되어야 할 것이다.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, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. will be.

Claims (12)

패각을 이용하여 하수관거의 악취물질을 제거하기 위한 질산염을 제조하는 방법에 있어서,
패각을 세정하고 소성시킴으로써 불순물을 제거하는 전처리 공정;
상기 전처리 공정에 의해 불순물이 제거된 패각을 질산수용액에 반응시킴으로써 질산염 수용액을 얻는 질산염 수용액 생성 공정;및
상기 질산염 수용액을 농축시킨 후 냉각시킴으로써 질산염 결정분말을 회수하는 질산염 결정분말 생성 공정을 포함하는
패각을 이용한 탈취용 질산염 제조방법.
In the method of manufacturing a nitrate to remove the odorous substances of the sewage pipe using a shell,
A pretreatment step of removing impurities by washing and firing the shells;
A nitrate aqueous solution generation step of obtaining an aqueous nitrate solution by reacting a shell in which impurities are removed by the pretreatment step with an aqueous nitrate solution; and
Concentrating the nitrate aqueous solution and then cooling to recover the nitrate crystal powder comprising the step of producing a nitrate crystal powder
Deodorizing nitrate manufacturing method using shell.
제1항에 있어서,
상기 전처리 공정은
상기 소성과정에 의해 불순물이 제거된 패각을 분쇄하여 패각 분말을 생성하는 분쇄공정을 포함하는
패각을 이용한 탈취용 질산염 제조방법.
The method of claim 1,
The pretreatment process
And a pulverizing process of pulverizing the shell from which impurities are removed by the firing process to produce shell powder.
Deodorizing nitrate manufacturing method using shell.
제2항에 있어서,
상기 분쇄공정은
상기 패각 분말의 입도가 2 ~ 300 ㎛가 되도록 상기 패각을 분쇄하는
패각을 이용한 탈취용 질산염 제조방법.
The method of claim 2,
The grinding process is
Grinding the shell so that the particle size of the shell powder is 2 ~ 300 ㎛
Deodorizing nitrate manufacturing method using shell.
제1항에 있어서,
상기 전처리공정은
상기 패각을 세정한 후, 400 ~ 500℃의 온도로 소성처리하는
패각을 이용한 탈취용 질산염 제조방법.
The method of claim 1,
The pretreatment process
After washing the shell, firing at a temperature of 400 ~ 500 ℃
Deodorizing nitrate manufacturing method using shell.
제1항에 있어서,
상기 질산염 수용액 생성공정은
상기 패각에 7 ~ 12N의 질산수용액을 10 ~ 55 mL/min의 속도로 투입하여 20 ~ 60분간 교반하는
패각을 이용한 탈취용 질산염 제조방법.
The method of claim 1,
The nitrate aqueous solution generation process
7 ~ 12N nitric acid solution to the shell at a rate of 10 ~ 55 mL / min and stirred for 20 to 60 minutes
Deodorizing nitrate manufacturing method using shell.
제5항에 있어서,
상기 질산염 수용액 생성공정은
상온에서 실시되는
패각을 이용한 탈취용 질산염 제조방법.
The method of claim 5,
The nitrate aqueous solution generation process
Conducted at room temperature
Deodorizing nitrate manufacturing method using shell.
제1항에 있어서,
상기 질산염 수용액 생성공정은
생성된 질산염 수용액과 염기성 수용액을 서로 중화반응시키는
패각을 이용한 탈취용 질산염 제조방법.
The method of claim 1,
The nitrate aqueous solution generation process
Neutralizing the produced aqueous nitrate solution and basic aqueous solution
Deodorizing nitrate manufacturing method using shell.
제7항에 있어서,
상기 질산염 수용액은
상기 중화반응에 의해 5 ~ 9 pH를 가지는
패각을 이용한 탈취용 질산염 제조방법.
The method of claim 7, wherein
The nitrate aqueous solution is
Having a pH of 5 to 9 by the neutralization reaction
Deodorizing nitrate manufacturing method using shell.
제7항에 있어서,
상기 염기성 수용액은
수산화칼슘 또는 산화칼슘수용액인
패각을 이용한 탈취용 질산염 제조방법.
The method of claim 7, wherein
The basic aqueous solution is
Calcium hydroxide or calcium oxide
Deodorizing nitrate manufacturing method using shell.
제1항에 있어서,
상기 질산염 수용액 생성공정은
상기 질산염 수용액 이외의 성분을 여과하는 여과공정을 포함하는
패각을 이용한 탈취용 질산염 제조방법.
The method of claim 1,
The nitrate aqueous solution generation process
Filtration process of filtering components other than the said nitrate aqueous solution
Deodorizing nitrate manufacturing method using shell.
제1항에 있어서,
상기 질산염 결정분말 생성 공정은
상기 질산염 수용액을 50 ~ 100℃의 온도로 20 ~ 60분간 가열한 후, 냉각시킴으로써 질산염 결정분말을 회수하는
패각을 이용한 탈취용 질산염 제조방법.
The method of claim 1,
The nitrate crystal powder production process
Recovering the nitrate crystal powder by heating the aqueous nitrate solution at a temperature of 50 to 100 ° C. for 20 to 60 minutes and then cooling the solution.
Deodorizing nitrate manufacturing method using shell.
제11항에 있어서,
상기 질산염 결정분말 생성 공정은
상기 가열 및 냉각 공정을 다수회 반복 실시하는
패각을 이용한 탈취용 질산염 제조방법.
12. The method of claim 11,
The nitrate crystal powder production process
Repeating the heating and cooling process a number of times
Deodorizing nitrate manufacturing method using shell.
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Cited By (1)

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KR102038445B1 (en) * 2019-06-17 2019-10-30 황길택 Manufacturing method of high purity 1,2-hexanediol having non-odor change property

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KR20010054343A (en) * 1999-12-06 2001-07-02 박정수 Admixure synthesizing method for construction materials by using oyster shell
KR20010106574A (en) * 2000-05-22 2001-12-07 이혜경 Biofilter for purification of waste gas
KR20020083715A (en) * 2001-04-30 2002-11-04 김용곤 Multi-functional material emitting far-infrared ray in aqueous phase and the use thereof
KR100523245B1 (en) * 2002-05-03 2005-10-24 전병철 Deodorant Polyethylene Resin Composition for Package

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KR20010054343A (en) * 1999-12-06 2001-07-02 박정수 Admixure synthesizing method for construction materials by using oyster shell
KR20010106574A (en) * 2000-05-22 2001-12-07 이혜경 Biofilter for purification of waste gas
KR20020083715A (en) * 2001-04-30 2002-11-04 김용곤 Multi-functional material emitting far-infrared ray in aqueous phase and the use thereof
KR100523245B1 (en) * 2002-05-03 2005-10-24 전병철 Deodorant Polyethylene Resin Composition for Package

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102038445B1 (en) * 2019-06-17 2019-10-30 황길택 Manufacturing method of high purity 1,2-hexanediol having non-odor change property

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