Comparative study of zeolite 5A and zeolite 13X in air separation by pressure swing adsorption

Ehsan Javadi Shokroo,Danial Jafari Farsani,Hadiseh Khalilpour Meymandi,Nadia Yadollahi 한국화학공학회 2016 Korean Journal of Chemical Engineering Vol.33 No.4

The performance of zeolites 5A and 13X is numerically investigated in oxygen separation from air by a two-bed PSA system. The effect of operating variables such as adsorption step time, PH/PL ratio and cycle time was investigated on product purity and recovery. The simulation results showed that nitrogen adsorption capacity on zeolite 13X was slightly more than the one on zeolite 5A. In the completely same operating conditions, zeolite 5A had a larger mass transfer zone than zeolite 13X. Therefore, the adsorption and desorption rate of nitrogen on zeolite 5A is less than zeolite 13X. Moreover, for the equal volume of adsorbed nitrogen on both adsorbents, zeolite 5A is more capable rather than zeolite 13X to desorb much more volume of nitrogen at certain time. Furthermore, for achieving oxygen with purity of 96%, utilizing zeolite 5A is more economical than zeolite 13X, when 5.5<PH/PL<7 and 75<cycle time≤90.

활성탄과 제올라이트 13X 충진탑을 사용한 TSA 공정에서 조업조건이 벤젠의 흡착 및 탈착에 미치는 영향

정민영 ( Min-young Jung ),서성섭 ( Sung-sup Suh ) 한국공업화학회 2018 공업화학 Vol.29 No.5

본 연구는 VOC 제거 기술인 TSA 공정에서 제올라이트 13X와 활성탄이 채워진 두 종류의 탑을 사용하여 원료농도, 질소 유량, 수증기 유량, 탑 온도 등 조업조건의 영향을 분석하였다. 본 연구의 TSA 사이클은 흡착단계, 수증기 탈착단계, 건조 및 냉각단계로 구성되었다. 2% 벤젠 농도에서 제올라이트 13X와 활성탄의 사이클 당 전체 흡착량은 각각 4.44 g과 3.65 g으로 활성탄보다 충전밀도가 큰 제올라이트 13X가 더 많은 양의 벤젠을 흡착할 수 있었다. 수증기 탈착의 결과에서 수증기 유량을 증가시키고 탑의 외부 가열로 온도를 높이면 탈착시간이 짧아지고 배출되는 벤젠의 농도가 높아지는 것으로 나타났다. 2% 벤젠 농도에서 수증기 유량을 75 g/hr로 증가시키면 탈착시간이 1 hr에서 최대 33 min까지 단축되어 상대적으로 건조 및 냉각단계의 시간이 늘어나 수증기 제거와 탑 냉각을 충분히 진행할 수 있었다. 탑 온도를 높이면 탈착량이 증가하나 150 ℃ 이상에서는 에너지소비는 증가하는 반면 탈착량은 거의 일정했다. 연속 사이클 조업에서 재생단계 완료 시 잔존하게 되는 벤젠의 비율이 늘어나면 흡착제 working capacity 감소의 원인이 될 수 있다. 제올라이트 13X를 이용해 연속 사이클 공정실험을 수행한 결과 탑 내부에 잔존하는 벤젠의 비율이 4번째 사이클 이후 일정한 값으로 유지되었다. The effects of operating conditions such as benzene concentration, nitrogen flow rate, steam flow rate, and bed temperature on TSA process were experimentally investigated as a potential VOC removal technology using two kinds of beds packed with activated carbon and zeolite 13X. The TSA cycle studied was composed of the adsorption step, steam desorption step, and drying and cooling step. At 2% benzene concentration, the total adsorption amounts of zeolite 13X and activated carbon were 4.44 g and 3.65 g, respectively. Since the zeolite 13X has a larger packing density than that of the activated carbon, the larger benzene amount could be adsorbed in a single cycle. Increasing the water vapor flow rate to 75 g/hr at 2% benzene concentration reduced the desorption time from 1 hr to a maximum of 33 min. If the desorption time is shortened, the drying and cooling step period can be relatively increased. Accordingly, the steam removal and bed cooling could be sufficiently performed. The desorption amounts increased with the increase of the bed temperature. However, the energy consumption increased while the desorption amount was almost constant above 150 ℃. In the continuous cycle process, when the amount of remained benzene at the completion of the regeneration step increased, it might cause a decrease in the working capacity of the adsorbent. The continuous cycle process experiment for zeolite 13X showed that the amount of remained benzene at the end of regeneration step maintained a constant value after the fourth cycle.

활성탄과 제올라이트 13X에서 벤젠, 톨루엔 및 자일렌 증기의 흡착 및 확산 특성

정민영,서성섭 한국화학공학회 2019 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.57 No.3

Adsorption equilibrium and intraparticle diffusion characteristics of benzene, toluene, and xylene vapors on activated carbon and zeolite 13X were investigated. Static adsorption experiments were carried out under the pressure range of 0.01~0.07 bar while changing the adsorption temperature to 293.15 K, 303.15 K, and 313.15 K, respectively. Adsorption equilibrium was analyzed by Langmuir, Freundlich and Toth models. The adsorption energy was 5.26~31.0 kJ/mol representing physical adsorption characteristics. The maximum adsorption capacity on activated carbon was the largest for benzene, and the smallest for xylene. Toluene was in between. In the case of zeolite 13X, the maximum adsorption capacity was the largest for xylene, and the smallest for benzene as opposed to activated carbon. The effective diffusion coefficients of gas adsorbate were measured to be about 10-5~10-4 cm2/s, and increased with temperature. As the pressure increased, the effective diffusion coefficients were decreased. The dependence of effective diffusion coefficients on temperature and pressure was greater in zeolite 13X particles than in activated carbon. Therefore, it is necessary to express the diffusion coefficients as a function of pressure in order to predict the precise dynamic behavior of the adsorption process using zeolite 13X where the pressure fluctuation occurs abruptly. 본 연구에서는 활성탄과 제올라이트 13X에 대한 벤젠, 톨루엔 및 자일렌 증기의 기체 흡착평형과 입자내부의 확산특성을 조사하였다. 압력 범위 0.01~0.07 bar 사이에서 흡착온도를 각각 293.15 K, 303.15 K, 313.15 K로 변화시키면서 정적흡착실험을 수행하였다. 흡착평형은 Langmuir, Freundlich 및 Toth 흡착등온식을 적용하여 해석하였다. 그 결과 표준편차는 Langmuir 식과 Toth 식에서 낮았으며, Freundlich 식에서 표준편차가 가장 컸다. Langmuir 상수를Arrhenius 식의 형태로 표현하여 구한 흡착에너지는 5.26~31.0 kJ/mol 정도로 물리흡착의 특성을 나타냈다. 흡착제에따른 흡착질의 최대 흡착량은 활성탄의 경우 벤젠, 톨루엔, 자일렌으로 갈수록 최대 흡착량이 감소했으며, 제올라이트13X의 경우 활성탄과는 반대로 최대 흡착량이 자일렌에서 가장 크고 벤젠에서 가장 작게 나타났다. 벤젠, 톨루엔 및자일렌 증기의 유효확산계수는 약 10-5~10-4 cm2/s 정도로 나타났으며, 압력이 증가함에 따라 값이 작아지고 온도가 증가함에 따라 값이 커지는 경향을 보였다. 온도와 압력의 변화에 따른 유효확산계수의 변화는 활성탄보다 제올라이트13X에서 민감하게 나타났다. 따라서 압력 변동이 급격하게 발생하는 흡착공정에서 제올라이트 13X를 사용할 경우 정밀한 동적거동 예측을 위해서는 확산계수를 압력에 대한 함수로 표현하는 것이 필요하다.

분말 소화약제가 흡착된 제올라이트의 소화 특성

신창섭 ( Chang Sub Shin ),박호준 ( Ho Jun Park ) 한국안전학회(구 한국산업안전학회) 2012 한국안전학회지 Vol.27 No.6

The use of dry chemical powder has been increased as it can be stored for a long period and sustain in stable condition compared to gas of liquid phase extinguishing agents. A new type of dry chemical powder using Zeolite was produced in the research. Chemical powder was adsorbed into Zeolite 13X, a porous material appearing negative catalytic effect, to create extinguishing powder botaining core shell structure and measured physical pro-perties and run a small scale fire extinguishment. SEM, XRD, TA analysis was also executed, and extinguishing characteristics were measured by fire extinguishing experiment on oil pool fire. The experiment showed that the average particle size of Zeolite 13X was equivalent, indicating about 3±1 μm and thermal analysis result illustrated that Zeolite 13X showed exothermic reaction peaks at 900℃ due to solid-state transformation. Extinguishing charac-teristics on oil fire of NaHCO(3)/Zeolite 13X and NH(4)H(2)PO(4)/Zeolite were improved, influenced by adsorbed extingui-shing powders on Zeolite 13X and Zeolite 13X that contains high phase transition temperature.

분말 소화약제가 흡착된 제올라이트의 소화 특성

신창섭,박호준 한국안전학회 2012 한국안전학회지 Vol.26 No.6

The use of dry chemical powder has been increased as it can be stored for a long period and sustain in stable condition compared to gas or liquid phase extinguishing agents. A new type of dry chemical powder using Zeolite was produced in the research. Chemical powder was adsorbed into Zeolite 13X, a porous material appearing negative catalytic effect, to create extinguishing powder obtaining core shell structure and measured physical properties and run a small scale fire extinguishment. SEM, XRD, TA analysis was also executed, and extinguishing characteristics were measured by fire extinguishing experiment on oil pool fire. The experiment showed that the average particle size of Zeolite 13X was equivalent, indicating about 3±1 μm and thermal analysis result illustrated that Zeolite 13X showed exothermic reaction peaks at 900oC due to solid-state transformation. Extinguishing characteristics on oil fire of NaHCO3/Zeolite 13X and NH4H2PO4/Zeolite were improved, influenced by adsorbed extinguishing powders on Zeolite 13X and Zeolite 13X that contains high phase transition temperature

제올라이트 13X에 의한 배가스 성분의 흡착 특성 및 불순물의 영향

서성섭 ( Sung-sup Suh ),이호진 ( Ho-jin Lee ) 한국화학공학회 2016 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.54 No.6

산업체에서 많이 사용되는 연소공정은 배가스 성분의 회수나 제거를 필요로 한다. 최근에는 배가스로부터 이산화탄소를 회수하기 위해 제올라이트 13X를 사용하는 MBA(이동상흡착) 공정이 개발되었다. 본 연구에서는 제올라이트 13X에 대한 이산화탄소, 질소, 이산화황 및 수증기의 흡착 실험을 수행하여 흡착평형 및 고체입자 안으로의 흡착속도를 조사하였다. 여러 실험온도에서의 흡착데이터를 Langmuir, Toth, Freundlich 등온흡착식에 적용하여 각 흡착등온식의 파라미터를 구했고, 이론식에 의한 예측값과 실험데이터가 잘 일치함을 확인하였다. 이산화황과 수증기가 불순물로 존재할 경우에 주성분인 이산화탄소의 흡착량을 측정하였다. 이성분 흡착 데이터는 순수 성분에 대해 얻어진 파라미터를 extended Langmuir 등온흡착식에 적용하여 예측한 결과와 잘 일치하였다. 다만, H₂O 불순물이 대략 ~10^-5 H₂O mol/g zeolite 13X 이하 존재할 때에는 CO₂ 흡착량이 순수 CO₂의 흡착보다 오히려 소량 증가하는 현상이 관찰되었다. 실험으로 측정한 흡착속도를 구형 입자 확산모델에 적용하여 이산화탄소, 이산화황, 질소, 수분의 확산계수와 활성화에너지를 구했다. 미량의 불순물이 흡착되어있을 때는 이산화탄소나 이산화황의 확산계수가 줄어들었다. 본 연구에서 얻어진 파라미터 값들은 실제 흡착공정의 설계에 유용할 것이다. Most of combustion processess used in industries require recovering or removing flue gas components. Recently a new MBA (moving bed adsorption) process for recovering CO₂ using zeolite 13X was developed. In this study, adsorption experiments for carbon dioxide, nitrogen, sulfur dioxide, and water vapor on zeolite 13X were carried out. Adsorption equilibrium and adsorption rate into solid particle were investigated. Langmuir, Toth, and Freundlich isotherm parameters were calculated from the experiment data at various temperatures. Experimental results were con-sistent with the theoretically predicted values. Also CO₂ adsorption amount was measured under the conditions with impurities such as SO₂ and H₂O. Binary adsorption data were well fitted to the extended Langmuir isotherm using parameters obtained from pure component experiment. However, H₂O impurity less than, roughly, ~10^-5 H₂O mol/g zeo-lite 13X enhanced slightly CO₂ adsorption. Spherical particle diffusion model well described experimentally measured adsorption rate. Diffusion coefficients and activation energies of CO₂, SO₂, N₂, H₂O were obtained. Diffusion coeffi-cients of CO₂ and SO₂ decreased with small amount of preadsorbed impurity. Parameter values from this study will be helpful to design of real commercial adsorption process.

Zeolite 13X를 이용한 열저장 시스템에 대한 비정상 상태 성능 평가 연구

문석우(Seok-woo Moon),김경호(Gyeong-ho Kim),홍성국(Sung-kook Hong),윤시원(Si-won Yoon),위덕재,김범석(Beom Seok Kim),Jong-kyu Kim 대한기계학회 2022 대한기계학회 춘추학술대회 Vol.2022 No.11

Sorption thermal energy storage is a unique technology with high energy-storage density and low heat loss. We design an adsorption storage system that facilitates the packed bed with Zeolite 13X as the heat-generating material. The adsorption reaction between the water and Zeolite is analyzed using ANSYS Fluent. We assessed the reactors transient pressure drop and local exothermic characteristics and compared them with experimental results to validate analytic results. We investigate spatial and transient temperature variations and mass fraction inside the reactor, which are performance factors describing whether the Zeolite 13X reacted thoroughly during the adsorption process. Finally, we demonstrate that Zeolite 13X can efficiently react inside the reactor according to the proper operating conditions. Through this study, we attempt to present a feasible design of sorption thermal energy systems.

13X 제올라이트 흡착제 충진에 의한 Na형 Faujasite 제올라이트 분리막의 CO2/N2 선택도 및 CO2 투과도 동시 증가 현상

Churl Hee Cho,Jeong Gu Yeo,Young Soo Ahn,Moon Hee Han,Jong Ho Moon,Chang Ha Lee 한국막학회 2007 멤브레인 Vol.17 No.3

분리층 두께가 5 μm이며 Si/Al 몰비가 1.5인 Na형 faujasite 제올라이트 분리막을 이차성장 공정에 의하여 제조하였고, 투과부에 13X 제올라이트 흡착제 충진 전후의 진공모드에서의 CO2/N2 분리거동을 CO2/N2 몰비가 1인 혼합기체에 대하여 30℃에서 평가하였다. 충진된 13X 제올라이트 흡착제는 CO2 투과도와 CO2/N2 선택도를 동시에 증진시켰다. 이 현상은 13X 제올라이트 흡착제 충진이 다공성 α-알루미나 지지체의 기공채널을 통한 CO2 탈출을 증진시킴으로써 faujasite 제올라이트/α-알루미나 상계면에서의 CO2 탈착을 증진시켰기 때문으로 설명되었다. 본 논문으로부터 흡착제와 분리막의 혼성화는 일반적으로 보여지는 선택도와 투과도의 역비례 관계를 획기적으로 개선할 방법임이 확인되었다. Sodium type faujasite(FAU) zeolite membranes with a thickness of 5 μm and a Si/Al molar ratio of 1.5 were prepared by the secondary growth process. The CO2/N2 separation in the vacuum mode was investigated at 30℃ for an equimolar CO2-N2 mixed gas before and after embedding 13X zeolite beads in the permeate side. The embedded 13X zeolite beads improved both CO2 permeance and CO2/N2 separation factor, simultaneously. The phenomenon was explained by an increment in the CO2 desorption rate at the FAU zeolite/α-Al2O3 phase boundary due to an enhanced CO2 escaping through the pore channels of the α-Al2O3 support layer. In the present paper, it will be emphasized that a hybridization of a membrane with an adsorbent can provide a key to break through the trade-off between permeance and separation factor, generally shown in a membrane separation.

Zeolite 13X를 이용한 열저장 시스템에 대한 비정상 상태 성능 평가 연구

문석우(Seok-woo Moon),김경호(Gyeong-ho Kim),홍성국(Sung-kook Hong),윤시원(Si-won Yoon),위덕재,김범석(Beom Seok Kim),Jong-kyu Kim 대한기계학회 2022 대한기계학회 춘추학술대회 Vol.2022 No.11

Sorption thermal energy storage is a unique technology with high energy-storage density and low heat loss. We design an adsorption storage system that facilitates the packed bed with Zeolite 13X as the heat-generating material. The adsorption reaction between the water and Zeolite is analyzed using ANSYS Fluent. We assessed the reactors transient pressure drop and local exothermic characteristics and compared them with experimental results to validate analytic results. We investigate spatial and transient temperature variations and mass fraction inside the reactor, which are performance factors describing whether the Zeolite 13X reacted thoroughly during the adsorption process. Finally, we demonstrate that Zeolite 13X can efficiently react inside the reactor according to the proper operating conditions. Through this study, we attempt to present a feasible design of sorption thermal energy systems.

A Simultaneous Improvement in $CO_2$ Flux and $CO_2/N_2$ Separation Factor of Sodium-type FAU Zeolite Membranes through 13X Zeolite Beads Embedding

조철희,여정구,안영수,한문희,문종호,이창하,Cho, Churl-Hee,Yeo, Jeong-Gu,Ahn, Young-Soo,Han, Moon-Hee,Moon, Jong-Ho,Lee, Chang-Ha The Membrane Society of Korea 2007 멤브레인 Vol.17 No.3

분리층 두께가 5${\mu}m$이며 Si/Al 몰비가 1.5인 Na형 faujasite 제올라이트 분리막을 이차성장 공정에 의하여 제조하였고, 투과부에 13X 제올라이트 흡착제 충진 전후의 진공모드에서의 $CO_2/N_2$ 분리거동을 $CO_2/N_2$ 몰비가 1인 혼합기체에 대하여 $30^{\circ}C$에서 평가하였다. 충진된 13X 제올라이트 흡착제는 $CO_2$ 투과도와 $CO_2/N_2$ 선택도를 동시에 증진시켰다. 이 현상은 13X 제올라이트 흡착제 충진이 다공성 $\alpha$-알루미나 지지체의 기공채널을 통한 $CO_2$ 탈출을 증진시킴으로써 faujasite 제올라이트/$\alpha$-알루미나 상계면에서의 $CO_2$ 탈착을 증진시켰기 때문으로 설명되었다. 본 논문으로부터 흡착제와 분리막의 혼성화는 일반적으로 보여지는 선택도와 투과도의 역비례 관계를 획기적으로 개선할 방법임이 확인되었다. Sodium type faujasite(FAU) zeolite membranes with a thickness of 5${\mu}m$ and a Si/Al molar ratio of 1.5 were prepared by the secondary growth process. The $CO_2/N_2$ separation in the vacuum mode was investigated at $30^{\circ}C$ for an equimolar $CO_2-N_2$ mixed gas before and after embedding 13X zeolite beads in the permeate side. The embedded 13X zeolite beads improved both $CO_2$ permeance and $CO_2/N_2$ separation factor, simultaneously. The phenomenon was explained by an increment in the $CO_2$ desorption rate at the FAU zeolite/$\alpha-Al_2O_3$ phase boundary due to an enhanced $CO_2$ escaping through the pore channels of the $\alpha-Al_2O_3$ support layer. In the present paper, it will be emphasized that a hybridization of a membrane with an adsorbent can provide a key to break through the trade-off between permeance and separation factor, generally shown in a membrane separation.