KR102271800B1 - Preparation method of glycerol-impregnated modified hybrid coal - Google Patents
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Abstract
본 발명은 바이오디젤 공정에서 부산물로 발생되는 글리세롤과 황산 혼합액을 저급탄에 함침시켜 글리세롤의 휘발온도 이상에서 석탄의 반탄화 과정을 진행하여도 석탄에 함침된 글리세롤이 휘발되는 것을 방지하여 발열량이 더욱 향상된 하이브리드 석탄을 제조할 수 있는 글리세롤이 함침된 개질 하이브리드 석탄의 제조방법에 관한 것이다.
본 발명은, 석탄을 준비하는 단계(S10)와; 글리세롤과 황산용액을 혼합하는 단계(S20)와; 글리세롤 황산 혼합액에 석탄을 함침시키는 단계(S30)와; 글리세롤-황산 혼합액이 함침된 석탄을 건조시키는 단계(S40)와; 건조된 석탄을 질소조건 하에서 반탄화시키는 단계(S50);를 포함한다. The present invention impregnates the low-grade coal with a mixed solution of glycerol and sulfuric acid generated as a by-product in the biodiesel process to prevent the glycerol impregnated in the coal from volatilizing even when the coal is torrefied at a temperature higher than the volatilization temperature of glycerol. It relates to a method for producing a modified hybrid coal impregnated with glycerol capable of producing an improved hybrid coal.
The present invention, preparing the coal (S10) and; Mixing the glycerol and sulfuric acid solution (S20) and; Impregnating the coal in the glycerol sulfuric acid mixture (S30) and; drying the coal impregnated with the glycerol-sulfuric acid mixture (S40); and torrefied the dried coal under nitrogen condition (S50).
Description
본 발명은 하이브리드 석탄 및 그의 제조 방법에 관한 것으로, 더욱 상세하게는 바이오디젤 공정에서 부산물로 발생되는 글리세롤과 황산 혼합액을 저급탄에 함침시켜 글리세롤의 휘발온도 이상에서 석탄의 반탄화 과정을 진행하여도 석탄에 함침된 글리세롤이 휘발되는 것을 방지하여 발열량이 더욱 향상된 하이브리드 석탄을 제조할 수 있는 글리세롤이 함침된 개질 하이브리드 석탄의 제조방법에 관한 것이다.The present invention relates to hybrid coal and a method for producing the same, and more particularly, by impregnating a low-grade coal with a mixed solution of glycerol and sulfuric acid generated as a by-product in the biodiesel process, even if the torrefaction process of coal is performed above the volatilization temperature of glycerol. It relates to a method for producing a modified hybrid coal impregnated with glycerol, capable of producing hybrid coal with a further improved calorific value by preventing the glycerol impregnated in the coal from volatilizing.
최근 지속적으로 상승하는 유가와 원자력 에너지의 안정성에 대한 불신 등의 원인으로 에너지원으로서의 석탄에 대한 관심이 다시 고조되고 있다. 그러나 석탄은 화석연료 중 이산화탄소 발생량이 가장 많은 것으로서 지구 온난화 문제를 감안하면 경쟁력이 취약한 에너지원인 셈이다. 따라서 현재 에너지원으로서 세계적으로 이슈화 되고 있는 것 중에 신재생에너지의 이용 및 보급을 들 수 있는데, 이는 기존의 석유, 석탄 등 화석연료에 비하여 이산화탄소의 배출이 저감되어 지구온난화 및 기후변화에 대응할 수 있는 에너지원으로서 각광받고 있기 때문이다. 그러나 국내에서는 아직까지 태양광 또는 풍력 등의 신재생에너지원을 발전용 또는 난방용으로 사용하는 경우에는 화석연료와 비교하면 발전단가 등의 차이로 인하여 획기적인 이용 및 보급이 제한적인 상황이었다.Recently, interest in coal as an energy source is rising again due to reasons such as continuously rising oil prices and distrust in the stability of nuclear energy. However, coal produces the largest amount of carbon dioxide among fossil fuels, so it is a weak energy source considering global warming. Therefore, one of the current global issues as an energy source is the use and dissemination of new and renewable energy, which reduces carbon dioxide emissions compared to the existing fossil fuels such as petroleum and coal, so that it can respond to global warming and climate change. Because it is in the spotlight as an energy source. However, in the case of using renewable energy sources such as solar power or wind power for power generation or heating in Korea, epoch-making use and dissemination were limited due to the difference in power generation cost compared to fossil fuels.
우리나라도 화석연료의 고갈과 더불어 국제조약인 기후변화협약 대응에 따른 온실가스 감축이 대두되면서 신재생에너지 의무할당제가 거론되기 시작한 이래 2012년부터 신재생에너지 의무할당제[Renewable Portfolio Standard(RPS)]가 도입됨으로써 에너지 사업자들에게는 부담으로 작용하는 것이 사실이다. 이에 따라 발전사에서는 석탄의 이산화탄소 발생을 감축시키는 노력으로 석탄가스화복합발전[Integrated Gasification Combined Cycle(IGCC)] 및 바이오매스 혼소 등을 시도하고 있지만, IGCC는 기존의 석탄 화력 발전시설을 이용할 수 없고, 1기당 약 1조 3천억원 규모의 막대한 건설비용이 필요하며, 이산화탄소 처리를 위하여 이산화탄소 포집 및 저장설비[Carbon Capture and Storage(CCS)]를 추가로 설치해야 하는 기술로서 경제적인 부담이 매우 크다. 그리고 바이오매스 혼소의 경우에는 석탄에 비하여 상대적으로 낮은 발열량의 바이오매스를 연소함에 따른 발전효율 감소 등의 문제점을 안고 있다.In Korea, as well as the depletion of fossil fuels and the rise of greenhouse gas reduction in response to the international treaty on climate change, the mandatory quota system for renewable energy began to be discussed. Since 2012, the mandatory quota system for renewable energy [Renewable Portfolio Standard (RPS)] has been introduced. It is true that the introduction puts a burden on energy providers. Accordingly, power generation companies are attempting Integrated Gasification Combined Cycle (IGCC) and biomass co-firing as an effort to reduce carbon dioxide emissions from coal, but IGCC cannot use existing coal-fired power generation facilities. It requires a huge construction cost of about 1.3 trillion won per unit, and it is a technology that additionally needs to install a carbon capture and storage facility [Carbon Capture and Storage (CCS)] for carbon dioxide treatment, which is very economically burdensome. And in the case of biomass co-firing, there is a problem such as a decrease in power generation efficiency due to combustion of biomass having a relatively low calorific value compared to coal.
또한, 최근 역청탄과 같은 고급탄의 공급이 불안정해지면서 발전사에서도 저급탄을 불가피하게 이용할 수밖에 없는 상황인데, 저급탄의 높은 수분 함량 때문에 저급탄을 혼소할 경우 발전성능을 저해하는 결과를 초래하게 되고, CO2 발생량이 고급탄에 비해 20%이상 증가하는 문제가 발생한다. 그러므로 이러한 저급탄이 전체 석탄 매장량의 약 50%를 차지하는 것을 고려하면 저급탄의 고부가가치화는 저급탄을 효율적으로 이용하기 위해서라도 반드시 필요한 기술이다.In addition, as the supply of high-grade coal such as bituminous coal has recently become unstable, power generation companies inevitably have no choice but to use low-grade coal. Due to the high moisture content of low-grade coal, co-firing low-grade coal results in impaired power generation performance. , there is a problem that the amount of CO2 generated increases by more than 20% compared to high-grade coal. Therefore, considering that such low-grade coal occupies about 50% of the total coal reserves, the high value-added of low-grade coal is a necessary technology for efficient use of low-grade coal.
이에 따라 저급탄을 단순건조, 열수를 이용한 고압건조, 또는 고온의 유기용매를 이용한 건조 등의 저급탄 건조에 관한 연구가 활발히 진행 중에 있지만, 공정이 복잡하다는 문제점 및 건조 후에 수분이 재흡착되어 발전효율이 떨어지는 문제점을 여전히 안고 있다. 또한, 건조된 석탄에 수분이 재흡착되면서 자연발화가 발생하고 이로 인해 저장된 석탄이 손실되는 문제점도 있다.Accordingly, research on low coal drying such as simple drying of low coal, high pressure drying using hot water, or drying using high temperature organic solvent is being actively conducted, but there is a problem that the process is complicated and moisture is re-adsorbed after drying to generate power. There is still the problem of low efficiency. In addition, there is a problem in that spontaneous ignition occurs as moisture is re-adsorbed to the dried coal, and thus stored coal is lost.
또한, 바이오매스 건류 생성물 중의 타르를 석탄에 부착시키는 방법으로 저급탄을 고품질로 개질하는 기술도 공지되어 있으나, 수분의 재흡착에 대한 평가는 이루어지지 않았다. In addition, a technique for high-quality reforming of low-grade coal by a method of attaching tar in a biomass dry distillation product to coal is also known, but the re-adsorption of moisture has not been evaluated.
한편, 최근에 바이오디젤 생산공정에서 부산물로 얻어지는 글리세롤을 자원화하는 기술에도 관심이 집중되고 있으나, 이러한 글리세롤을 재활용하여 고부가가치 자원으로 전환하기 위해서는 원하는 화합물에 대한 높은 수율을 확보하여야 하는 어려움이 있으며, 고압의 반응조건이 필요하여 공정비용이 비싸다는 단점이 있다. 따라서 특정 화합물에 대한 높은 수율이 요구되지 않고, 고비용의 생산공정을 필요로 하지 않는 바이오디젤 생산공정에 서 부산물로 얻어지는 글리세롤을 그대로 자원화 시키고자 하는 시도가 있었는바, 유기성 슬러지와 폐글리세롤을 혼합 및 가열 건조하여 고형 연료를 제조한 예가 공지되어 있으나, 이는 유기성 슬러지와 폐글리세롤을 단순히 혼합 및 가열건조하여 성형한 것으로 건조시 함수율에 따른 발열량만 고려했을 뿐, 건조 후 수분의 재흡착에 대한 평가와 표면의 소수성에 대한 평가는 역시 이루어지지 않았다.On the other hand, recently, attention has been focused on the technology of recycling glycerol obtained as a by-product in the biodiesel production process as a resource, but in order to recycle such glycerol and convert it into a high value-added resource, there is a difficulty in securing a high yield of the desired compound, There is a disadvantage in that the process cost is high because a high-pressure reaction condition is required. Therefore, an attempt has been made to recycle glycerol obtained as a by-product in the biodiesel production process that does not require high yield for specific compounds and does not require an expensive production process. An example of manufacturing a solid fuel by heating and drying is known, but this is formed by simply mixing and heating and drying organic sludge and waste glycerol, and only considers the calorific value according to the moisture content during drying. The hydrophobicity of the surface was also not evaluated.
이에 따라 한국특허등록 제10-1210928호에서 석탄에 글리세롤을 함침시켜 고발열량의 하이브리드 석탄을 제조한 바 있으나, 그러나 저급탄의 발열량을 증가시키기 위해서 반탄화 공정이 필요하지만 반탄화 공정이 글리세롤의 휘발온도 이상에서 이루어지기 때문에 단순히 글리세롤을 건조할 수밖에 없었다.Accordingly, in Korea Patent Registration No. 10-1210928, coal is impregnated with glycerol to produce hybrid coal with high calorific value. However, in order to increase the calorific value of low-grade coal, a torrefaction process is required, but the torrefaction process requires volatilization of glycerol. Because it was done above the temperature, there was no choice but to simply dry the glycerol.
본 발명이 해결하고자 하는 과제는 바이오디젤 공정에서 부산물로 발생되는 글리세롤과 황산 혼합액을 저급탄에 함침시켜 글리세롤의 휘발온도 이상에서 석탄의 반탄화 과정을 진행하여도 석탄에 함침된 글리세롤이 휘발되는 것을 방지하여 발열량이 더욱 향상된 하이브리드 석탄을 제조할 수 있는 글리세롤이 함침된 개질 하이브리드 석탄의 제조방법을 제공하는 데 있다.The problem to be solved by the present invention is that the glycerol impregnated in the coal is volatilized even when the coal is torrefied at a temperature higher than the volatilization temperature of glycerol by impregnating the low-grade coal with a mixture of glycerol and sulfuric acid generated as a by-product in the biodiesel process An object of the present invention is to provide a method for producing a modified hybrid coal impregnated with glycerol capable of producing hybrid coal with a further improved calorific value by preventing it.
본 발명에 따른 글리세롤이 함침된 개질 하이브리드 석탄의 제조방법은, 석탄을 준비하는 단계(S10)와; 글리세롤과 황산용액을 혼합하는 단계(S20)와; 글리세롤 황산 혼합액에 석탄을 함침시키는 단계(S30)와; 글리세롤-황산 혼합액이 함침된 석탄을 건조시키는 단계(S40)와; 건조된 석탄을 질소조건 하에서 반탄화시키는 단계(S50);를 포함한다. A method for producing a modified hybrid coal impregnated with glycerol according to the present invention, the step of preparing the coal (S10); Mixing the glycerol and sulfuric acid solution (S20) and; Impregnating the coal in the glycerol sulfuric acid mixture (S30) and; drying the coal impregnated with the glycerol-sulfuric acid mixture (S40); and torrefied the dried coal under nitrogen condition (S50).
바람직하게, 혼합하는 단계에서 석탄의 다수의 기공에 글리세롤이 함침되는 것을 특징으로 한다.Preferably, in the step of mixing, it is characterized in that glycerol is impregnated into a plurality of pores of the coal.
바람직하게, 글리세롤과 황산용액의 혼합액은 석탄을 기준으로 각각 5 내지 80 중량%인 것을 특징으로 한다.Preferably, the mixed solution of glycerol and sulfuric acid solution is characterized in that 5 to 80% by weight, respectively, based on coal.
바람직하게, 글리세롤과 황산용액의 혼합비는 1:0.1~1:0.5의 중량비인 것을 특징으로 한다.Preferably, the mixing ratio of glycerol and sulfuric acid solution is characterized in that the weight ratio of 1:0.1 to 1:0.5.
바람직하게, 석탄의 건조단계는 80~120℃에서 이루어지는 것을 특징으로 한다. Preferably, the drying step of the coal is characterized in that it is made at 80 ~ 120 ℃.
바람직하게, 석탄의 반탄화 단계는 200~250℃에서 이루어지는 것을 특징으로 한다.Preferably, the torrefaction step of coal is characterized in that it is made at 200 ~ 250 ℃.
바람직하게, 반탄화된 석탄을 세척하고 건조시키는 단계(S60)를 더 포함하는 것을 특징으로 한다. Preferably, it characterized in that it further comprises a step (S60) of washing and drying torrefied coal.
본 발명에 의하면 석탄에 글리세롤과 함께 사용되는 황산에 의해서 발열량을 증가시키기 위해서 글리세롤의 휘발온도 이상에서 진행되는 반탄화 과정을 수행하여도 글리세롤이 휘발되는 것을 방지할 수 있는 효과가 있다.According to the present invention, in order to increase the calorific value by sulfuric acid used together with glycerol in coal, there is an effect that can prevent glycerol from volatilizing even when the torrefaction process is performed above the volatilization temperature of glycerol.
또한, 탄화된 글리세롤이 함침된 하이브리드 석탄은 안정적인 투-인-원 연료(Two-in-one fuel)의 연소 특징으로 에너지 효율이 증가되어도, 다단연소가 일어나지 않아 미연소탄소가 적게 배출되는 장점이 있다.In addition, the hybrid coal impregnated with carbonized glycerol has the advantage of emitting less unburned carbon because multi-stage combustion does not occur even if energy efficiency is increased due to the stable combustion characteristic of two-in-one fuel. have.
또한 본 발명에 따른 하이브리드 석탄은 저급탄에서 고발열량을 증가시켜 고급탄을 대체하여 저급탄의 활용을 촉진할 수 있다.In addition, the hybrid coal according to the present invention can promote the utilization of the low-grade coal by replacing the high-grade coal by increasing the high calorific value of the low-grade coal.
또한, 바이오디젤 공정에서 부산물로 발생되는 글리세롤을 사용하기 때문에 신재생에너지 의무할당제를 충적시키면서도 에너지 효율도 증가시킬 수 있는 향상된 효과가 있다.In addition, since glycerol generated as a by-product in the biodiesel process is used, there is an improved effect of increasing energy efficiency while filling the mandatory renewable energy quota system.
도 1은 본 발명에 따른 글리세롤이 함침된 개질 하이브리드 석탄의 제조과정에 대한 플로차트.
도 2는 본 발명에 따른 글리세롤이 함침된 개질 하이브리드 석탄의 개념도이다.
도 3은 본 발명에 따른 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄의 연소특성 그래프.
도 4는 본 발명에 따른 실시예1과 비교예의 활성화에너지 그래프.
도 5는 본 발명에 따른 실시예1,2,3과 비교예의 UBC 배출 그래프.
도 6은 본 발명에 따른 실시예1,2,3과 비교예의 황화수소 배출 그래프.1 is a flowchart for the manufacturing process of glycerol-impregnated reformed hybrid coal according to the present invention.
2 is a conceptual diagram of a reformed hybrid coal impregnated with glycerol according to the present invention.
Figure 3 is a graph of combustion characteristics of hybrid coal torrefied after impregnation with glycerol according to the present invention.
4 is an activation energy graph of Example 1 and Comparative Example according to the present invention.
5 is a UBC emission graph of Examples 1, 2, 3 and Comparative Example according to the present invention.
6 is a hydrogen sulfide emission graph of Examples 1, 2, 3 and Comparative Example according to the present invention.
이하, 첨부된 도면을 참조하여 본 발명의 실시예를 설명한다.Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
이하에서는 본 발명에 따라 수분을 포함하고 있는 원탄 또는 건조탄의 친수성 기공 및 친수성 표면에 바이오디젤 생산공정의 부산물인 글리세롤을 함침시키고 건조하여 소수성으로 개질함으로써 건조 후에도 수분의 재흡착이 현저하게 억제된 고발열량 하이브리드 석탄의 제조방법 및 그에 의하여 제조된 글리세롤이 함침된 고발열량 하이브리드 석탄으로부터 저급탄을 고급화하는 기술에 관하여 첨부된 도면과 함께 상세히 설명하기로 한다.Hereinafter, according to the present invention, by impregnating the hydrophilic pores and hydrophilic surface of raw coal or dry coal containing moisture with glycerol, a by-product of the biodiesel production process, and drying it to make it hydrophobic, re-adsorption of moisture is significantly suppressed even after drying. A method for producing a high calorific value hybrid coal and a technology for upgrading a low-grade coal from a high calorific value hybrid coal impregnated with glycerol produced thereby will be described in detail with the accompanying drawings.
도 1 및 도 2에 도시된 바와 같이, 본 발명에 따른 하이브리드 석탄의 제조방법은 석탄을 준비하는 단계(S10)와; 글리세롤과 황산용액을 혼합하는 단계(S20)와; 글리세롤 황산 혼합액에 석탄을 함침시키는 단계(S30)와; 글리세롤-황산 혼합액이 함침된 석탄을 건조시키는 단계(S40)와; 건조된 석탄을 질소조건 하에서 반탄화시키는 단계(S50);를 포함한다. 이때, 반탄화된 석탄을 세척하고 건조시키는 단계(S60)를 더 포함할 수 있다.1 and 2, the method for producing hybrid coal according to the present invention includes the steps of preparing coal (S10); Mixing the glycerol and sulfuric acid solution (S20) and; Impregnating the coal in the glycerol sulfuric acid mixture (S30) and; drying the coal impregnated with the glycerol-sulfuric acid mixture (S40); and torrefied the dried coal under nitrogen condition (S50). At this time, the step of washing and drying torrefied coal (S60) may be further included.
S10단계의 석탄은 표면에 다수의 기공이 형성되어 있는 것으로 이탄, 갈탄, 아역청탄, 역청탄 또는 무연탄이 사용될 수 있으며, 이것에 한정되는 것은 아니다. 본 발명에서는 기본적으로 갈탄, 아역청탄과 같이 수분 함량, 예컨대 20 내지 60 중량%로 높은 저급탄을 사용하는 것이 바람직하지만 이에 한정되는 것은 아니다. 이때, 석탄의 준비단계에서 석탄의 수분을 제거하는 것이 바람직하다.The coal of step S10 has a plurality of pores formed on the surface, and peat, lignite, sub-bituminous coal, bituminous coal or anthracite coal may be used, but is not limited thereto. In the present invention, it is preferable to use low-grade coal with a high moisture content, for example, 20 to 60% by weight, such as brown coal and sub-bituminous coal, but is not limited thereto. In this case, it is preferable to remove moisture from the coal in the preparation stage of the coal.
S20, S30단계의 글리세롤 황산 혼합액은 석탄이 함침되면서 페이스트를 형성한다. 글리세롤은 바이오디젤 공정에서 부산물로 발생되는 상온에서 액상의 물질로서 석탄의 친수성 기공 및 친수성 표면에 함침된다. 석탄의 친수성 표면은 석탄의 회분 표면이거나 -COOH(카르복실기), -NH2(아민기), -OH(하이드록실기) 기능기를 갖는 석탄의 고정탄소 및 휘발분 표면일 수도 있다. 글리세롤은 바이오매스의 생산공정에서 부산물로 얻어지는 글리세롤인 것이 바람직하지만, 화학적 또는 생물학적인 방법에 의하여 통상적으로 수득되는 글리세롤을 사용할 수도 있다.The glycerol sulfuric acid mixture of steps S20 and S30 forms a paste while impregnating with coal. Glycerol is a liquid substance at room temperature that is generated as a by-product in the biodiesel process and is impregnated into hydrophilic pores and hydrophilic surfaces of coal. The hydrophilic surface of coal may be an ash surface of coal or a surface of fixed carbon and volatile matter of coal having -COOH (carboxyl group), -NH2 (amine group), -OH (hydroxyl group) functional groups. The glycerol is preferably glycerol obtained as a by-product in the production process of biomass, but glycerol obtained conventionally by a chemical or biological method may be used.
글리세롤 황산 혼합액은 석탄 중량 대비 5~80 중량% 첨가하는 것이 바람직하다. 이때, 글리세롤의 첨가량이 5 중량% 미만이면 석탄의 친수성 기공 및 친수성 표면 내에 침투하는 글리세롤의 양이 미미하여 석탄의 친수성 기공 및 친수성 표면에 충분하게 함침될 수 없어 석탄의 친수성 기공 및 친수성 표면을 소수성으로 개질하기 어렵고, 80 중량%를 초과하면 페이스트 성상을 얻기 어려워 가공성이 떨어진다. It is preferable to add 5 to 80 wt% of the glycerol sulfuric acid mixture based on the weight of the coal. At this time, if the amount of glycerol added is less than 5% by weight, the amount of glycerol penetrating into the hydrophilic pores and hydrophilic surface of coal is insignificant, so that the hydrophilic pores and hydrophilic surface of coal cannot be sufficiently impregnated. It is difficult to modify, and when it exceeds 80% by weight, it is difficult to obtain a paste property and the workability is deteriorated.
황산은 글리세롤의 휘발온도 이상에서 석탄에 함침된 글리세롤이 반탄화 단계에 휘발되지 않도록 사용된다. 이때, 글리세롤에 대하여 황산의 혼합량은 1:0.1~1:0.5의 중량비로 혼합되는 것을 특징으로 한다. 황산의 혼합비가 0.1 중량비 미만이면 탄화시에 글리세롤의 휘발을 방지하기 어려워지고, 혼합량의 중량비가 5 이상이 되면 다량의 황산을 사용하여 오염물질이 생성되는 단점이 있다.Sulfuric acid is used so that glycerol impregnated in coal is not volatilized in the torrefaction step above the volatilization temperature of glycerol. At this time, the mixing amount of sulfuric acid with respect to glycerol is characterized in that it is mixed in a weight ratio of 1:0.1 to 1:0.5. When the mixing ratio of sulfuric acid is less than 0.1 weight ratio, it becomes difficult to prevent volatilization of glycerol during carbonization, and when the weight ratio of the mixing amount is 5 or more, a large amount of sulfuric acid is used to generate contaminants.
S40단계에서 석탄이 글리세롤-황산 혼합액이 함침되면 글리세롤-황산 혼합액의 이 석탄의 친수성 기공 및 친수성 표면에 코팅되도록 글리세롤의 휘발온도 이하에서 건조시킨다. 건조온도는 80~120℃인 것이 바람직하다. 건조과정에 의해서 글리세롤-황산 혼합물이 친수성 기공 및 친수성 표면에 달라붙으면서 코팅층을 형성하게 되어 수분의 재흡착을 감소시키게 된다.When the coal is impregnated with the glycerol-sulfuric acid mixture in step S40, the glycerol-sulfuric acid mixture is dried below the volatilization temperature of glycerol so as to be coated on the hydrophilic pores and hydrophilic surface of the coal. The drying temperature is preferably 80 ~ 120 ℃. By the drying process, the glycerol-sulfuric acid mixture adheres to the hydrophilic pores and the hydrophilic surface to form a coating layer, thereby reducing the re-adsorption of moisture.
S50단계에서 석탄의 건조과정을 통해서 글리세롤-황산 혼합액이 석탄의 친수성 기공 및 친수성 표면에 달라붙으면 질소분위기에서 200~250℃로 가열하여 반탄화시킨다. 이때, 글리세롤에 혼합된 황산에 의해 반탄화 온도가 글리세롤이 휘발온도인 180~200℃에서 진행되더라도 글리세롤이 휘발되지 않고 석탄의 친수성 기공 및 친수성 표면에 남아 있게 된다. 도 2에 도시된 바와 같이, 이러한 반탄화 과정을 통해 석탄의 친수성 기공 및 친수성 표면에 달라붙은 글리세롤에 새로운 기능기(C=C)가 생성되고, 친수성 기능기들이 제거된다. 이에 따라 수분의 재흡수율을 낮출 수 있게 되어 석탄의 발열량을 유지하고 수송, 저장 시 비용 절감과 더불어 수분에 의한 자연발화를 방지할 수 있게 된다. In step S50, if the glycerol-sulfuric acid mixture adheres to the hydrophilic pores and hydrophilic surface of the coal through the drying process of the coal, it is torrefied by heating at 200 to 250° C. in a nitrogen atmosphere. At this time, even if the torrefaction temperature by the sulfuric acid mixed with glycerol proceeds at 180-200° C., which is the volatilization temperature of glycerol, the glycerol does not volatilize and remains in the hydrophilic pores and hydrophilic surface of the coal. As shown in FIG. 2 , a new functional group (C=C) is generated in the hydrophilic pores of coal and glycerol adhered to the hydrophilic surface through this torrefaction process, and the hydrophilic functional groups are removed. Accordingly, it is possible to lower the reabsorption rate of moisture, thereby maintaining the calorific value of coal, reducing costs during transportation and storage, and preventing spontaneous combustion due to moisture.
한편, S60단계에서 반탄화된 석탄을 세척하고 건조시키는 과정을 통해서 반탄화된 석탄에 남아 있는 황산을 추가로 제거하여 황산화물의 발생을 더욱 낮출 수 있다.On the other hand, through the process of washing and drying the torrefied coal in step S60, sulfuric acid remaining in the torrefied coal may be additionally removed to further reduce the generation of sulfur oxides.
이러한 S50단계 또는 S60단계를 통해 석탄의 반탄화 과정을 거친 이후에 펠렛 등으로 성형하여 고발열량 하이브리드 석탄을 제조한다.After going through the torrefaction process of coal through step S50 or step S60, high calorific value hybrid coal is manufactured by molding it into pellets or the like.
상기 제조방법에 의하여 제조된 글리세롤이 함침되고 반탄화 과정을 거친 하이브리드 석탄은 안정적인 투-인-원 연료(Two-in-one fuel)의 연소 특징을 보인다. 이로 인해 본 발명에 따른 하이브리드 석탄은 고위발열량은 원탄에 비하여 약 1,100 kcal/kg 이상 높은 에너지 효율을 증대시킬 수 있다.The hybrid coal impregnated with glycerol and subjected to the torrefaction process prepared by the above manufacturing method exhibits stable combustion characteristics of a two-in-one fuel. For this reason, the hybrid coal according to the present invention has a high calorific value and can increase energy efficiency higher than about 1,100 kcal/kg compared to raw coal.
이에 따라 본 발명에 따른 하이브리드 석탄은 저급탄을 활용하여 고급탄으로 변화시킬 수 있기 때문에, 저급탄의 활용을 촉진할 수 있다.Accordingly, since the hybrid coal according to the present invention can be changed to high-grade coal by using low-grade coal, it is possible to promote the use of low-grade coal.
이하 구체적인 실시예를 상세히 설명한다.Hereinafter, specific examples will be described in detail.
(실시예 1~3, 비교예 1~2)(Examples 1-3, Comparative Examples 1-2)
글리세롤 10g 및 황산 1g의 혼합액에 입자크기가 75 μm이하인 건조된 아역청탄(BC) 100g를 혼합하여 갈탄에 글리세롤 10%를 함침시켰다. 그리고, 120℃에서 6 시간 동안 건조한 후, 질소분위기 하에서 250℃에서 1 시간 동안 반탄화 과정을 수행하여 실시예1의 글리세롤이 함침된 개질 하이브리드 석탄을 제조하였다(BC-10). 100 g of dried sub-bituminous coal (BC) having a particle size of 75 μm or less was mixed with a mixed solution of 10 g of glycerol and 1 g of sulfuric acid, and 10% of glycerol was impregnated into the lignite. Then, after drying at 120° C. for 6 hours, the torrefaction process was performed at 250° C. for 1 hour under a nitrogen atmosphere to prepare the modified hybrid coal impregnated with glycerol of Example 1 (BC-10).
실시예 2는 실시예 1과 동일한 조건하에서 글리세롤 20g 및 황산 2g의 혼합액을 사용하여 갈탄에 글리세롤 20%를 함침시켜 글리세롤이 함침된 개질 하이브리드 석탄을 제조하였으며(BC-20), 실시예 3은 글리세롤 30g 및 황산 3g의 혼합액을 사용하여 갈탄에 글리세롤 30%를 함침시켜 글리세롤이 함침된 개질 하이브리드 석탄을 제조하였다(BC-30). In Example 2, using a mixture of 20 g of glycerol and 2 g of sulfuric acid under the same conditions as in Example 1, lignite was impregnated with 20% of glycerol to prepare a modified hybrid coal impregnated with glycerol (BC-20), Example 3 was glycerol Using a mixture of 30 g and 3 g of sulfuric acid, lignite was impregnated with 30% glycerol to prepare glycerol-impregnated reformed hybrid coal (BC-30).
실시예 4는 실시예 1의 글리세롤이 함침된 개질 하이브리드 석탄(BC-10)을 물에 세척하고, 120℃에서 6 시간 동안 건조하였다((BC-10-washing). In Example 4, the modified hybrid coal (BC-10) impregnated with glycerol of Example 1 was washed in water and dried at 120° C. for 6 hours ((BC-10-washing).
비교예 1은 건조된 갈탄을 사용하였다(BC-D).In Comparative Example 1, dried lignite was used (BC-D).
(실시예 5~7, 비교예 2)(Examples 5-7, Comparative Example 2)
실시예 4~7은 실시예1~3과 동일한 조건 하에서 갈탄(KC)을 사용하여 글리세롤이 함침된 개질 하이브리드 석탄을 제조하였다(KC-10, KC-20, KC-30).In Examples 4-7, glycerol-impregnated reformed hybrid coal was prepared using lignite (KC) under the same conditions as Examples 1-3 (KC-10, KC-20, KC-30).
비교예 2는 건조된 아역청탄을 그대로 사용하였다(KC-D)In Comparative Example 2, dried sub-bituminous coal was used as it was (KC-D)
<글리세롤의 연소특성 확인><Confirmation of combustion characteristics of glycerol>
실시예 1~7 및 비교예 1~2의 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄의 연소온도 및 원단의 연소 특성을 측정하여 도 3에 나타내었다. After the glycerol of Examples 1 to 7 and Comparative Examples 1 to 2 was impregnated, the combustion temperature of the torrefied hybrid coal and the combustion characteristics of the fabric were measured and shown in FIG. 3 .
도 3에 나타난 바와 같이, 글리세롤은 200℃에서 휘발되지만, 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄은 글리세롤의 연소패턴이 사라지고 기존 석탄의 연소패턴과 유사한 것을 확인할 수 있다. As shown in Figure 3, glycerol is volatilized at 200 ℃, but after glycerol is impregnated in hybrid coal torrefied, the combustion pattern of glycerol disappears and it can be confirmed that it is similar to the combustion pattern of conventional coal.
<기공특성확인><Confirmation of pore characteristics>
실시예 1~3의 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄과 비교예 1의 단순 건조한 원탄의 기공 크기 분포도를 나타낸 그래프이다.It is a graph showing the pore size distribution of the torrefied hybrid coal and the simple dry raw coal of Comparative Example 1 after being impregnated with glycerol of Examples 1 to 3.
(m2/g) BET specific surface area
(m 2 /g)
(m2/g) pore area
(m 2 /g)
(m2/g) pore surface area
(m 2 /g)
(cm3/g) gun skin
(cm 3 /g)
(cm3/g) pore volume
(cm 3 /g)
(BC-D )Comparative Example 1
(BC-D)
(BC-10) Example 1
(BC-10)
(BC-20) Example 2
(BC-20)
(BC-30) Example 3
(BC-30)
표 1에 나타난 바와 같이, 실시예 1~3의 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄은 글리세롤이 석탄 기공속으로 함침되어 있어 비표면적, 기공면적 등이 비교예2의 원탄에 비하여 현저하게 감소된 것을 확인할 수 있다.<활성화에너지 확인>As shown in Table 1, in the hybrid coal torrefied after impregnation with glycerol of Examples 1 to 3, glycerol was impregnated into the pores of the coal, so that the specific surface area, pore area, etc. were significantly reduced compared to the raw coal of Comparative Example 2 It can be confirmed that the activation energy has been changed. <Confirmation of activation energy>
실시예1의 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄과 비교예 1의 원탄의 활성화에너지를 확인하여 도 4에 나타내었다.After the glycerol of Example 1 was impregnated, the activation energy of the torrefied hybrid coal and the raw coal of Comparative Example 1 was confirmed and shown in FIG. 4 .
도 4에 나타난 바와 같이, 비교예 1인 원탄의 활성화에너지가 9.68Kcal/mol이였지만 실시예 1의 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄은 7.44Kcal/mol로 낮아진 것을 확인할 수 있다. 이러한 낮은 활성화에너지에 의해서 빠른 점화가 이루어지고, 이러한 빠른 점화는 UBC(Unburned Carbon)를 절감시킬 수 있게 된다.As shown in Figure 4, although the activation energy of the raw coal of Comparative Example 1 was 9.68 Kcal/mol, it can be confirmed that the torrefied hybrid coal after impregnation with glycerol of Example 1 was lowered to 7.44 Kcal/mol. Fast ignition is achieved by such low activation energy, and this rapid ignition can reduce UBC (Unburned Carbon).
<UBC 배출 확인><Check UBC emission>
실시예 1,2,3의 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄 및 비교예 1의 원탄을 연소시켜 UBC(Unburned Carbon) 배출을 확인하여 도 5의 그래프로 나타내었다.After the glycerol of Examples 1, 2, and 3 was impregnated, the torrefied hybrid coal and the raw coal of Comparative Example 1 were burned to confirm the emission of Unburned Carbon (UBC), which is shown in the graph of FIG. 5 .
도 5에 나타난 바와 같이, 연소시 배출되는 UBC가 비교예 1의 원탄에서는 37.87%였지만, 실시예 1,2,3의 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄에서는 각각 27.44% 29.99%, 24.61%로 낮아진 것을 확인할 수 있다. 이러한 낮은 UBC(Unburned Carbon)는 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄의 Two-in-one fuel 연소 특성과 빠른 점화에 의한 것임을 알 수 있었다. 또한, 글리세롤의 함침량이 많을수록 UBC 배출이 낮아진 것을 확인할 수 있었다.As shown in FIG. 5 , the UBC emitted during combustion was 37.87% in the raw coal of Comparative Example 1, but 27.44% 29.99%, 24.61% in the hybrid coal that was torrefied after the glycerol of Examples 1, 2, and 3 was impregnated, respectively. It can be seen that the lowered This low UBC (Unburned Carbon) was found to be due to the two-in-one fuel combustion characteristics of the torrefied hybrid coal after impregnation with glycerol and the rapid ignition. In addition, it was confirmed that the more the amount of glycerol impregnated, the lower the UBC emission.
<수분 재흡착율 확인><Check moisture re-adsorption rate>
실시예1,2,3의 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄 및 원탄을 과량의 물에 담가 10분간 교반하면서 기공내로 물이 흡착되게 한 후, 20분간 여과하여 외부 수분을 제거하고 무게를 측정한다. 외부수분이 제거된 석탄은 다시 105℃ 오븐에서 12시간 동안 건조하여 기공 내의 수분까지 제거한다. 수분 재흡착율은 아래와 같이 계산하여 표 2에 나타내었다.After the glycerol of Examples 1, 2, and 3 was impregnated, the torrefied hybrid coal and raw coal were soaked in excess water and stirred for 10 minutes to allow water to be adsorbed into the pores, then filtered for 20 minutes to remove external moisture and weighed. measure The coal from which external moisture has been removed is dried again in an oven at 105° C. for 12 hours to remove moisture in the pores. The moisture resorption rate was calculated as follows and shown in Table 2.
수분 재흡착율(wt%) = (Cwet - Cdry)/Cwet * 100[Cwet 는 여과 후의 석탄 무게, Cdry는 오븐 건조 후의 석탄 무게]Moisture resorption rate (wt%) = (Cwet - Cdry)/Cwet * 100 [Cwet is the weight of coal after filtration, Cdry is the weight of coal after oven drying]
(BC-D)Comparative Example 1
(BC-D)
(BC-10 )Example 1
(BC-10)
(BC-20) Example 2
(BC-20)
(BC-30) Example 3
(BC-30)
표 2에 나타난 바와 같이, 비교예 1의 원탄에서는 수분 재흡수율을 53.89%이였지만, 실시예 1,2,3의 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄에서는 수분 재흡수율을 12.86%, 10.31%, 8.55%로 각각 낮아진 것을 확인할 수 있었다. 이러한 특징은 반탄화 과정을 글리세롤에 새로운 기능기(C=C)가 생성되고, 친수성 기능기들이 제거됨으로 인하여 석탄의 수분 흡착을 방해하는 것으로 확인할 수 있다.<황산화물발생 확인>As shown in Table 2, in the raw coal of Comparative Example 1, the moisture reabsorption rate was 53.89%, but in the hybrid coal torrefied after impregnation with glycerol of Examples 1, 2, and 3, the moisture reabsorption rate was 12.86%, 10.31% , it was confirmed that it was lowered to 8.55%, respectively. This characteristic can be confirmed that the torrefaction process interferes with the moisture adsorption of coal due to the creation of new functional groups (C = C) in glycerol and the removal of hydrophilic functional groups. <Confirmation of Sulfur Oxide Generation>
실시예1의 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄(BC-10), 실시예 4의 세척한 하이브리드 석탄(BC-10-washing) 및 비교예 1의 원탄(BC-D)을 연소시켜 황산화물의 배출을 확인하여 도 6의 그래프로 나타내었다.After being impregnated with glycerol of Example 1, the torrefied hybrid coal (BC-10), the washed hybrid coal of Example 4 (BC-10-washing) and the raw coal of Comparative Example 1 (BC-D) were burned to sulfuric acid The discharge of the cargo was confirmed and shown in the graph of FIG. 6 .
도 6에 나타난 바와 같이, 실시예1의 글리세롤이 함침된 후에 반탄화된 하이브리드 석탄에서는 제조과정에서 황산이 추가 되었음에도 불구하고 SOX 배출량이 크게 증가하지 않았으며, 실시예 4와 같이 세척할 경우 비교예 1의 원탄과 비슷한 수준의 황산화물이 배출되는 것을 확인할 수 있었다.As shown in FIG. 6 , in the hybrid coal torrefied after impregnation with glycerol of Example 1, SOX emissions did not significantly increase despite the addition of sulfuric acid during the manufacturing process, and when washed as in Example 4, Comparative Example It was confirmed that the same level of sulfur oxides as the raw coal of No. 1 was emitted.
<발열량 확인><Check the calorific value>
실시예 1 내지 7의 글리세롤이 함침된 하이브리드 석탄 및 비교예 1 내지 4의 원탄의 공업분석 결과와 발열량을 아래 표 3에 나타내었다.The industrial analysis results and calorific value of the hybrid coals impregnated with glycerol of Examples 1 to 7 and the raw coal of Comparative Examples 1 to 4 are shown in Table 3 below.
발열량
(kcal/kg) factorial
calorific value
(kcal/kg)
(kcal/kg) true calorific value
(kcal/kg)
(BC-D)Comparative Example 1
(BC-D)
(BC-10)Example 1
(BC-10)
(BC-20)Example 2
(BC-20)
(BC-30)Example 3
(BC-30)
(BC-10-washing) Example 4
(BC-10-washing)
(KC-D)Comparative Example 2
(KC-D)
(KC-10)Example 5
(KC-10)
(KC-20) Example 6
(KC-20)
(KC-30)Example 7
(KC-30)
상기 표 3에서 보는 것처럼 본 발명의 실시예 1~3의 갈탄을 사용하여 제조된 글리세롤이 함침되고 반탄화된 하이브리드 석탄(KC-10, KC-20, KC-30)은 비교예 1의 원탄에 비해 참 발열량(고유수분의 증발잠열을 고려한 경우)은 약 1,766 ~ 1,956 kcal/kg이 더 높았고, 발전소에서 일반적으로 사용하는 인수식 발열량의 경우는 약 1,900 ~ 2,128 kcal/kg가 더 높은 것으로 확인되었다. 그리고, 실시예 4~6의 아역청탄을 사용하여 제조된 글리세롤이 함침되고 반탄화된 하이브리드 석탄(BC-10, BC-20, BC-30)도 비교예 2의 원탄에 비해 참 발열량은 약 1,072 ~ 1,258 kcal/kg 더 높았고, 발전소에서 일반적으로 사용하는 인수식 발열량의 경우는 약 1,189 ~ 1,124 kcal/kg 더 높은 것으로 확인되었다. 또한 실시예 7과 같이 글리세롤이 함침되고 세척된 하이브리드 석탄((BC-10-washing)도 참 발열량은 1,012 kcal/kg 더 높았고, 인수식 발열량도 1,124 kcal/kg 높은 것으로 확인되었다.이와 같이 본 발명의 글리세롤이 함침되고 반탄화된 하이브리드 석탄은 원탄보다 매우 높게 발열량이 향상되어 저급탄도 고급탄과 같이 사용할 수 있다. 아울러, 본 발명의 글리세롤이 함침되고 반탄화된 하이브리드 석탄은 원탄에 비하여 수분의 함량을 현저하게 낮게 유지할 수 있고, 휘발분과 고정탄소가 높은 것으로 나타났다. As shown in Table 3 above, glycerol-impregnated and torrefied hybrid coals (KC-10, KC-20, KC-30) prepared using the lignite of Examples 1 to 3 of the present invention were mixed with the raw coal of Comparative Example 1. Compared to that, the true calorific value (when the latent heat of evaporation of intrinsic moisture is considered) was about 1,766 ~ 1,956 kcal/kg higher, and it was confirmed that about 1,900 ~ 2,128 kcal/kg was higher in the case of the takeover type calorific value generally used in power plants. . Also, the hybrid coals impregnated with glycerol and torrefied by using the sub-bituminous coals of Examples 4 to 6 (BC-10, BC-20, BC-30) also had a true calorific value of about 1,072 compared to the raw coal of Comparative Example 2 ~ 1258 kcal/kg was higher, and in the case of takeover calorific value commonly used in power plants, it was confirmed that it was about 1,189 ~ 1,124 kcal/kg higher. In addition, it was confirmed that the hybrid coal impregnated with glycerol and washed as in Example 7 ((BC-10-washing) also had a higher calorific value of 1,012 kcal/kg and a higher calorific value of 1,124 kcal/kg. Hybrid coal impregnated with glycerol and torrefied of glycerol has improved calorific value much higher than that of raw coal, and thus can be used with low-grade coal as well as high-grade coal. can be kept remarkably low, and volatile matter and fixed carbon were found to be high.
이상과 같이, 본 발명은 비록 한정된 실시예와 도면에 의해 설명되었으나, 본 발명은 이것에 의해 한정되지 않으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 본 발명의 기술사상과 아래에 기재될 청구범위의 균등범위 내에서 다양한 수정 및 변형이 가능함은 물론이다.As described above, although the present invention has been described with reference to limited embodiments and drawings, the present invention is not limited thereto, and the technical idea of the present invention and the following by those of ordinary skill in the art to which the present invention pertains Of course, various modifications and variations are possible within the scope of equivalents of the claims to be described.
Claims (7)
글리세롤과 황산용액을 혼합하는 단계(S20)와;
글리세롤 황산 혼합액에 석탄을 함침시키는 단계(S30)와;
글리세롤-황산 혼합액이 함침된 석탄을 건조시키는 단계(S40)와;
건조된 석탄을 질소조건 하에서 반탄화시키는 단계(S50);를 포함하는 것을 특징으로 하는 글리세롤이 함침된 개질 하이브리드 석탄의 제조방법. Preparing coal (S10) and;
Mixing the glycerol and sulfuric acid solution (S20) and;
Impregnating the coal in the glycerol sulfuric acid mixture (S30) and;
drying the coal impregnated with the glycerol-sulfuric acid mixture (S40);
A method for producing a modified hybrid coal impregnated with glycerol, comprising a; torrefoiling the dried coal under nitrogen condition (S50).
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