KR20150108121A - Process for Annulling Deliquescence of Calcium Nitrate in Solid Fuel Compound - Google Patents
Process for Annulling Deliquescence of Calcium Nitrate in Solid Fuel Compound Download PDFInfo
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
- C10L5/447—Carbonized vegetable substances, e.g. charcoal, or produced by hydrothermal carbonization of biomass
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
- C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/34—Other details of the shaped fuels, e.g. briquettes
- C10L5/36—Shape
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/24—Mixing, stirring of fuel components
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/28—Cutting, disintegrating, shredding or grinding
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
Description
본 발명은 질산칼슘의 조해성(潮解性)을 해소한 고체연료화합물의 제조방법에 관한 것이다.The present invention relates to a method for producing a solid fuel compound in which the deliquescence of calcium nitrate is solved.
고체연료 조성물은 천연 숯이 산림자원의 보호로 공급이 제한되는 상황에서 개발된 대체품이다. 고체연료조성물은 간벌 등으로 폐기되는 잡목이나 야자껍질, 톱밥 등을 탄화시킨 숯 분말을 주재로 하므로 자원재활용과 원가 면에서 유리하다.The solid fuel composition is a substitute developed in a situation where natural charcoal is limited in supply due to the protection of forest resources. The solid fuel composition is advantageous from the viewpoint of resource recycling and cost because it is made mainly of charcoal powder which is carbonized by bark, coconut shell, sawdust and the like.
고체연료 조성물은 숯가루를 주재로 하고 이에 조연제, 점화제, 바인더, 명반, 벤토나이트, 제오라이트 등이 혼합된다. 점화제는 초석이 널리 사용되고 있으며, 바인더는 호화전분이 일반적이고 나머지 성분들은 연소 시 또는 연소 후 재가 분산 또는 비산되는 것을 저감시키는 역할을 한다. The solid fuel composition is based on charcoal powder and is blended with a combustion agent, an igniter, a binder, alum, bentonite, zeolite and the like. Corundum is widely used in corundum, the binder is a general starch, and the other components reduce the scattering or scattering of ash during or after combustion.
인조 고체연료 개발의 관건은 점화가 용이하고 연소시간이 충분히 지속되어야 하며 특히, 조연제에서 인체에 해로운 유독가스가 발생하지 않아야 한다는 조건을 충족시켜야 한다. 그간 다양한 고체연료 조성물이 개발되어 왔으나 대부분 실용화되지 못하고 있다. 다만 조연제로 바륨화합물을 사용한 고체 연료조성물 또는 착화탄이 널리 사용되고 있으나 연소 시 발생하는 바륨가스의 유해성 문제가 남는다. The key to the development of artificial solid fuels is that they must be easy to ignite and to have a sufficiently long burning time, especially in the presence of toxic gases harmful to the human body. Various solid fuel compositions have been developed in the past, but most of them have not been put to practical use. However, solid fuel compositions or ignition coals using a barium compound as a combustion stabilizer are widely used, but the problem of harmfulness of barium gas generated in combustion remains.
본 발명과 관련된 선행기술로 발명특허 제 583937호인 ‘고체연료 조성물’이 알려진 바 있다. 이 선행발명은 인체에 무해하며 원가가 낮은 조연제를 제공하기 위한 기술로서 조연제인 질산바륨을 질산칼슘으로 대체한 기술이다. As a prior art related to the present invention, the 'solid fuel composition' of the invention No. 583937 is known. This prior art is a technique for providing a low-cost low-cost smelting agent that is harmless to human body and substituting calcium nitrate for barium nitrate, which is a stabilizer.
여기서 선택한 질산칼슘(Calcium nitrate)는 융점이 50℃로서 함수율이 높아 고체연료의 조연제로 사용하기가 부적합하므로 이를 미세하게 분말화한 후 저온에서 건조시킨 후 함수율이 충분히 낮아진 상태에서 다른 소재들과 혼합하는 방법을 택하고 있다. 하지만 고체연료를 제조하는 경우 포장을 완벽하게 밀봉하기가 어려우므로 유통과정이 길어지거나 장기 보관하는 경우 질산칼슘의 조해성으로 인하여 발화 및 연소기능이 현저히 감소될 뿐만 아니라 그 형태조차 유지할 수 없는 상태가 되는 문제점이 있다.The selected calcium nitrate has a high melting point of 50 ° C and is not suitable for use as a smelting aid for solid fuel. Therefore, it is necessary to finely pulverize it and dry it at a low temperature, and then mixed with other materials . However, since it is difficult to completely seal the package when producing solid fuel, when the circulation process is prolonged or stored for a long period of time, the ignitability and combustion function are remarkably reduced due to the deliquescence of calcium nitrate, There is a problem.
본 발명은 이러한 문제점에 착안하여 조연제인 질산칼슘의 조해성을 개선하여 유통과정에서 발화성과 연소성이 유지되면서 장기간 성형상태를 온전히 유지할 수 있는 고체연료화합물을 제공하는데 목적이 있다.It is an object of the present invention to provide a solid fuel compound capable of improving the deliquescence of calcium nitrate, which is a stabilizing agent, to keep the pyrolytic and combustible properties in a circulation process and to maintain the molding state for a long time.
본 발명은 조연제인 질산칼슘의 점화성 및 연소성을 유지하면서도 조해성을 해소하는 물질과 반응시키며, 투입되는 물질의 최적 조성비와 반응시간을 찾아내는데 주안을 두고 있다. The present invention focuses on finding the optimum composition ratio of the input material and the reaction time while reacting with the substance which resolves the deliquescence while maintaining the ignitability and combustibility of the calcium nitrate as the stabilizer.
본 발명에 사용되는 물질과 분자식은 아래와 같다.The materials and molecular formulas used in the present invention are as follows.
Calcium Nitrate. Ca(N0₃)₂ Calcium Nitrate. Ca (N0₃) ₂
Sodium Nitrate. NaN0₃ Sodium Nitrate. NaN03
Sodium Carbonate. Na₂CO₃ 또는 Calcium Carbonate. CaCO₃ Sodium Carbonate. Na2CO3 or Calcium Carbonate. CaCO3
이상의 물질을 적정 성분비로 혼합하여 반응조에서 가열 및 교반하면 고열의 화합반응을 거쳐 단단한 고체로 응결된다. 이를 미세하게 분쇄하고 숯가루와 소량의 물을 혼합한 다음 성형하면 고체연료가 완성된다.When the above materials are mixed in the proper proportions and heated and stirred in a reaction tank, the mixture is subjected to a high-temperature combination reaction and solidified into a solid. This is finely crushed, mixed with charcoal powder and a small amount of water, and then molded to complete a solid fuel.
본 발명에 의하여 생성된 고체연료화합물은 대기 중에 장기간 노출되어도 습기를 흡수하여 녹는 현상이 없다. 또한 산성이고 중금속을 함유한 다른 발화제나 조연제가 연소 시에 많은 인체에 유해한 가스를 방출하는 것과 달리 칼슘과 나트륨만 함유하고 있고 약알칼리성을 띠고 있어서 인체에 유해성이 없다. The solid fuel compound produced by the present invention does not melt and absorb moisture even when exposed to the atmosphere for a long period of time. Other acidic, heavy metal-containing or ignitable fumes release many harmful gases to the human body during combustion. Containing only calcium and sodium, they are weakly alkaline and not harmful to human body.
본 발명은 국내에서 생산할 수 있어서 경제성이 높을 뿐만 아니라 초기 발화를 위해 별도의 발화제를 사용하지 않고 숯가루에 혼합하여 고체연료를 만드는데 사용될 수 있다. The present invention is not only economical because it can be produced domestically, but also can be used for making solid fuel by mixing with charcoal powder without using any other burning agent for initial ignition.
본 발명의 조성물은 조해성을 개선하였으므로 소량의 물로 용해한 후 다시 건조하여 고체연료를 성형하였을 경우에도 조해성이 나타나지 않는다. Since the composition of the present invention improves the deliquescence, even if the solid fuel is molded by dissolving in a small amount of water and drying again, the deliquescence does not appear.
본 발명에 사용되는 물질은 칼슘니트레이트, 소디움니트레이트 그리고 소디움카보네이트 또는 칼슘카보네이트 중의 하나이다. The material used in the present invention is one of calcium nitrate, sodium nitrate and sodium carbonate or calcium carbonate.
칼슘니트레이트는 인체에 무해하며 우수한 조연제로 사용된다. 소디움니트레이트는 가연성 물질이 가해지면 폭발하는 성질을 가지는데 고체연료에 불을 붙였을 때 즉시 착화되는 발화제로 사용된다. 칼슘니트레이트는 조해성이 있지만 한편으로는 바인더 역할을 하므로 화합물의 응결을 촉진시켜주는 작용도 한다. Calcium nitrate is harmless to the human body and is used as a good smelting agent. Sodium nitrate has the property of exploding when a combustible material is added, which is used as an ignitant to ignite immediately when the solid fuel is ignited. Calcium nitrate is a deliquescent compound, but on the other hand it acts as a binder, thus accelerating the condensation of the compound.
소디움 카보네이트와 칼슘 카보네이트는 반응을 촉진할 뿐만 아니라 발화 및 연소를 촉진해준다. 소디움 카보네이트는 칼슘 카보네이트보다 가격이 1/3정도로 저렴하고, 칼슘카보네이트는 연소 시 고열을 발생시킨다. Sodium carbonate and calcium carbonate not only promote the reaction but also promote ignition and combustion. Sodium carbonate is about one-third less expensive than calcium carbonate, and calcium carbonate generates high heat when it is burned.
본 발명의 원료 중 하나인 질산칼슘(Calcium Nitrate)은 솔루션인 경우 SG 1.45~1.50, 4수염[Ca(N0₃)₂·4H₂O], 무수염[Ca(N0₃)₂] 중 어느 것도 가능하나 무수염이 가장 조해성을 해소하는데 유리하다. Calcium nitrate, one of the raw materials of the present invention, can be any of SG 1.45 to 1.50, 4 hydrates [Ca (N0₃) ₂ · 4H₂O] and anhydrous salts [Ca (N0₃) ₂] This is most advantageous in solving the delusion.
이상의 물질을 반응시킬 때 적정한 성분비는 아래와 같다. 다만, 성분비는 중량부이며, 순수 Ca(N0₃)₂ 상태로 계산한 것이다. When the above materials are reacted, the appropriate composition ratios are as follows. However, the composition ratio is calculated in terms of pure Ca (N0₃) ₂ in parts by weight.
Ca(N0₃)₂: 46% , NaNO₃: 24%, Na₂CO₃: 30% 또는Ca (N0₃) ₂: 46%, NaNO₃: 24%, Na₂CO₃: 30% or
Ca(N0₃)₂: 47%, NaNO₃: 24.34%, CaCO₃: 28.66% Ca (NO3) ₂ 47%, NaNO3 24.34%, CaCO3 28.66%
이상의 성분비로 반응시킬 때의 반응식은 아래와 같다. The reaction formula for the reaction in the above proportions is as follows.
Ca(N0₃)₂+ NaNO₃+ Na₂CO₃→ Ca(N0₃)₂·NaN0₃·Na₂O + CO₂↑Ca (N03) ₂ + NaNO3 + Na2CO3 → Ca (N03) ₂ · NaN03 · Na2O + CO2 ↑
Ca(N0₃)₂+ NaNO₃+ CaCO₃→ Ca(N0₃)₂·NaN0₃·CaO + CO₂↑Ca (N03) ₂ + NaNO3 + CaCO3 → Ca (N03) ₂ · NaN03 · CaO + CO2 ↑
위 반응식에서 알 수 있는 바와 같이 탄산 칼슘과 탄산나트륨은 산에 용해되어서 CO₂를 발생시킨다. 여기서 관찰하게 되는 것은 화합물에서 Ca의 함량이 높아지면 열량이 증가함과 동시에 조해성도 높아진다는 것이다. As can be seen from the above equation, calcium carbonate and sodium carbonate dissolve in the acid to generate CO2. What we observe here is that as the content of Ca in the compound increases, the calories increase and the calmness increases.
이상의 반응형성과 조연제로서 함량이 가장 적합한 비율이며 또한 반응성을 용이하게 하기 위해서 원료 중 탄산나트륨, 질산나트륨은 분말상태로도 반응이 가능하나 교반이 잘 이루어지게 하기 위하여 가열하여 용해시켜서 사용하는 것이 바람직하다. 액상의 탄산나트륨과 질산나트륨에 질산칼슘과 탄산칼슘을 반응조에서 온도를 120~150°C로 유지하면서 교반하면 수분은 증발되어 슬러지 상태로 변하면서 온도가 230~250°C로 급상승하다가 서서히 하강하면서 반응이 종료된다. 이때 매우 단단한 결정상태의 고체연료화합물을 얻는다.In order to facilitate the reactivity, sodium carbonate and sodium nitrate in the raw material can be reacted in the form of powder, but it is preferable to use them by heating and dissolving in order to make stirring well Do. When sodium carbonate and sodium carbonate are mixed with liquid sodium carbonate and calcium carbonate while maintaining the temperature at 120 ~ 150 ° C in the reaction tank, the water is evaporated and changed into sludge, and the temperature rises rapidly to 230 ~ 250 ° C, Lt; / RTI > At this time, a solid solid fuel compound in a very hard crystalline state is obtained.
반응의 소요시간은 1시간 내지 1시간 20분이며 결정 상태를 325mesh로 분쇄하여 고체연료화합물을 완성한다. 완성된 고체연료화합물 적량을 숯가루에 투입한 후 가수하여 고체연료를 성형한다. 성형된 고체연료를 건조시키면 건조 상태가 오래 지속되고 장기간 대기 중에 노출되어도 조해작용이 일어나지 않는다. The time required for the reaction is from 1 hour to 1 hour and 20 minutes, and the crystalline state is pulverized to 325mesh to complete the solid fuel compound. The solid fuel composition is filled into a charcoal powder and then mixed to form a solid fuel. When the molded solid fuel is dried, the drying state is long, and even if exposed to the atmosphere for a long period of time, the deterioration does not occur.
필요에 따라 발화제인 소디움니트레이트를 사용하지 않는 경우도 있는데 이때는 고체연료 생산자가 별도로 발화제를 투여하여 고체연료를 제조한다. 이때 적정한 조성비 중량부는 Calcium Nitrate: 49%, Sodium Carbonate 또는 Calcium Carbonate 51%이다. In some cases, sodium nitrate, which is an ignition agent, is not used. In this case, the solid fuel producer separately injects a burning agent to produce a solid fuel. In this case, the proper composition ratio is 49% of Calcium Nitrate, 51% of Sodium Carbonate or Calcium Carbonate.
실시예 1. Example 1.
Calcium Nitrate 35%, Sodium Nitrate 40%, Sodium Carbonate 또는 Calcium Carbonate 25% 중량부를 반응조에서 120~150°C로 교반하여 1시간 경과 후 결정상태의 고체연료화합물을 얻었다. 이를 숯가루와 함께 가수하여 고체연료를 성형하였다.35% of Calcium Nitrate, 40% of Sodium Nitrate, 25% of Sodium Carbonate or 25% of Calcium Carbonate were stirred at 120 to 150 ° C in the reaction tank to obtain a solid fuel compound in a crystalline state after 1 hour. This was mixed with charcoal powder to form solid fuel.
대기 중에 20일 간 노출하였더니 조해성은 거의 없었으나 착화가 다소 느렸고, 착화한 후 측정해보니 발열량과 발열시간이 보통의 고체연료보다 3% 감소했다. After 20 days of exposure in the atmosphere, there was little compromise, but the ignition was somewhat slower and when measured after ignition, the calorific value and the heating time were reduced by 3% from the normal solid fuel.
실시예 2.Example 2.
Calcium Nitrate 45%, Sodium Nitrate 30%, Sodium Carbonate 또는 Calcium Carbonate 25% 중량부를 반응조에서 120~150°C로 교반하여 1시간 경과 후 결정상태의 고체연료화합물을 얻었다. 이를 숯가루와 함께 가수하여 고체연료를 성형하였다.45% of Calcium Nitrate, 30% of Sodium Nitrate, 25% of Sodium Carbonate or 25% of Calcium Carbonate were stirred at 120 to 150 ° C in the reaction tank and after 1 hour, a solid state fuel compound was obtained. This was mixed with charcoal powder to form solid fuel.
대기 중에 20일 간 노출하였더니 착화는 쉽게 이루어졌으나 착화한 후 측정해보니 발열량과 발열시간이 보통의 고체연료보다 4%가 증가했으나 조해성이 기대치를 상회하였다. After 20 days of exposure in the atmosphere, the ignition was easy, but when measured after ignition, the calorific value and the heating time increased 4% over the normal solid fuel, but the delusion exceeded the expectation.
실시예 3.Example 3.
Calcium Nitrate 40~50%, Sodium Nitrate 35~22%, Sodium Carbonate 또는 Calcium Carbonate 25~28% 중량부를 성분비의 범위 내에서 다양하게 변화시키면서 반응조에서 120~150°C로 교반하여 1시간 경과 후 결정상태의 고체연료화합물을 얻은 후 숯가루와 함께 가수하여 고체연료를 성형하였다.The mixture was stirred at 120 to 150 ° C in a reaction tank while varying 40 to 50% of calcium nitrate, 35 to 22% of sodium nitrate, and 25 to 28% of sodium carbonate or 25 to 28% Of the solid fuel compound, and then mixed with the charcoal powder to form a solid fuel.
대기 중에 20일 간 노출하였더니 조해성이나 착화시간, 발열량, 발열시간이 전체적으로 적정하여 보통의 고체연료와 균등한 정도가 되었다.When exposed to the atmosphere for 20 days, comprehensibility, ignition time, calorific value, and heat generation time were totally adequate, which was equivalent to normal solid fuel.
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