吸液驱气法在多孔材料微孔结构表征中的应用
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摘要
多孔材料对气体的吸附容量和吸附选择性主要由其微孔结构和表面性质决定。精确地测量多孔材料的微孔结构是气体吸附分离用多孔材料的制备和应用基础。77K N2吸附是测定多孔材料孔结构的标准方法之一。在77K低温下,N2分子动能很低,使得N2分子扩散到较窄的微孔(孔径小于0.7nm)内达到吸附平衡所需时间较长,难以准确测定较小微孔结构信息。而室温下小分子气体探针吸附则较77KN2吸附可以测量到更小的孔,获得更丰富的微孔信息。
本文提出了通过分析多孔材料吸液驱气体积或速率获得其微孔结构参数的想法,即吸液驱气法。并建立了测量多孔材料吸液驱气体积和速率的装置。
根据巨正则蒙特卡洛法模拟得到的N2在炭分子筛内的理论表观密度,由测量的炭分子筛吸水驱替出的N2体积计算N2在炭分子筛微孔内的表观密度,得到炭分子筛的微孔孔径。该方法测量得到的炭分子筛微孔孔径与常温N2吸附法测量得到的结果一致。根据液体只可进入孔径尺寸比其分子直径大的孔内的原理,通过比较炭分子筛吸液驱N2的体积得到炭分子筛的微孔孔口尺寸分布。该方法测量得到的炭分子筛微孔孔口尺寸主要分布在0.28-0.37nm。同时利用该方法跟踪了化学气相沉积制备炭分子筛过程中样品微孔孔径及孔口尺寸分布的变化。
根据液体只可进入孔径尺寸比其分子直径大的孔的原理,通过比较活性炭吸液驱CH4和N2的体积得到活性炭的微孔孔径分布。与77K N2吸附法测量的结果相比,该方法能够测量到活性炭中更小尺寸的孔。得到活性炭的微孔孔径分布后,结合动态法测量的CH4/N2分离因子分析了活性炭的微孔结构对其选择吸附CH4/N2混合气中CH4的影响。结果表明,活性炭样品微孔孔径分布不同,其CH4/N2分离因子也不相同,其微孔孔径分布,尤其是孔径<0.48nm的微孔对其选择吸附混合气CH4/N2中的CH4起着非常重要的作用。
通过比较测量的ZSM-5吸液驱CH4和N2的体积得到ZSM-5的微孔孔径分布。吸液驱气法测量的ZSM-5的微孔孔径主要分布在0.48nm左右,与77K N2吸附测量的结果一致。
考察了温度、气体种类、粒度、液体粘度和极性等对炭分子筛、活性炭和沸石分子筛吸液驱气速率的影响。结果表明,炭分子筛、活性炭和ZSM-5吸水驱气的速率随着温度的升高,样品粒度的减小而加快,炭分子筛吸水驱气的速率受气体分子直径的影响。炭分子筛、活性炭和沸石分子筛吸水驱N2过程同时受大孔和微孔扩散控制。当炭分子筛和ZSM-5粒度分别减小至0.250-0.180mm和0.850-1.400mm时,样品吸水驱N2速率不再随粒度变化而变化,粒度分别减小至0.250-0.180mm和0.850-1.400mm的炭分子筛和ZSM-5吸水驱N2的过程只受微孔控制。活性炭和13X沸石分r筛吸液驱N2的速率受液体探针的极性和粘度影响。在此基础上,考察了化学气相沉积时间对炭分子筛微孔吸水驱N2速率影响,进而计算了该过程的活化能。实验结果表明,炭分子筛微孔吸水驱N2的速率随化学气相沉积时间的延长减慢；活化能随之增加。
The gas adsorption capacity and gas mixture selectivity of porous materials may be mainly caused by the micropore texture and surface properties. Hence, to develop better porous materials for the gas mixture separation and evaluate whether they are appropriate for application, an accurate means for assessing the micropore texture of the porous materials is needed. N2adsorption at77K is currently employed as a standard technique for the pore size determination. However, the application of this technique to ultramicropore is limited because N2is adsorbed at unreasonably slow rates in this kind pore at cryogenic temperature. The pore size characterized by smaller gas adsorption at ambient temperature extends to samller than that by N2adsorption at77K.
In this dissertation, characterization of microporous texture of porous materials by analyzing the volume or rate of gas recovered by liquid imbibition is proposed. An experimental set-up was built to measure the volume or rate of gas recovered by liquid imbibition.
The volume of gas recovered by the water imbibition was measured and applied to evaluate the density of the N2adsorbed in the carbon molecular sieves. The micropore size of the carbon molecular sieves was determined by comparing the N2density from the water-N2imbibition with that calculated by Grand Canonical Monte Carlo simulation. The micropore size evaluated by the liquid-gas imbibition coincides with that obtained by N2adsorption at ambient temperature. The size-exclusion property of the carbon molecular sieves was estimated by comparing the volume of N2recovered by imbibition of liquids with varied molecular dimensions, because the liquid can probe only pores with mouth larger than the size of liquid molecules and only the gas in these pores can be replaced. The mian micropore mouth size distribution of the carbon molecular sieves for air separation dominates in0.28-0.37nm. Furthermore, the effect of chemical vapor deposition treatment on the porous texture of the carbon molecular sieves was revealed by the liquid-gas imbibition.
The micropore size distribution of the activated carbons was estimated by comparing the volume CH4and N2recovered by imbibition of liquids with varied molecular dimensions, respectively, because the liquid can probe only pores with size larger than the size of liquid molecules and only the gas in these pores can be replaced. The results showed that the pore sizes characterized by spontaneous liquid-gas imbibition extend to smaller than that by N2 adsorption at77K. The influence of micropore size on their selective adsorption of CH4from CH4/N2mixture is analyzed with the CH4/N2separation factors obtained by dynamic method. The separation factor for CH4/N2on activated carbons changes with the micropore size distribution. The micropore of activated carbons plays an important role in their selective adsorption of CH4from CH4/N2mixture, particularly those pores smaller than0.48nm.
The micropore size distribution of the ZSM-5was estimated by comparing the volume CH4and N2recovered by imbibition of liquids with varied molecular dimensions, respectively, because the liquid can probe only pores with mouth larger than the size of liquid molecules and only the gas in these pores can be replaced. The results showed that the dominated micropore size of the ZSM-5is about0.48nm, and the micropore size evaluated by the liquid-gas imbibition coincides with that obtained by N2adsorption at77K.
The effect of temperature, the kinds of gases, particle size, liquid viscosity and polarity on the rate of gas recovered by water imbibition in carbon molecular sieves, activated carbon and ZSM-5was investigated. The experimental results showed that the rate of N2recovered by water imbibition increases with the temperature incrcasea and the particle size decreases, showing that the rate of gas recovered by water imbibition is controlled by both the macropore and the micropore. The kinds of gases play some role in the rate of gas recovered by water imbibition in carbon molecular sieves. There is a critical particle size0.250-0.180mm and0.850-1.400mm for carbon molecular sieves and ZSM-5, respectively, below which the rate of N2recovered by water imbibition is independent of the particle size, showing that the rate of N2recovered by water imbibition in carbon molecular sieves and ZSM-5is only controlled by the micropore when the particle size of carbon molecular sieves and ZSM-5below0.250-0.180mm and0.850-1.400mm, respectively. The viscosity and polarity of the liquid, can influence the rate of N2recovered by imbibition in activated carbons and13X. Furthermore, the effect of chemical vapor deposition time on the rate of N2recovered by water imbibition in micropore of carbon molecular sieves is investigated. The experimental results show that the rate of N2recovered by water imbibition in micropore of carbon molecular sieves decrease as the time of chemical vapor deposition increases and the activation energy of N2recovered by water imbibition in micropore of carbon molecular sieves increases as the time of chemical vapor deposition increases.
本文提出了通过分析多孔材料吸液驱气体积或速率获得其微孔结构参数的想法,即吸液驱气法。并建立了测量多孔材料吸液驱气体积和速率的装置。
根据巨正则蒙特卡洛法模拟得到的N2在炭分子筛内的理论表观密度,由测量的炭分子筛吸水驱替出的N2体积计算N2在炭分子筛微孔内的表观密度,得到炭分子筛的微孔孔径。该方法测量得到的炭分子筛微孔孔径与常温N2吸附法测量得到的结果一致。根据液体只可进入孔径尺寸比其分子直径大的孔内的原理,通过比较炭分子筛吸液驱N2的体积得到炭分子筛的微孔孔口尺寸分布。该方法测量得到的炭分子筛微孔孔口尺寸主要分布在0.28-0.37nm。同时利用该方法跟踪了化学气相沉积制备炭分子筛过程中样品微孔孔径及孔口尺寸分布的变化。
根据液体只可进入孔径尺寸比其分子直径大的孔的原理,通过比较活性炭吸液驱CH4和N2的体积得到活性炭的微孔孔径分布。与77K N2吸附法测量的结果相比,该方法能够测量到活性炭中更小尺寸的孔。得到活性炭的微孔孔径分布后,结合动态法测量的CH4/N2分离因子分析了活性炭的微孔结构对其选择吸附CH4/N2混合气中CH4的影响。结果表明,活性炭样品微孔孔径分布不同,其CH4/N2分离因子也不相同,其微孔孔径分布,尤其是孔径<0.48nm的微孔对其选择吸附混合气CH4/N2中的CH4起着非常重要的作用。
通过比较测量的ZSM-5吸液驱CH4和N2的体积得到ZSM-5的微孔孔径分布。吸液驱气法测量的ZSM-5的微孔孔径主要分布在0.48nm左右,与77K N2吸附测量的结果一致。
考察了温度、气体种类、粒度、液体粘度和极性等对炭分子筛、活性炭和沸石分子筛吸液驱气速率的影响。结果表明,炭分子筛、活性炭和ZSM-5吸水驱气的速率随着温度的升高,样品粒度的减小而加快,炭分子筛吸水驱气的速率受气体分子直径的影响。炭分子筛、活性炭和沸石分子筛吸水驱N2过程同时受大孔和微孔扩散控制。当炭分子筛和ZSM-5粒度分别减小至0.250-0.180mm和0.850-1.400mm时,样品吸水驱N2速率不再随粒度变化而变化,粒度分别减小至0.250-0.180mm和0.850-1.400mm的炭分子筛和ZSM-5吸水驱N2的过程只受微孔控制。活性炭和13X沸石分r筛吸液驱N2的速率受液体探针的极性和粘度影响。在此基础上,考察了化学气相沉积时间对炭分子筛微孔吸水驱N2速率影响,进而计算了该过程的活化能。实验结果表明,炭分子筛微孔吸水驱N2的速率随化学气相沉积时间的延长减慢；活化能随之增加。
The gas adsorption capacity and gas mixture selectivity of porous materials may be mainly caused by the micropore texture and surface properties. Hence, to develop better porous materials for the gas mixture separation and evaluate whether they are appropriate for application, an accurate means for assessing the micropore texture of the porous materials is needed. N2adsorption at77K is currently employed as a standard technique for the pore size determination. However, the application of this technique to ultramicropore is limited because N2is adsorbed at unreasonably slow rates in this kind pore at cryogenic temperature. The pore size characterized by smaller gas adsorption at ambient temperature extends to samller than that by N2adsorption at77K.
In this dissertation, characterization of microporous texture of porous materials by analyzing the volume or rate of gas recovered by liquid imbibition is proposed. An experimental set-up was built to measure the volume or rate of gas recovered by liquid imbibition.
The volume of gas recovered by the water imbibition was measured and applied to evaluate the density of the N2adsorbed in the carbon molecular sieves. The micropore size of the carbon molecular sieves was determined by comparing the N2density from the water-N2imbibition with that calculated by Grand Canonical Monte Carlo simulation. The micropore size evaluated by the liquid-gas imbibition coincides with that obtained by N2adsorption at ambient temperature. The size-exclusion property of the carbon molecular sieves was estimated by comparing the volume of N2recovered by imbibition of liquids with varied molecular dimensions, because the liquid can probe only pores with mouth larger than the size of liquid molecules and only the gas in these pores can be replaced. The mian micropore mouth size distribution of the carbon molecular sieves for air separation dominates in0.28-0.37nm. Furthermore, the effect of chemical vapor deposition treatment on the porous texture of the carbon molecular sieves was revealed by the liquid-gas imbibition.
The micropore size distribution of the activated carbons was estimated by comparing the volume CH4and N2recovered by imbibition of liquids with varied molecular dimensions, respectively, because the liquid can probe only pores with size larger than the size of liquid molecules and only the gas in these pores can be replaced. The results showed that the pore sizes characterized by spontaneous liquid-gas imbibition extend to smaller than that by N2 adsorption at77K. The influence of micropore size on their selective adsorption of CH4from CH4/N2mixture is analyzed with the CH4/N2separation factors obtained by dynamic method. The separation factor for CH4/N2on activated carbons changes with the micropore size distribution. The micropore of activated carbons plays an important role in their selective adsorption of CH4from CH4/N2mixture, particularly those pores smaller than0.48nm.
The micropore size distribution of the ZSM-5was estimated by comparing the volume CH4and N2recovered by imbibition of liquids with varied molecular dimensions, respectively, because the liquid can probe only pores with mouth larger than the size of liquid molecules and only the gas in these pores can be replaced. The results showed that the dominated micropore size of the ZSM-5is about0.48nm, and the micropore size evaluated by the liquid-gas imbibition coincides with that obtained by N2adsorption at77K.
The effect of temperature, the kinds of gases, particle size, liquid viscosity and polarity on the rate of gas recovered by water imbibition in carbon molecular sieves, activated carbon and ZSM-5was investigated. The experimental results showed that the rate of N2recovered by water imbibition increases with the temperature incrcasea and the particle size decreases, showing that the rate of gas recovered by water imbibition is controlled by both the macropore and the micropore. The kinds of gases play some role in the rate of gas recovered by water imbibition in carbon molecular sieves. There is a critical particle size0.250-0.180mm and0.850-1.400mm for carbon molecular sieves and ZSM-5, respectively, below which the rate of N2recovered by water imbibition is independent of the particle size, showing that the rate of N2recovered by water imbibition in carbon molecular sieves and ZSM-5is only controlled by the micropore when the particle size of carbon molecular sieves and ZSM-5below0.250-0.180mm and0.850-1.400mm, respectively. The viscosity and polarity of the liquid, can influence the rate of N2recovered by imbibition in activated carbons and13X. Furthermore, the effect of chemical vapor deposition time on the rate of N2recovered by water imbibition in micropore of carbon molecular sieves is investigated. The experimental results show that the rate of N2recovered by water imbibition in micropore of carbon molecular sieves decrease as the time of chemical vapor deposition increases and the activation energy of N2recovered by water imbibition in micropore of carbon molecular sieves increases as the time of chemical vapor deposition increases.
引文
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