KR101538639B1 - Manufacturing method of carbon-based carbon dioxide adsorbents - Google Patents
Manufacturing method of carbon-based carbon dioxide adsorbents Download PDFInfo
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Abstract
본 발명은 탄소기반 이산화탄소 흡착제의 제조방법에 관한 것으로서, 더욱 상세하게는 셀룰로오즈와 같은 탄소전구체를 기반으로 우수한 이산화탄소 포집능과 재생성을 갖는 이산화탄소 흡착제를 제조하는 방법에 관한 것이다.
상기와 같은 본 발명에 따르면, 셀룰로오즈 섬유와 같은 탄소전구체를 이용한 탄소기반 이산화탄소 흡착제는 탄소화 공정 전단계로 100 내지 300 ℃에서 산화안정화 표면처리하는 공정을 통해 열안정성을 확보하여 고수득률을 가질 뿐만 아니라, 스팀분사를 통한 활성화 공정을 통해 고비표면적을 갖고 초미세기공을 다량 함유하는 효과가 있다.
또한, 본 발명에 따른 이산화탄소 흡착제는 우수한 이산화탄소 포집능력과 재생성을 나타내는 효과가 있다.The present invention relates to a method for producing a carbon-based carbon dioxide adsorbent, and more particularly, to a method for producing a carbon dioxide adsorbent having excellent carbon dioxide capture ability and regeneration based on a carbon precursor such as cellulose.
According to the present invention, the carbon-based carbon dioxide adsorbent using a carbon precursor such as cellulose fiber has a high yield by securing thermal stability through oxidation stabilizing surface treatment at 100 to 300 ° C in the pre-carbonization step , And has an effect of having a high specific surface area and containing a large amount of ultrafine pores through an activation process through steam injection.
In addition, the carbon dioxide adsorbent according to the present invention has an effect of exhibiting excellent carbon dioxide capture ability and regeneration ability.
Description
본 발명은 탄소기반 이산화탄소 흡착제의 제조방법에 관한 것으로서, 더욱 상세하게는 셀룰로오즈와 같은 탄소전구체를 기반으로 우수한 이산화탄소 포집능과 재생성을 갖는 이산화탄소 흡착제를 제조하는 방법에 관한 것이다.
The present invention relates to a method for producing a carbon-based carbon dioxide adsorbent, and more particularly, to a method for producing a carbon dioxide adsorbent having excellent carbon dioxide capture ability and regeneration based on a carbon precursor such as cellulose.
일반적으로 활성탄소섬유은 주성분이 탄소이고 고비표면적 및 다공성 구조를 특징으로 하며, 뛰어난 흡착특성(빠른 흡/탈착 속도 및 고 흡착능력)을 지님에 따라 다양한 용도에 적용하기가 용이하다. 또한, 입자상 (granular), 분말상 (powder), 섬유상 (fibers)의 비면직물 (non-woven) 구조뿐만 아니라, 면직(woven) 구조, 면편직(knitted fabrics) 구조 등의 다양한 형태 가공이 가능하여 수처리 필터, 공기정화 필터, 에너지 저장소재, 전자소재, 멤브레인, 약물 지지체 등에 다양하게 사용된다. Generally, the activated carbon fiber is characterized by a high-specific surface area and a porous structure as a main component, and has excellent adsorption characteristics (fast adsorption / desorption rate and high adsorption ability), so that it can be easily applied to various applications. In addition, it is possible to process various shapes such as a woven structure and a knitted fabrics structure as well as a non-woven structure of granular, powder, and fibers, Filters, air purification filters, energy storage materials, electronic materials, membranes, drug supports, and the like.
활성탄은 넓은 비표면적을 가지고 있어 악취를 비롯한 기체분자에 대한 흡착용량이 크며 발달된 미세공이 세공표면에 노출되어 있어 흡착속도가 빠른 장점을 가지고 있기 때문에 기체상 오염물질의 제거능력이 높은 편이다. 잘 알려진 이산화탄소 흡수제인 제올라이트와는 달리 상대적으로 수분에 대한 영향이 적고 저렴한 가격으로 널리 사용되고 있으나 온실가스이며 실내공기 오염물질 가운데 하나인 이산화탄소에 대한 포집능력이 매우 낮기 때문에 다양한 표면개질을 통하여 이를 극복하고자 하는 노력이 이루어지고 있다.Activated carbon has a wide specific surface area, and it has a high adsorption capacity for gas molecules including odor, and developed pores are exposed on the pore surface, so that the adsorption rate is fast, so that the ability to remove gaseous pollutants is high. Unlike zeolite, which is a well-known carbon dioxide absorbent, it has relatively little effect on moisture and is widely used at a low price. However, since it is a greenhouse gas and has a low ability to capture carbon dioxide, which is one of indoor air pollutants, Efforts are being made.
활성탄소섬유의 제조단계에서 활성화 과정은 제조된 탄소의 표면에 미세기공을 부여하기 위한 공정으로서, 스팀, 이산화탄소, 공기 등을 이용한 물리적 활성화법과 알칼리, 알칼리토금속 염을 포함한 화학적 활성제를 이용한 화학적 활성화법이 주로 이용되고 있다. 화학적 활성화법은 다량의 화학적 첨착제를 이용한 고온 열처리법으로 탄소질의 표면에 미세기공을 다량 발현하는데 유용하나, 약품처리에서 수반하는 첨착 및 세척단계 등의 공정상의 복잡성, 2차 오염 등의 단점이 있다. 반면, 물리적 활성화법은 주로 주입되는 가스의 화학적 성질, 반응온도, 및 주입속도 등에 따라 활성탄소소재의 수득률 및 기공특성 등의 물성이 결정된다. Activation process in the production process of activated carbon fiber is a process for applying micro pores to the surface of the produced carbon. It is a chemical activation method using physical activation method using steam, carbon dioxide, air, and a chemical activator including alkali and alkaline earth metal salt Is mainly used. The chemical activation method is useful for the large-scale expression of micropores on the surface of carbonaceous materials by a high-temperature heat treatment method using a large amount of chemical impregnating agents. However, the disadvantages of process complexity such as impregnation and washing steps involved in chemical treatment and secondary contamination have. On the other hand, the physical activation method mainly determines the physical properties such as the yield of the activated carbon material and the pore characteristics depending on the chemical properties of the gas to be injected, the reaction temperature, and the injection rate.
관련 선행문헌으로 한국 등록특허 10-1267986(이산화탄소 흡착제의 제조방법 및 상기 흡착제를 이용한 다단 흡착필터), 한국 등록특허 10-0562020(이산화탄소 고정화 흡착제와 그의 제조방법) 등이 있지만, 셀룰로오즈와 같은 탄소전구체를 이용하여 최적의 스팀활성화법을 적용해 이산화탄소 포집능과 재생성이 향상시킨 탄소기반의 이산화탄소 흡착제에 관해서는 개시된 바가 없다.
Korean Patent No. 10-1267986 (a method for producing a carbon dioxide adsorbent and a multi-stage adsorption filter using the adsorbent) and Korean Patent No. 10-0562020 (a method for preparing a carbon dioxide-immobilized adsorbent and the like) Based carbon dioxide adsorbent having improved carbon dioxide capture ability and regeneration by applying an optimum steam activation method using a carbon dioxide adsorbent.
본 발명의 목적은 고비표면적을 갖고 초미세기공을 다량 함유하며 이산화탄소 포집능과 재생성이 우수한 탄소기반의 이산화탄소 흡착제를 제조하는 방법을 제공함에 있다.
An object of the present invention is to provide a method for producing a carbon-based carbon dioxide adsorbent having a high specific surface area, a large amount of ultrafine pores, and excellent carbon dioxide capture ability and regeneration ability.
상기 목적을 달성하기 위하여, 본 발명은 (1) 탄소전구체를 과산화수소, 붕산, 초산, 인산, 황산암모늄, 염화암모늄, 질산암모늄, 초산암모늄, 수산화암모늄, 탄산암모늄 및 인산암모늄을 포함하는 군에서 선택되는 1 이상의 화학적 첨착제를 이용하여 화학적 첨착시키는 단계; (2) 상기 (1)단계에서 화학적 첨착시킨 탄소전구체를 100 내지 300 ℃에서 10 내지 120 분간 열처리하여 산화안정화시키는 단계; (3) 상기 (2)단계에서 산화안정화시킨 탄소전구체를 600 내지 1200 ℃에서 10 내지 120 분간 열처리하여 탄소화시키는 단계; 및 (4) 상기 (3)단계에서 탄소화시킨 탄소전구체를 600 내지 1200 ℃에서 10 내지 120 분간 스팀을 분사하여 스팀활성화시키는 단계;를 포함하는 탄소기반 이산화탄소 흡착제의 제조방법을 제공한다.In order to achieve the above object, the present invention provides a method for producing a carbon precursor composition, comprising the steps of: (1) selecting a carbon precursor in the group including hydrogen peroxide, boric acid, acetic acid, phosphoric acid, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium acetate, ammonium hydroxide, ammonium carbonate and ammonium phosphate Chemical impregnation with one or more chemical additives; (2) oxidizing and stabilizing the carbon precursor chemically impregnated in the step (1) by heating at 100 to 300 ° C for 10 to 120 minutes; (3) carbonizing the carbon precursor oxidized and stabilized in the step (2) by heat treatment at 600 to 1200 ° C for 10 to 120 minutes; And (4) steam-activating the carbon precursor carbonized in the step (3) by spraying steam at 600 to 1200 ° C. for 10 to 120 minutes to steam-activate the carbon-based carbon dioxide adsorbent.
상기 (1)단계에서 탄소전구체는 셀룰로오즈 섬유, 셀룰로오즈 입자, 사이잘 섬유, 사이잘 입자, 폴리아크릴로니트릴계 섬유, 폴리아크릴로니트릴계 입자, 폴리스타이렌계 섬유, 폴리스타이렌계 입자, 레이온계 섬유, 레이온계 입자, 리그닌계 섬유, 리그닌계 입자 및 페놀계 수지를 포함하는 군에서 선택되는 1 이상인 것을 특징으로 한다.In the step (1), the carbon precursor may be at least one selected from the group consisting of cellulose fibers, cellulose particles, sisal fibers, sisal particles, polyacrylonitrile fibers, polyacrylonitrile particles, polystyrene- Based particles, lignin-based fibers, lignin-based particles, and phenolic resin.
상기 (1)단계에서 탄소전구체를 화학적 첨착하기 전에 증류수 및 에탄올이 혼합된 용액을 이용하여 탄소전구체를 세척한 후 건조시키는 전처리 과정을 더 포함하는 것을 특징으로 한다.The method may further include a pretreatment step of washing and drying the carbon precursor using a mixed solution of distilled water and ethanol before chemically attaching the carbon precursor in the step (1).
또한, 본 발명은 상기와 같은 방법으로 제조된 탄소기반 이산화탄소 흡착제를 제공한다.
The present invention also provides a carbon-based carbon dioxide adsorbent produced by the above-described method.
상기와 같은 본 발명에 따르면, 셀룰로오즈 섬유와 같은 탄소전구체를 이용한 탄소기반 이산화탄소 흡착제는 탄소화 공정 전단계로 100 내지 300 ℃에서 산화안정화 표면처리하는 공정을 통해 열안정성을 확보하여 고수득률을 가질 뿐만 아니라, 스팀분사를 통한 활성화 공정을 통해 고비표면적을 갖고 초미세기공을 다량 함유하는 효과가 있다.According to the present invention, the carbon-based carbon dioxide adsorbent using a carbon precursor such as cellulose fiber has a high yield by securing thermal stability through oxidation stabilizing surface treatment at 100 to 300 ° C in the pre-carbonization step , And has an effect of having a high specific surface area and containing a large amount of ultrafine pores through an activation process through steam injection.
또한, 본 발명에 따른 이산화탄소 흡착제는 우수한 이산화탄소 포집능력과 재생성을 나타내는 효과가 있다. 실제 화력발전소 배가스의 운용온도인 40 내지 80 ℃에서 고효율 이산화탄소 포집능력을 지니며 우수한 재생성을 지님에 따라, 유동층 또는 고정층 이산화탄소 포집공정의 흡착소재로 유용하게 사용될 수 있을 뿐만 아니라, 고도정수처리 나노필터 담체, 에너지 저장용 전극소재 및 각종 촉매 지지체 등 여러 분야에 응용 가능하여 고부가가치가 창출되는 있는 효과가 있다.
In addition, the carbon dioxide adsorbent according to the present invention has an effect of exhibiting excellent carbon dioxide capture ability and regeneration ability. Since it has a high-efficiency carbon dioxide capture ability at an operating temperature of an actual thermal power plant flue gas of 40 to 80 ° C and has excellent regeneration capability, it can be usefully used as an adsorbent material in a fluidized bed or fixed bed carbon dioxide capture process, It can be applied to various fields such as a carrier, an electrode material for energy storage, and various catalyst supports, thereby creating high added value.
도 1은 본 발명에 따른 이산화탄소 흡착제의 이산화탄소 포집능력 및 재생성을 나타냄.1 shows the carbon dioxide capture ability and regeneration of the carbon dioxide adsorbent according to the present invention.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 (1) 탄소전구체를 과산화수소, 붕산, 초산, 인산, 황산암모늄, 염화암모늄, 질산암모늄, 초산암모늄, 수산화암모늄, 탄산암모늄 및 인산암모늄을 포함하는 군에서 선택되는 1 이상의 화학적 첨착제를 이용하여 화학적 첨착시키는 단계; (2) 상기 (1)단계에서 화학적 첨착시킨 탄소전구체를 100 내지 300 ℃에서 10 내지 120 분간 열처리하여 산화안정화시키는 단계; (3) 상기 (2)단계에서 산화안정화시킨 탄소전구체를 600 내지 1200 ℃에서 10 내지 120 분간 열처리하여 탄소화시키는 단계; 및 (4) 상기 (3)단계에서 탄소화시킨 탄소전구체를 600 내지 1200 ℃에서 10 내지 120 분간 스팀을 분사하여 스팀활성화시키는 단계;를 포함하는 탄소기반 이산화탄소 흡착제의 제조방법을 제공한다.The present invention relates to a process for preparing a carbon precursor comprising the steps of: (1) mixing a carbon precursor with at least one chemical additive selected from the group consisting of hydrogen peroxide, boric acid, acetic acid, phosphoric acid, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium acetate, ammonium hydroxide, ammonium carbonate, Chemically impregnating the substrate; (2) oxidizing and stabilizing the carbon precursor chemically impregnated in the step (1) by heating at 100 to 300 ° C for 10 to 120 minutes; (3) carbonizing the carbon precursor oxidized and stabilized in the step (2) by heat treatment at 600 to 1200 ° C for 10 to 120 minutes; And (4) steam-activating the carbon precursor carbonized in the step (3) by spraying steam at 600 to 1200 ° C. for 10 to 120 minutes to steam-activate the carbon-based carbon dioxide adsorbent.
상기 (1)단계에서 탄소전구체는 셀룰로오즈 섬유, 셀룰로오즈 입자, 사이잘 섬유, 사이잘 입자, 폴리아크릴로니트릴계 섬유, 폴리아크릴로니트릴계 입자, 폴리스타이렌계 섬유, 폴리스타이렌계 입자, 레이온계 섬유, 레이온계 입자, 리그닌계 섬유, 리그닌계 입자 및 페놀계 수지를 포함하는 군에서 선택되는 1 이상인 것이 바람직하다.In the step (1), the carbon precursor may be at least one selected from the group consisting of cellulose fibers, cellulose particles, sisal fibers, sisal particles, polyacrylonitrile fibers, polyacrylonitrile particles, polystyrene- Based particles, lignin-based fibers, lignin-based particles, and phenolic resin.
상기 (1)단계에서 탄소전구체를 화학적 첨착하기 전에 증류수 및 에탄올이 혼합된 용액을 이용하여 탄소전구체를 세척한 후 건조시키는 전처리 과정을 더 포함하는 것이 바람직하다. 상온에서 증류수 및 에탄올 혼합용액으로 1 내지 12 시간 동안 교반하는 것을 3 회 이상 반복하여 세척함으로써, 탄소전구체 구조에 존재하는 미반응 저분자 유기물질 등을 제거하는 효과가 있다. 또한, 상기 세척 공정 후 이루어지는 건조 공정은 80 ℃ 이상의 온도에서 6 내지 24 시간, 바람직하게는 12 시간 동안 완전히 건조시키는 것이 바람직하다. Preferably, the method further comprises a pretreatment step of washing the carbon precursor using a mixed solution of distilled water and ethanol before chemically attaching the carbon precursor in step (1) and drying the carbon precursor. Stirring at room temperature for 1 to 12 hours with distilled water and ethanol mixed solution is repeated three times or more to remove unreacted low molecular weight organic substances existing in the carbon precursor structure. Also, it is preferable that the drying step after the washing step is completely dried at a temperature of 80 ° C or higher for 6 to 24 hours, preferably 12 hours.
상기 (1)단계에서 첨착 공정은 상온에서 0.01 내지 20 vol.%, 바람직하게는 0.05 내지 10 vol.%의 농도를 갖는 화학적 첨착제를 이용하여 1 내지 24 시간, 바람직하게는 5 내지 120 분간 첨착하는 것이 바람직하다. 상기와 같이 산화안정화 공정 전에 세척 및 화학적 첨착을 통해 기공을 다량 발현시킬 수 있는 효과가 있다.In the step (1), the impregnation process may be carried out at room temperature for 1 to 24 hours, preferably 5 to 120 minutes, using a chemical extruder having a concentration of 0.01 to 20 vol.%, Preferably 0.05 to 10 vol. It is desirable to be good. As described above, there is an effect that a large amount of pores can be expressed through washing and chemical impregnation before the oxidation stabilization process.
상기 (2)단계에서 산화안정화 공정은 탄소전구체의 물리적 및 기계적 물성을 증대시키기 위한 과정으로서 활성탄소소재의 수율 증대를 위해 필수적인 공정이다. 이는 머플퍼니스를 이용하여 공기 분위기 하에서 승온속도 0.1 내지 10 ℃/min, 바람직하게는 0.5 내지 5 ℃/min으로 승온시켜 열처리하는 것이 바람직하며, 30 내지 60 분간 열처리하는 것이 최적의 효과를 나타낸다. In the step (2), the oxidation stabilization process is an essential process for increasing the yield of the activated carbon material as a process for increasing the physical and mechanical properties of the carbon precursor. It is preferable that the heat treatment is performed by raising the temperature at a heating rate of 0.1 to 10 占 폚 / min, preferably 0.5 to 5 占 폚 / min in an air atmosphere by using a muffle furnace, and heat treatment for 30 to 60 minutes is optimal.
산화안정화 온도가 100 ℃보다 낮을 경우 산화안정화가 거의 이루어지지 않고, 300 ℃보다 높을 경우 탄소전구체의 구조붕괴 등의 손실 현상이 나타나는 문제가 있다. 또한, 산화안정화 승온속도가 0.1 ℃/min 이하일 경우 총 산화안정화 처리시간이 비효율적으로 증가하고, 10 ℃/min 이상일 경우 탄소전구체 구조의 붕괴 및 최종산물의 수율 저하에 영향을 미치므로 바람직하지 않다.When the oxidation stabilization temperature is lower than 100 ° C, oxidation stabilization is hardly achieved, and when the oxidation stabilization temperature is higher than 300 ° C, there is a problem that a loss phenomenon such as structural collapse of the carbon precursor occurs. Also, when the oxidation stabilization temperature raising rate is 0.1 캜 / min or less, the total oxidative stabilization treatment time increases inefficiently, and when it is 10 캜 / min or more, the carbon precursor structure collapses and the yield of the final product decreases.
상기 (3)단계 및 (4)단계에서 탄소화 및 스팀활성화 공정은 튜브형 스팀퍼니스를 이용하여 질소 분위기 하에서 이루어지는 것이 바람직하다. 이때, 탄소화 공정에서 승온속도는 1 내지 5 ℃/min, 스팀활성화 공정에서 스팀분사속도는 0.001 내지 1 sccm/min, 바람직하게는 0.01 내지 0.5 sccm/min인 것이 최적의 효과를 나타낸다. 스팀분사속도 0.01 sccm/min 이하에서는 충분한 스팀이 공급되지 않아 미세기공의 발현이 다소 어렵고, 0.5 sccm/min 이상에서는 다량의 스팀 공급으로 인하여 반응로 내부의 과도한 압력증가 및 미세한 온도감소 현상이 나타나는 문제가 있다.In the steps (3) and (4), the carbonization and steam activation process is preferably performed in a nitrogen atmosphere using a tubular steam furnace. At this time, the temperature raising rate in the carbonization process is 1 to 5 占 폚 / min, and the steam injection rate in the steam activation process is 0.001 to 1 sccm / min, preferably 0.01 to 0.5 sccm / min. When the steam injection rate is less than 0.01 sccm / min, sufficient steam is not supplied and the micropores are difficult to express. When the flow rate is more than 0.5 sccm / min, excessive steam is supplied to the inside of the reaction chamber due to excessive steam supply, .
탄소화(탄화) 공정은 탄화수소 및 유기 휘발분 등을 완전히 제거하고 탄소질 원료 내에서 탈수 및 탈산 등의 분해를 통해 산소결합이 끊어지면서 산소가 물, 일산화탄소, 이산화탄소 등의 기체 형태도 방출되고 고정탄소만 남게 되는 과정이다. 또한, 스팀을 이용한 스팀활성화법은 알칼리염이나 알칼리토금속 등의 화학적 첨착제를 이용한 화학적 고온 활성화법에 비하여 다량의 알칼리계 첨착제나 세척용 산 용액을 필요로 하지 않는 장점이 있어, 매우 경제적이고 친환경적인 방법이다.Carbonization (carbonization) process completely removes hydrocarbons and organic volatiles, and oxygen is broken through decomposition such as dehydration and deoxidation in a carbonaceous raw material, so oxygen is released in gas form such as water, carbon monoxide and carbon dioxide, It is the process that remains. In addition, the steam-based steam activation method has an advantage in that it does not require a large amount of an alkali-based impregnant or an acid solution for cleaning, compared with a chemical high-temperature activation method using a chemical additive such as an alkali salt or an alkaline earth metal, It is a method.
또한, 본 발명은 상기와 같은 방법으로 제조된 탄소기반 이산화탄소 흡착제를 제공한다.
The present invention also provides a carbon-based carbon dioxide adsorbent produced by the above-described method.
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 해석되지 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 embodiments are merely illustrative of the present invention and that the scope of the present invention is not construed as being limited by these embodiments.
측정예 1. 스팀활성화법으로 제조된 탄소기반 흡착제의 기공특성 분석Measurement example 1. Analysis of pore characteristics of carbon-based adsorbent prepared by steam activation method
스팀활성화법으로 제조된 탄소기반 흡착제의 기공특성은 액체 질소(77 K) 분위기 하에서 시료 약 0.1 g을 채취하여 질소 기체를 흡착질로 하여 흡착량을 측정하였다. 시료의 전처리는 200 ℃에서 시료 내 잔류 압력이 10-3 torr 이하로 될 때까지 약 12 시간 동안 탈기시키고, 질소 등온흡착시험 후에는 P/P0(P: 부분압력, P0: 포화 증기압)이 약 0.05에서 0.25까지의 범위의 흡착량에 대해서 BET 파라미터 변환 후, 직선의 기울기를 이용하여 BET 비표면적을 구하였다. 또한. 전체 기공부피는 P/P0가 0.99인 점에서 흡착된 양을 기초로 구하였다.
The adsorption amount of the carbon - based adsorbent prepared by the steam activation method was measured by using nitrogen gas as an adsorbent. About 0.1 g of the sample was collected under liquid nitrogen (77 K) atmosphere. P / P 0 (P: partial pressure, P 0 : saturated vapor pressure) was measured after nitrogen isothermic adsorption test for about 12 hours until the residual pressure in the sample became less than 10 -3 torr at 200 ° C., The BET specific surface area was obtained using the slope of the straight line after the BET parameter conversion for the adsorption amount ranging from about 0.05 to 0.25. Also. The total pore volume was determined based on the adsorbed amount at a P / P 0 of 0.99.
측정예 2. 스팀활성화법으로 제조된 탄소기반 흡착제의 이산화탄소 포집거동 분석Measurement example 2. Carbon dioxide capture behavior analysis of carbon-based adsorbent prepared by steam activation method
스팀활성화법으로 제조된 탄소기반 흡착제의 이산화탄소 포집능력 및 재생성 분석은 열중량분석법을 사용하였으며, 시료 약 20 mg을 백금챔버에 옮긴 후, 시료의 전처리는 밸런스기체를 질소로 하여 200 ℃에서 약 12 시간 동안 탈기시키고 상온으로 냉각한 후 이산화탄소 포집거동을 분석하였다. 전체기체의 부피대비 이산화탄소 기체를 15 %로 고정(이산화탄소/질소, 약 15 : 85 v/v)하여 총 유량속도 60 cc/min, 온도조건 40 ℃에서 시료질량 대비 증가한 이산화탄소 기체의 질량변화를 통해 이산화탄소 포집량을 분석하였고, 탈착은 동일한 온도에서 질소기체의 배기를 통해 이루어졌으며, 각 이산화탄소 흡/탈착 분석 사이클은 10 회 반복하였다.The carbon dioxide capture ability and regeneration of the carbon-based adsorbent prepared by the steam activation method were analyzed by thermogravimetric analysis. After transferring about 20 mg of the sample to the platinum chamber, the pretreatment of the sample was carried out at about 200 ° C. for about 12 Deg.] C, cooled to room temperature, and analyzed for carbon dioxide capture behavior. By changing the mass of carbon dioxide gas relative to the sample mass at a total flow rate of 60 cc / min and a temperature condition of 40 ° C, the carbon dioxide gas was fixed at 15% (carbon dioxide / nitrogen, about 15: 85 v / The amount of carbon dioxide capture was analyzed, and the desorption was carried out through nitrogen gas exhaust at the same temperature, and each carbon dioxide adsorption / desorption analysis cycle was repeated ten times.
그 결과, 본 발명에 따른 탄소기반 이산화탄소 흡착제는 질소 및 이산화탄소의 혼합배가스 조성 85 : 15 (v/v) 및 흡/탈착 온도조건 40 ℃에서 우수한 이산화탄소 포집능력 및 재생성을 나타내는 것을 알 수 있었다.
As a result, it was found that the carbon-based carbon dioxide adsorbent according to the present invention exhibits excellent carbon dioxide capture ability and regeneration at a mixed flue gas composition of 85: 15 (v / v) of nitrogen and carbon dioxide and an inlet / desorption temperature condition of 40 ° C.
실시예 1.Example 1.
셀룰 로오즈 섬유 1 g을 상온에서 증류수 및 에탄올 용액에 2 시간정도 교반하여 완전히 세척하여 80℃에서 12시간 이상 완전히 건조한 후, 1%의 과산화수소 수용액에 30분 동안 첨착시키고, 80℃에서 24 시간 완전 건조하여 준비하였다. 화학적 첨착처리된 셀룰로오즈 섬유를 머플퍼니스에 넣고 공기 분위기하에서 2 ℃/min의 승온속도로 180℃까지 승온시켜 30분간 유지시켜 산화안정화된 셀룰로오즈 섬유를 얻었다. 준비된 산화안정화된 셀룰로오즈 섬유는 튜브형 퍼니스에 넣고 질소(N2) 분위기 하에서 2℃/분의 승온 속도로 800℃까지 승온 후, 1시간 유지시켜 탄소화과정을 거친다. 그 다음, 1시간 동안 0.3 sccm/min의 분사속도로 스팀을 주입하면서 스팀활성화한 후, 실온까지 냉각하였다. 상기와 같이 스팀활성화법을 통해 제조된 셀룰로오즈 기반 탄소기반 흡착제는 증류수에서 1~2회 세척하여 120℃의 진공오븐에서 12시간 이상 완전 건조시켰다.
1 g of cellulosic fiber was thoroughly washed with distilled water and ethanol solution at room temperature for 2 hours, completely dried at 80 ° C for more than 12 hours, then impregnated with 1% aqueous hydrogen peroxide solution for 30 minutes, Dried and prepared. The chemically impregnated cellulose fibers were placed in a muffle furnace and heated to 180 DEG C at a heating rate of 2 DEG C / min in an air atmosphere and held for 30 minutes to obtain oxidized stabilized cellulose fibers. The prepared oxidized stabilized cellulose fibers were put in a tube type furnace, heated to 800 ° C at a heating rate of 2 ° C / minute in a nitrogen (N 2 ) atmosphere, and maintained for 1 hour for carbonization. Then, steam was injected at an injection speed of 0.3 sccm / min for one hour while steam was injected, followed by cooling to room temperature. As described above, the cellulose-based carbon-based adsorbent prepared through the steam activation method was washed once or twice in distilled water and completely dried in a vacuum oven at 120 ° C. for 12 hours or more.
실시예 2.Example 2.
셀룰로오즈 섬유 1 g을 상온에서 증류수 및 에탄올 용액에 2 시간정도 교반하여 완전히 세척하여 80℃에서 12시간 이상 완전히 건조한 후, 1.5%의 과산화수소 수용액에 30분 동안 첨착시키고, 80℃에서 24 시간 완전 건조하여 준비하였다. 화학적 첨착처리된 셀룰로오즈 섬유를 머플퍼니스에 넣고 공기 분위기하에서 0.5 ℃/min의 승온속도로 150℃까지 승온시켜 60분간 유지시켜 산화안정화된 셀룰로오즈 섬유를 얻었다. 준비된 산화안정화된 셀룰로오즈 섬유는 튜브형 퍼니스에 넣고 질소(N2) 분위기 하에서 1℃/분의 승온 속도로 850℃까지 승온 후, 1시간 유지시켜 탄소화과정을 거친다. 그 다음, 1시간 30분간 0.2 sccm/min의 분사속도로 스팀을 주입하면서 스팀활성화한 후, 실온까지 냉각하였다. 상기와 같이 스팀활성화법을 통해 제조된 셀룰로오즈 기반 탄소기반 흡착제는 증류수에서 1~2회 세척하여 120℃의 진공오븐에서 12시간 이상 완전 건조시켰다.
1 g of the cellulose fiber was thoroughly washed with distilled water and ethanol solution at room temperature for about 2 hours, completely dried at 80 ° C for more than 12 hours, then impregnated in a 1.5% aqueous hydrogen peroxide solution for 30 minutes and completely dried at 80 ° C for 24 hours Prepared. The chemically impregnated cellulose fibers were placed in a muffle furnace and heated to 150 DEG C at a heating rate of 0.5 DEG C / min in an air atmosphere and held for 60 minutes to obtain oxidized stabilized cellulose fibers. The prepared oxidized stabilized cellulose fibers were put into a tube-type furnace, heated to 850 ° C at a heating rate of 1 ° C / min in an atmosphere of nitrogen (N 2 ), and then subjected to a carbonization process by being maintained for 1 hour. Then, steam was injected at an injection speed of 0.2 sccm / min for 1 hour and 30 minutes while steam was being injected, followed by cooling to room temperature. As described above, the cellulose-based carbon-based adsorbent prepared through the steam activation method was washed once or twice in distilled water and completely dried in a vacuum oven at 120 ° C. for 12 hours or more.
실시예 3.Example 3.
셀룰로오즈 섬유 1 g을 상온에서 증류수 및 에탄올 용액에 2 시간정도 교반하여 완전히 세척하여 80℃에서 12시간 이상 완전히 건조한 후, 3%의 과산화수소와 인산 혼합수용액(과산화수소:인산=50:50, v/v)에 20분 동안 첨착시키고, 80℃에서 24 시간 완전 건조하여 준비하였다. 화학적 첨착처리된 셀룰로오즈 섬유를 머플퍼니스에 넣고 공기 분위기하에서 1.5 ℃/min의 승온속도로 200℃까지 승온시켜 20분간 유지시켜 산화안정화된 셀룰로오즈 섬유를 얻었다. 준비된 산화안정화된 셀룰로오즈 섬유는 튜브형 퍼니스에 넣고 질소(N2) 분위기 하에서 2℃/분의 승온 속도로 1000℃까지 승온 후, 1시간 유지시켜 탄소화과정을 거친다. 그 다음, 30분간 0.4 sccm/min의 분사속도로 스팀을 주입하면서 스팀활성화한 후, 실온까지 냉각하였다. 상기와 같이 스팀활성화법을 통해 제조된 셀룰로오즈 기반 탄소기반 흡착제는 증류수에서 1~2회 세척하여 120℃의 진공오븐에서 12시간 이상 완전 건조시켰다.
1 g of cellulose fiber was thoroughly washed with distilled water and ethanol solution for 2 hours at room temperature and completely washed and dried at 80 ° C for more than 12 hours. Then, a 3% aqueous solution of hydrogen peroxide and phosphoric acid (hydrogen peroxide: phosphoric acid = 50:50, v / v ) For 20 minutes, and was completely dried at 80 DEG C for 24 hours. The chemically impregnated cellulose fibers were placed in a muffle furnace and heated to 200 DEG C at a rate of 1.5 DEG C / min in an air atmosphere and held for 20 minutes to obtain oxidized stabilized cellulose fibers. The prepared oxidized stabilized cellulose fibers were placed in a tube-type furnace, heated to 1000 ° C at a rate of 2 ° C / min under a nitrogen (N 2 ) atmosphere, and maintained for 1 hour for carbonization. Then, steam was injected for 30 minutes at an injection speed of 0.4 sccm / min while steam was injected, followed by cooling to room temperature. As described above, the cellulose-based carbon-based adsorbent prepared through the steam activation method was washed once or twice in distilled water and completely dried in a vacuum oven at 120 ° C. for 12 hours or more.
실시예 4.Example 4.
셀룰로오즈 섬유 1 g을 상온에서 증류수 및 에탄올 용액에 2 시간정도 교반하여 완전히 세척하여 80℃에서 12시간 이상 완전히 건조한 후, 2.5%의 인산 수용액에 20분 동안 첨착시키고, 80℃에서 24 시간 완전 건조하여 준비하였다. 화학적 첨착처리된 셀룰로오즈 섬유를 머플퍼니스에 넣고 공기 분위기하에서 1 ℃/min의 승온속도로 190℃까지 승온시켜 20분간 유지시켜 산화안정화된 셀룰로오즈 섬유를 얻었다. 준비된 산화안정화된 셀룰로오즈 섬유는 튜브형 퍼니스에 넣고 질소(N2) 분위기 하에서 2℃/분의 승온 속도로 950℃까지 승온 후, 1시간 유지시켜 탄소화과정을 거친다. 그 다음, 1시간 동안 0.25 sccm/min의 분사속도로 스팀을 주입하면서 스팀활성화한 후, 실온까지 냉각하였다. 상기와 같이 스팀활성화법을 통해 제조된 셀룰로오즈 기반 탄소기반 흡착제는 증류수에서 1~2회 세척하여 120℃의 진공오븐에서 12시간 이상 완전 건조시켰다.
1 g of the cellulose fiber was thoroughly washed with distilled water and ethanol solution at room temperature for about 2 hours, completely dried at 80 ° C. for 12 hours or more, then impregnated in a 2.5% aqueous solution of phosphoric acid for 20 minutes and completely dried at 80 ° C. for 24 hours Prepared. The chemically impregnated cellulose fibers were placed in a muffle furnace and heated to 190 DEG C at a heating rate of 1 DEG C / min in an air atmosphere and held for 20 minutes to obtain oxidized stabilized cellulose fibers. The prepared oxidized stabilized cellulose fibers were put into a tube-type furnace, heated to 950 ° C at a heating rate of 2 ° C / min under a nitrogen (N 2 ) atmosphere, and then carbonized by holding for 1 hour. Then, steam was injected at an injection speed of 0.25 sccm / min for 1 hour while steam was being injected, and then cooled to room temperature. As described above, the cellulose-based carbon-based adsorbent prepared through the steam activation method was washed once or twice in distilled water and completely dried in a vacuum oven at 120 ° C. for 12 hours or more.
실시예 5.Example 5.
셀룰로오즈 섬유 1 g을 상온에서 증류수 및 에탄올 용액에 2 시간정도 교반하여 완전히 세척하여 80℃에서 12시간 이상 완전히 건조한 후, 5%의 붕산 수용액에 60분 동안 첨착시키고, 80℃에서 24 시간 완전 건조하여 준비하였다. 화학적 첨착처리된 셀룰로오즈 섬유를 머플퍼니스에 넣고 공기 분위기하에서 4 ℃/min의 승온속도로 200℃까지 승온시켜 15분간 유지시켜 산화안정화된 셀룰로오즈 섬유를 얻었다. 준비된 산화안정화된 셀룰로오즈 섬유는 튜브형 퍼니스에 넣고 질소(N2) 분위기 하에서 2℃/분의 승온 속도로 700℃까지 승온 후, 1시간 유지시켜 탄소화과정을 거친다. 그 다음, 1시간 30분 동안 0.1 sccm/min의 분사속도로 스팀을 주입하면서 스팀활성화한 후, 실온까지 냉각하였다. 상기와 같이 스팀활성화법을 통해 제조된 셀룰로오즈 기반 탄소기반 흡착제는 증류수에서 1~2회 세척하여 120℃의 진공오븐에서 12시간 이상 완전 건조시켰다.
1 g of the cellulose fiber was thoroughly washed with distilled water and ethanol solution at room temperature for about 2 hours, completely dried at 80 ° C for more than 12 hours, then impregnated in a 5% boric acid aqueous solution for 60 minutes and completely dried at 80 ° C for 24 hours Prepared. The chemically impregnated cellulose fibers were placed in a muffle furnace and heated to 200 DEG C at a heating rate of 4 DEG C / min in an air atmosphere, followed by holding for 15 minutes to obtain oxidized stabilized cellulose fibers. The prepared oxidized stabilized cellulose fibers were put in a tubular furnace, heated to 700 ° C at a heating rate of 2 ° C / min under a nitrogen (N 2 ) atmosphere, and then carbonized by holding for 1 hour. Then, steam was injected at an injection speed of 0.1 sccm / min for 1 hour and 30 minutes while steam was being injected, followed by cooling to room temperature. As described above, the cellulose-based carbon-based adsorbent prepared through the steam activation method was washed once or twice in distilled water and completely dried in a vacuum oven at 120 ° C. for 12 hours or more.
실시예 6.Example 6.
셀룰로오즈 섬유 1 g을 상온에서 증류수 및 에탄올 용액에 2 시간정도 교반하여 완전히 세척하여 80℃에서 12시간 이상 완전히 건조한 후, 2%의 황산암모늄 수용액에 40분 동안 첨착시키고, 80℃에서 24 시간 완전 건조하여 준비하였다. 화학적 첨착처리된 셀룰로오즈 섬유를 머플퍼니스에 넣고 공기 분위기하에서 1.5 ℃/min의 승온속도로 200℃까지 승온시켜 30분간 유지시켜 산화안정화된 셀룰로오즈 섬유를 얻었다. 준비된 산화안정화된 셀룰로오즈 섬유는 튜브형 퍼니스에 넣고 질소(N2) 분위기 하에서 3℃/분의 승온 속도로 700℃까지 승온 후, 1시간 유지시켜 탄소화과정을 거친다. 그 다음, 1시간동안 0.25 sccm/min의 분사속도로 스팀을 주입하면서 스팀활성화한 후, 실온까지 냉각하였다. 상기와 같이 스팀활성화법을 통해 제조된 셀룰로오즈 기반 탄소기반 흡착제는 증류수에서 1~2회 세척하여 120℃의 진공오븐에서 12시간 이상 완전 건조시켰다.
1 g of cellulose fiber was thoroughly washed with distilled water and ethanol solution at room temperature for 2 hours, completely dried at 80 ° C. for more than 12 hours, then impregnated with 2% aqueous ammonium sulfate solution for 40 minutes and dried at 80 ° C. for 24 hours Respectively. The chemically impregnated cellulose fibers were placed in a muffle furnace and heated to 200 DEG C at a rate of 1.5 DEG C / min in an air atmosphere and held for 30 minutes to obtain oxidized stabilized cellulose fibers. The prepared oxidized stabilized cellulose fibers were put in a tube type furnace, heated to 700 ° C at a heating rate of 3 ° C / min in an atmosphere of nitrogen (N 2 ), and then carbonized by holding for 1 hour. Then, steam was injected at an injection speed of 0.25 sccm / min for 1 hour while steam was being injected, and then cooled to room temperature. As described above, the cellulose-based carbon-based adsorbent prepared through the steam activation method was washed once or twice in distilled water and completely dried in a vacuum oven at 120 ° C. for 12 hours or more.
비교예 1.Comparative Example 1
셀룰로오즈 섬유 1 g을 상온에서 증류수 및 에탄올 용액에 2 시간정도 교반하여 완전히 세척하여 80℃에서 12시간 이상 완전히 건조한 후, 머플퍼니스에 넣고 공기 분위기하에서 2 ℃/min의 승온속도로 200℃까지 승온시켜 30분간 유지시켜 산화안정화된 셀룰로오즈 섬유를 얻었다. 준비된 산화안정화된 셀룰로오즈 섬유는 튜브형 퍼니스에 넣고 질소(N2) 분위기 하에서 2℃/분의 승온 속도로 800℃까지 승온 후, 1시간 유지시켜 탄소화과정을 거친 후, 실온까지 냉각하였다. 상기와 같이 제조된 셀룰로오즈 기반 탄소기반 흡착제는 증류수에서 1~2회 세척하여 120℃의 진공오븐에서 12시간 이상 완전 건조시켰다.
1 g of the cellulose fiber was thoroughly washed with distilled water and ethanol solution at room temperature for about 2 hours, completely dried at 80 DEG C for more than 12 hours, then put in a muffle furnace and heated to 200 DEG C at a rate of 2 DEG C / min in an air atmosphere And then kept for 30 minutes to obtain oxidized and stabilized cellulose fibers. The prepared oxidized stabilized cellulose fibers were placed in a tubular furnace, heated to 800 ° C at a heating rate of 2 ° C / min in an atmosphere of nitrogen (N 2 ), maintained for 1 hour, carbonized, and then cooled to room temperature. The cellulose-based carbon-based adsorbent prepared as described above was washed once or twice in distilled water and completely dried in a vacuum oven at 120 ° C. for 12 hours or more.
이상, 본 발명내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적인 기술은 단지 바람직한 실시태양일 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, it will be apparent to those skilled in the art that this specific description is only a preferred embodiment and that the scope of the present invention is not limited thereby. It will be obvious. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (4)
(2) 상기 (1)단계에서 건조된 셀룰로오즈 섬유를 과산화수소, 붕산, 황산암모늄 중에서 선택되는 1 이상의 0.05 내지 10 vol.%의 농도를 갖는 화학적 첨착제를 이용하여 화학적 첨착시키는 단계;
(3) 상기 (2)단계에서 화학적 첨착시킨 셀룰로오즈 섬유를 150 ℃에서 60 분간 열처리하여 산화안정화시키는 단계;
(4) 상기 (3)단계에서 산화안정화시킨 셀룰로오즈 섬유를 850 ℃에서 60 분간 열처리하여 탄소화시키는 단계; 및
(5) 상기 (4)단계에서 탄소화시킨 셀룰로오즈 섬유를 850 ℃에서 90 분간 스팀을 분사하여 스팀활성화시키는 단계;를 포함하는 탄소기반 이산화탄소 흡착제의 제조방법.(1) a pretreatment step in which cellulose fibers are agitated for 1 to 12 hours in a mixed solution of distilled water and ethanol, washed repeatedly three or more times, and then dried for 12 hours;
(2) chemically impregnating the cellulose fibers dried in the step (1) with a chemical extender having a concentration of 0.05 to 10 vol.% Or more selected from hydrogen peroxide, boric acid and ammonium sulfate;
(3) oxidizing and stabilizing the cellulose fibers chemically impregnated in the step (2) by heat treatment at 150 ° C for 60 minutes;
(4) carbonizing the cellulose fibers oxidized and stabilized in step (3) by heating at 850 ° C for 60 minutes; And
(5) A method for producing a carbon-based carbon dioxide adsorbent, comprising the step of spraying steam at 850 ° C for 90 minutes in the cellulose fiber carbonized in step (4).
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| KR20050081606A (en) * | 2004-02-16 | 2005-08-19 | 최용석 | Chemical filter and making a mehod |
| KR100665537B1 (en) * | 2005-09-21 | 2007-01-10 | 서준석 | Method for producing activated carbon fiber. |
| KR20090095699A (en) * | 2008-03-06 | 2009-09-10 | 전남대학교산학협력단 | Manufacturing method of Fibrous Adsorbent by blend electrospinning for VOC absorbent |
| KR101329104B1 (en) * | 2013-04-18 | 2013-11-14 | 삼공물산 주식회사 | Manufacturing method of rayon -type activated carbon fiber using potassium permanganate |
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