KR101631180B1 - Manufacturing method of active carbon derived from rice husks for hydrogen storage using chemical activation - Google Patents
Manufacturing method of active carbon derived from rice husks for hydrogen storage using chemical activation Download PDFInfo
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Abstract
본 발명은 화학적 활성화를 이용한 왕겨 기반 수소저장용 활성탄소의 제조방법에 관한 것으로서, 더욱 상세하게는 탄소원료로서 왕겨를 사용하여 알칼리 용매 처리 후, 질소분위기에서 열처리 하는 탄화과정을 통해 단순한 공정과정만으로 고 비표면적과 미세기공성을 가지는 수소저장용 활성탄소를 제조하는 방법을 포함한다.
상기와 같은 본 발명에 따르면, 화학적 활성화를 통하여 비표면적과 기공부피가 크게 증가한 활성탄소를 제조할 수 있으며, 기존의 활성탄소 제법보다 단순한 공정과정을 통해 제조되는 활성탄소를 제공함으로써, 기체 흡착이나 저장에 유용한 활성탄소를 다양한 분야에 제공하는 효과가 있다. The present invention relates to a process for producing activated carbon for hydrogen storage based on rice husk using chemical activation, and more particularly, to a process for producing activated carbon for hydrogen storage based on hydrogen peroxide And a method for producing activated carbon for hydrogen storage having a specific surface area and micropores.
According to the present invention, activated carbon having a large specific surface area and a large pore volume can be produced through chemical activation, and activated carbon produced through a simple process than the existing activated carbon process can be provided, It is effective to provide various kinds of activated carbon useful for storage.
Description
본 발명은 화학적 활성화를 이용한 왕겨 기반 수소저장용 활성탄소의 제조방법에 관한 것으로서, 더욱 상세하게는 탄소원료로서 왕겨를 사용하여 알칼리 용매 처리 후, 질소분위기에서 열처리 하는 탄화과정을 통해 단순한 공정과정만으로 고 비표면적과 미세기공성을 가지는 수소저장용 활성탄소를 제조하는 방법에 관한 것이다. The present invention relates to a process for producing activated carbon for hydrogen storage based on rice husk using chemical activation, and more particularly, to a process for producing activated carbon for hydrogen storage based on hydrogen storage, To a method for producing activated carbon for hydrogen storage having specific surface area and micropores.
최근 화석에너지의 사용량이 현저하게 증가하고 이산화탄소의 배출로 인한 오존층 파괴, 지구온난화, 산성비 등의 지구환경문제가 대두되면서 청정의 재생에너지원인 수소에너지가 각광받고 있다. 수소에너지를 활용하기 위해서는 수소를 고효율이면서 안전하게 저장할 수 있는 기술이 필수적이다. 현재 연구되고 있는 금속수화물이나 액화수소 저장기술, 고압수소기체 저장기술 등은 액화 및 압축에 요구되는 에너지 손실이 매우 크고 상온 폭발성에 대한 안전성이 문제되며, 금속수화물의 경우 무게가 높아 효율적이지 못하다. Recently, the use of fossil energy has been remarkably increased, and global environmental problems such as ozone layer destruction, global warming and acid rain caused by the emission of carbon dioxide are emerging, and hydrogen energy as clean renewable energy is attracting attention. In order to utilize hydrogen energy, it is essential to have a technology capable of storing hydrogen efficiently and safely. Currently, metal hydrates, liquid hydrogen storage technology, high pressure hydrogen gas storage technology, etc. have a great energy loss required for liquefaction and compression, and safety against explosion at room temperature is problematic, and metal hydrates are inefficient due to their high weight.
이러한 이유로 흡착제를 이용한 수소저장이 연구되고 있는데, 대표적인 흡착제인 활성탄소는 경량이며, 재료가 매우 풍부하고, 탄소의 우수한 화학적 안정성, 고강도, 생체친화성 등을 갖추고 있다. 활성탄소의 흡착 능력 향상을 위해서는 비표면적이 크고, 미세기공이 잘 발달 되어 있어야 한다. 이에 대한 다양한 종래 기술이 제시된 바 있으나, 제조공정이 복잡하고 여러 단계에서 고온의 열처리 과정이 수반되기 때문에 많은 에너지가 소요되므로 경제적이지 못하다는 단점이 있다.For this reason, hydrogen storage using an adsorbent has been studied. As a representative adsorbent, activated carbon is light in weight, has a very rich material, and has excellent chemical stability, high strength and biocompatibility of carbon. In order to improve the adsorption capacity of activated carbon, it is necessary to have large specific surface area and well-developed micropores. Various conventional techniques have been proposed, but the manufacturing process is complicated and the heat treatment process at high temperatures is accompanied by a lot of energy, which is disadvantageous in that it is not economical.
한편, 관련 종래기술로는 대한민국 등록특허 제10-0259546(커피 폐기물을 재활용한 고품질 활성탄의 제조), 대한민국 등록특허 특1997-0002890(왕겨활성탄의 제조방법) 등이 있다. On the other hand, related related arts include Korean Patent No. 10-0259546 (manufacture of high-quality activated carbon recycled from coffee waste) and Korean Patent Registration No. 1997-0002890 (production method of rice hull activated carbon).
본 발명자는 탄소원료로서 왕겨를 이용하여 알칼리 용매 처리 후, 질소분위기에서 열처리하는 탄화과정을 통해, 단순한 공정과정만으로 고 비표면적과 미세기공성을 가지는 수소저장용 활성탄소를 제조할 수 있음을 실험적으로 확인함으로써 본 발명을 완성하게 되었다. The present inventors have experimentally found that the activated carbon for hydrogen storage having a high specific surface area and micropores can be produced only by a simple process through a carbonization process in which heat treatment is performed in an atmosphere of nitrogen after treating with an alkaline solvent using a rice husk as a carbon raw material The present invention has been completed.
결국, 본 발명의 목적은, 왕겨를 알칼리 용매 처리 후, 질소분위기에서 열처리 하는 탄화과정을 통해 활성탄소의 제조방법을 제공함에 있다. It is an object of the present invention to provide a method for producing activated carbon through a carbonization process in which rice husk is treated with an alkali solvent and then heat-treated in a nitrogen atmosphere.
상기 목적을 달성하기 위하여, 본 발명은 (1) 알칼리 수용액을 제조하는 단계; (2) 상기 (1)단계의 알칼리 수용액에 탄소원료를 투입하여 혼합한 후 건조하여 용매를 제거하는 단계; (3) 상기 (2)단계에서 건조된 시료를 질소분위기에서 열처리하는 단계; (4) 상기 (3)단계에서 생성된 생성물을 수세하고 건조시키는 단계; 를 포함하는 활성탄소의 제조방법을 제공한다.In order to accomplish the above object, the present invention provides a method for producing an alkaline aqueous solution, comprising the steps of: (1) preparing an aqueous alkali solution; (2) adding a carbon source to the aqueous alkaline solution of step (1), mixing and then drying to remove the solvent; (3) heat treating the sample dried in the step (2) in a nitrogen atmosphere; (4) washing and drying the product produced in the step (3); The present invention provides a method for producing activated carbon.
상기 (1)단계에서 알칼리 수용액은 증류수 100중량부에 대하여, 에탄올 10 내지 100 중량부를 혼합한 용액에 LiOH, KOH, NaOH을 포함하는 군에서 선택된 1종 또는 2종 이상을 혼합하는 것을 특징으로 한다.In the step (1), the alkaline aqueous solution is prepared by mixing one or more selected from the group consisting of LiOH, KOH, and NaOH into a solution obtained by mixing 10 to 100 parts by weight of ethanol with respect to 100 parts by weight of distilled water .
상기 (2)단계에서 알칼리 수용액과 탄소원료의 비율은 1:1 내지 1:5의 중량비인 것을 특징으로 한다.In the step (2), the ratio of the aqueous alkaline solution to the carbon source is 1: 1 to 1: 5.
상기 (3)단계의 열처리에서 활성화온도는 600℃ 내지 1000℃인 것을 특징으로 한다.In the heat treatment in the step (3), the activation temperature is 600 ° C to 1000 ° C.
상기 (3)단계의 열처리에서 활성화 시간은 30분 내지 3시간인 것을 특징으로 하는 활성탄소의 제조방법을 제공한다.Wherein the activating time in the heat treatment in the step (3) is 30 minutes to 3 hours.
상기와 같은 본 발명에 따르면, 화학적 활성화를 통하여 비표면적과 기공부피가 크게 증가한 활성탄소를 제조할 수 있으며, 기존의 활성탄소 제법보다 단순한 공정과정을 통해 제조되는 활성탄소를 제공함으로써, 기체 흡착이나 저장에 유용한 활성탄소를 다양한 분야에 제공하는 효과가 있다. According to the present invention, activated carbon having a large specific surface area and a large pore volume can be produced through chemical activation, and activated carbon produced through a simple process than the existing activated carbon process can be provided, It is effective to provide various kinds of activated carbon useful for storage.
도 1은 본 발명에 따른 왕겨 기반 수소저장용 활성탄소의 질소 흡탈착 등온선이다.
도 2는 본 발명에 따른 왕겨 기반 수소저장용 활성탄소의 수소 흡착 등온선이다.1 is a nitrogen adsorption / desorption isotherm of activated carbon for rice hull-based hydrogen storage according to the present invention.
2 is a hydrogen adsorption isotherm of activated carbon for rice hull-based hydrogen storage according to the present invention.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 (1) 알칼리 수용액을 제조하는 단계; (2) 상기 (1)단계의 알칼리 수용액에 탄소원료를 투입하여 혼합한 후 건조하여 용매를 제거하는 단계; (3) 상기 (2)단계에서 건조된 시료를 질소분위기에서 열처리하는 단계; (4) 상기 (3)단계에서 생성된 생성물을 수세하고 건조시키는 단계; 를 포함하는 활성탄소의 제조방법을 제공한다.(1) preparing an aqueous alkali solution; (2) adding a carbon source to the aqueous alkaline solution of step (1), mixing and then drying to remove the solvent; (3) heat treating the sample dried in the step (2) in a nitrogen atmosphere; (4) washing and drying the product produced in the step (3); The present invention provides a method for producing activated carbon.
상기 (1)단계에서 알칼리 수용액은 증류수 100중량부에 대하여, 에탄올 10 내지 100 중량부를 혼합한 용액에 LiOH, KOH, NaOH을 포함하는 군에서 선택된 1종 또는 2종 이상을 혼합하는 것을 특징으로 한다.In the step (1), the alkaline aqueous solution is prepared by mixing one or more selected from the group consisting of LiOH, KOH, and NaOH into a solution obtained by mixing 10 to 100 parts by weight of ethanol with respect to 100 parts by weight of distilled water .
상기 (2)단계에서 알칼리 수용액과 탄소원료의 비율은 1:1 내지 1:5의 중량비인 것을 특징으로 한다. 알칼리 수용액에 대하여 탄소원료의 비율이 1중량비 미만이면 과다한 활성화 반응으로 인해 기공벽이 파괴되어 기공도가 오히려 감소되고, 알칼리 수용액에 대하여 탄소원료의 비율이 5중량비를 초과하는 경우 화학적 활성화가 불완전하게 일어나 기공생성이 적어진다.In the step (2), the ratio of the aqueous alkaline solution to the carbon source is 1: 1 to 1: 5. If the ratio of the carbon source to the alkali aqueous solution is less than 1 part by weight, the pore wall is broken due to excessive activation reaction and the porosity is rather reduced. When the ratio of the carbon source to the alkali aqueous solution exceeds 5 parts by weight, the chemical activation is incomplete And the generation of porosity is reduced.
여기에서 탄소원료로는 벼도정시 부산물로 발생되는 왕겨(벼껍질)를 이용하였는데, 왕겨의 화학적 조성에는 탄소성분의 함량이 30~40%로 높은 비율을 차지하고 있어 활성탄소의 원료 물질로 적합하다. 또한 폐기물로 처리되던 왕겨를 부가가치가 높은 고품질의 활성탄소로 재사용 할 수 있는 효과를 제공한다.Here, rice husk (rice husk), which is a byproduct of rice, was used as a raw material of carbon. The chemical composition of rice hulls is 30 ~ 40%, which is suitable as raw material of activated carbon. In addition, the present invention provides the effect of reusing the rice husk that has been treated with waste as high-quality activated carbon having high added value.
상기 (3)단계의 열처리에서는 분당 1℃ 내지 10℃로 승온시키고, 활성화온도는 600℃ 내지 1000℃ 으로 하며, 활성화 시간은 30분 내지 3시간인 것을 특징으로 한다. 이 과정에서 탄소원료는 탄화되는데, 이 탄화과정은 활성탄소의 제조에 있어서 활성탄소의 기본구조를 이루는 열분해 단계이다. 상기 활성화 온도가 600℃ 미만이면, 활성화 반응속도가 느려 활성화 시간이 과다하게 소요되고, 1000℃를 초과하는 경우에는 과도한 활성화 반응으로 인해 공정의 제어가 어려워지고, 기공벽이 파괴되어 기공도가 감소하며 활성탄의 기계적 강도가 감소하는 문제가 발생한다. 즉, 활성화 온도는 제조된 활성탄의 기공도에 큰 영향을 주는 요인이므로 상기 범위를 유지하는 것이 바람직하다.In the heat treatment in the step (3), the temperature is raised to 1 to 10 DEG C per minute, the activation temperature is 600 to 1000 DEG C, and the activation time is 30 minutes to 3 hours. In this process, the carbon raw material is carbonized, which is a pyrolysis step that forms the basic structure of activated carbon in the production of activated carbon. If the activation temperature is less than 600 ° C., the activation reaction rate is slow and the activation time is excessive. If the activation temperature is more than 1000 ° C., the process is difficult to control due to excessive activation reaction, And the mechanical strength of the activated carbon is reduced. That is, the activation temperature is a factor that greatly affects the porosity of the produced activated carbon, so it is preferable to maintain the above range.
상기 (3)단계에서 탄화과정을 거친 탄화물은 30분 내지 3시간 동안 수세하며, 70 ℃ 내지 90℃에서 12 내지 72시간 동안 건조시키는 것을 특징으로 한다. The carbonized carbonized in the step (3) is washed with water for 30 minutes to 3 hours and dried at 70 ° C to 90 ° C for 12 to 72 hours.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지는 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.
실시예 1.Example 1.
왕겨를 출발물질로 하여 에탄올 50ml, 증류수 50ml로 혼합되어 있는 용매에 KOH 2g 을 용해시키고 왕겨 2g를 넣어 80 ℃에서 24시간 동안 교반하여 용매를 모두 제거하였다.2 g of KOH was dissolved in a solvent mixed with 50 ml of ethanol and 50 ml of distilled water using rice hulls as a starting material, and 2 g of rice hull was added and stirred at 80 ° C for 24 hours to remove all the solvent.
이렇게 얻은 시료를 질소 분위기에서 분당 2℃로 승온하여 800 ℃에서 30분간 유지하였다. 탄화된 시료를 증류수를 이용해 pH를 7 내지 8에 도달할 때까지 수세한다. 이후 증류수를 제거한 후, 80℃의 오븐에서 24 시간 동안 건조시켰다. The sample thus obtained was heated to 2 ° C per minute in a nitrogen atmosphere and maintained at 800 ° C for 30 minutes. The carbonized sample is washed with distilled water until the pH reaches 7 to 8. After removing the distilled water, it was dried in an oven at 80 DEG C for 24 hours.
실시예 2.Example 2.
상기 실시예 1.과 동일한 방법으로 제조하되, NaOH 2g을 사용하여 용매를 제조하고 분당 5℃로 승온시킨 후 600℃에서 1시간 동안 유지하였다.A solvent was prepared by using 2 g of NaOH, heated to 5 ° C / min, and maintained at 600 ° C for 1 hour.
실시예 3.Example 3.
상기 실시예 1.과 동일한 방법으로 제조하되, 900℃에서 1시간 동안 유지하였다.Was prepared in the same manner as in Example 1, and maintained at 900 DEG C for 1 hour.
실시예 4.Example 4.
상기 실시예 1.과 동일한 방법으로 제조하되, NaOH 2g을 사용하여 용매를 제조하고 분당 5℃로 승온시켜 700℃에서 2시간 동안 유지하였다.A solvent was prepared by using 2 g of NaOH, and the temperature was raised to 5 ° C per minute and maintained at 700 ° C for 2 hours.
실시예 5.Example 5.
상기 실시예 1.과 동일한 방법으로 제조하되, KOH 4g을 사용하고 용매를 제조하고 900℃에서 1시간 동안 유지하였다.Was prepared in the same manner as in Example 1, except that 4 g of KOH was used and a solvent was prepared and maintained at 900 DEG C for 1 hour.
실시예 6.Example 6.
상기 실시예 1.과 동일한 방법으로 제조하되, NaOH 4g을 사용하여 용매를 제조하고 분당 5℃로 승온시켜 800℃에서 2시간 동안 유지하였다.A solvent was prepared using 4 g of NaOH, and the temperature was raised to 5 ° C per minute and maintained at 800 ° C for 2 hours.
실시예 7.Example 7.
상기 실시예 1.과 동일한 방법으로 제조하되, NaOH 2g 과 KOH 2g 을 혼합하여 용매를 제조하고 700℃에서 30분간 유지하였다.2 g of NaOH and 2 g of KOH were mixed to prepare a solvent, and the mixture was maintained at 700 ° C for 30 minutes.
실시예 8.Example 8.
상기 실시예 1.과 동일한 방법으로 제조하되, NaOH 2g 과 KOH 2g 을 혼합하여 용매를 제조하고 분당 5℃로 승온시켜 800℃에서 1시간 동안 유지하였다.2 g of NaOH and 2 g of KOH were mixed to prepare a solvent. The temperature was raised to 5 ° C per minute and maintained at 800 ° C for 1 hour.
비교예 1.Comparative Example 1
순수 왕겨만을 분당 5℃로 승온하여 700℃에서 2시간 동안 탄화시켜 제조한다.Only the pure rice husk is heated up to 5 ° C per minute and carbonized at 700 ° C for 2 hours.
비교예 2.Comparative Example 2
상기 비교예 1.과 동일한 방법으로 제조하되, 분당 2℃로 승온하여 800℃에서 1시간 동안 탄화시켜 제조한다.Was prepared in the same manner as in Comparative Example 1, but the temperature was raised to 2 ° C per minute and carbonized at 800 ° C for 1 hour.
비교예 3.Comparative Example 3
상기 비교예 1.과 동일한 방법으로 제조하되, 분당 10℃ 승온하여 900℃에서 30분 동안 탄화시켜 제조한다.Manufactured by the same method as in Comparative Example 1, and carbonized at 900 ° C for 30 minutes by heating at a rate of 10 ° C per minute.
측정예 1. 왕겨 기반 활성탄소의 기공구조 특성Measurement example 1. Pore structure characteristic of activated carbon based on rice husk
본 발명에 따른 왕겨 기반 활성탄소의 기공구조 특성을 77 K 액체 질소 분위기 하에서 시료 약 0.1 g을 채취하여 질소 기체를 흡착질로 하여 흡착량을 측정하여 관찰하였다. The pore structure of the rice husk-based activated carbon according to the present invention was measured by measuring the amount of adsorbed nitrogen gas as an adsorbate by taking about 0.1 g of the sample under a 77 K liquid nitrogen atmosphere.
시료의 전처리는 200 ℃에서 시료 내 잔류 압력이 10-3 torr 이하가 될 때까지 약 12 시간 동안 탈기시키고, 질소등온흡착시험 후에는 P/P0(P: 부분압력; P0: 포화 증기압)이 약 0.05에서 0.25까지 범위의 흡착량에 대해서 BET 파라미터 변환 후 직선의 기울기를 이용하여 BET 비표면적을 구하였다. P / P 0 (P: partial pressure; P 0 : saturation vapor pressure) after degassing for about 12 hours until the residual pressure in the sample becomes less than 10 -3 torr at 200 ° C., The BET specific surface area was obtained by using the slope of the straight line after the BET parameter conversion for the adsorption amount ranging from about 0.05 to 0.25.
또한, 전체 기공부피는 P/P0가 0.99인 점에서 흡착된 양을 기초로 하여 구하였다.Also, the total pore volume was determined based on the adsorbed amount at a P / P 0 of 0.99.
측정예 2. 왕겨 기반 활성탄소의 수소저장 용량Measurement example 2. Hydrogen storage capacity of activated carbon based on rice husk
본 발명에 따른 왕겨 기반 활성탄소의 수소저장 용량을 77 K 액체 질소 분위기 하에서 시료 약 0.1 g을 채취하여 고순도 수소 기체를 흡착질로 하여 수소 흡착량을 측정하여 관찰하였다.The hydrogen storage capacity of the rice husk-based activated carbon according to the present invention was measured by measuring the hydrogen adsorption amount using high purity hydrogen gas as an adsorbent by collecting about 0.1 g of the sample under 77 K liquid nitrogen atmosphere.
시료의 전처리는 200 ℃에서 시료 내 잔류 압력이 10-3 torr 이하가 될 때까지 약 12 시간 동안 탈기시킨 후, 샘플의 온도가 상온으로 떨어질 때 까지 기다린 후, 수소 흡착량을 측정한다.
The sample is pre-treated at 200 ° C. for about 12 hours until the residual pressure in the sample reaches 10 -3 torr or less, wait until the temperature of the sample falls to room temperature, and then measure the amount of hydrogen adsorption.
이상, 본 발명내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적인 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의해 정의된다고 할 것이다. Having described specific portions of the present invention in detail, those skilled in the art will appreciate that these specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (5)
(2) 상기 (1)단계에서 제조된 알칼리 수용액에 알칼리 수용액 대 왕겨를 1 : 1 내지 1 : 5의 중량비로 하여 넣고 교반하여 상기 왕겨를 화학적으로 활성화시키는 단계;
(3) 상기 (2)단계에서 화학적으로 활성화된 왕겨를 건조하여 용매를 제거하는 단계;
(4) 상기 (3)단계에서 건조된 시료를 질소분위기에서 900℃ 내지 1000℃의 온도 범위로 열처리하여 탄화시키는 단계; 및
(5) 상기 (4)단계에서 탄화된 시료를 수세하고 건조시키는 단계를 포함하는 수소저장용 활성탄소의 제조방법.
(1) preparing an aqueous alkali solution by mixing KOH, NaOH or a combination thereof with a solution obtained by mixing distilled water and ethanol;
(2) chemically activating the rice hull by adding an alkali aqueous solution to rice hull at a weight ratio of 1: 1 to 1: 5 to the alkali aqueous solution prepared in the step (1) and stirring;
(3) drying the chemically activated rice husk in the step (2) to remove the solvent;
(4) carbonizing the sample dried in the step (3) by heat treatment in a nitrogen atmosphere at a temperature ranging from 900 ° C to 1000 ° C; And
(5) The method for producing activated carbon for hydrogen storage, which comprises washing the carbonized sample in step (4) with water and drying.
상기 (2)단계는,
알칼리 수용액에 왕겨를 넣고 80℃에서 24시간 동안 교반하는 것을 특징으로 하는 수소저장용 활성탄소의 제조방법.
The method according to claim 1,
The step (2)
The method for producing activated carbon for hydrogen storage according to any one of claims 1 to 3, wherein the hydrogen peroxide solution is added to the aqueous alkaline solution and stirred at 80 DEG C for 24 hours.
상기 (5)단계는,
탄화된 시료를 증류수를 이용하여 pH가 7 내지 8에 도달할 때까지 수세하는 것을 특징으로 하는 수소저장용 활성탄소의 제조방법. The method according to claim 1,
The step (5)
Wherein the carbonized sample is washed with distilled water until the pH reaches 7 to 8.
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| KR20230093903A (en) | 2021-12-20 | 2023-06-27 | 재단법인 한국탄소산업진흥원 | Carbon-based adsorbent prepared with pitch and manufacturing method thereof |
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| CN110734063A (en) * | 2019-12-03 | 2020-01-31 | 武汉理工大学 | method for preparing rice hull based nitrogen-doped active carbon |
| KR102497078B1 (en) * | 2020-12-31 | 2023-02-06 | 대진대학교 산학협력단 | Manufacturing method of carbon material using plant biomass |
| CN115504468B (en) * | 2022-09-27 | 2024-10-11 | 东莞理工学院 | Modification method for improving toluene adsorption breakthrough time of walnut shell-based activated carbon |
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