垮越临界温度的分子筛吸附: 微孔体积填充理论的适用性

用高真空重量法测定了NaX分子筛对不同吸附质NH3, H2O, C2H5OH等的吸附等温线, 用微孔体积填充理论对吸附等温线进行非线性拟合, 得到满意结果。表明该理论不但可扩展到以静电场为主的吸附体系, 还可适用于吸附温度高于吸附质临界温度的吸附体系。计算结果表明, NaX吸附不同吸附质测得的极限空腔体积基本相同, 且与结构分析得到的空腔体积一致, 进一步表明微孔体积填充理论对该体系的适用性。计算了各种吸附质的极限吸附量, 以及某填充度下的蚊分吸附热随着温度的变化趋势。可为固体吸附式制冷系统的设计与制造提供理论依据及有关掺数。     

ZSM-5沸石的吸附性能和微孔体积填充理论适用性的研究

用真空重量法测定了自制的ZSM-5沸石对苯(20—300℃)和水(20—200℃)的吸附等温线;比较了用或不用有机胺合成的该沸石的吸水性能;探讨了微孔体积填充理论(TVFM)对沸石—蒸气体系的适用性。对ZSM-5—C_6H_6和ZSM-5—H_2O体系分别给出n值为1.3和0.9的指数式吸附平衡方程,并在较宽温度和填充率范围内计算吸附等温线和用这种新的形式确定沸石微孔体积,得到了与实验值较为一致的结果。     

若干吸附理论对在ZSM-5沸石上吸附的适用性

测定了饱和烃和不饱和烃分子在一价阳离子交换型ZSM-5沸石分子筛上的吸附等温线。探讨了微孔体积填充理论、Wilkins方程和Langmuir吸附理论对以上吸附体系的适用性;测得的吸附等温线用最小二乘法和解线性方程组借助电子计算机进行拟合得出相应的回归方程。实验结果表明,Langmuir吸附理论能较好地描述环己烷在氢型和碱金属阳离子交换型ZSM-5沸石上的吸附体系,计算出的极限吸附量a_o值与实验值相符,但对其他体系未得满意结果:二常数的Wilkins方程可用于求算吸附体系的初始吸附热,并能较好地描述等温线的低压部分;与以上各理论比较,微孔体积填充理论能更满意地表征我们所研究的吸附体系,籍以计算了极限吸附量a_o,分布级数n和特征吸附功E值三个物理常数,并为一价阳离子交换型ZSM-5沸石上对苯和环己烷等分子的吸附作用主要是色散力作用提供有力依据。     

ZSM-35沸石对水和苯的吸附及其孔结构

用高真空重量法测定了20—200℃范围内,ZSM-35佛石对水和苯的吸附等温线。讨论了Langmuir,BET理论和微孔体积填充理论对ZSM-35—H_2O体系的适用性,提出了用Pickett三参数方程描述沸石—蒸气体系吸附平衡,确定沸石表面积及用W_0=10~(-4)·S·n＇·t式计算沸石微孔体积的方法。在ZSM-35—H_2O体系具有特征曲线温度不变性的基础上,给出了该体系吸附平衡方程θ=exp[-(A/3800)~(1.1)],并由此外推计算了吸附等温线和确定了沸石的孔体积。结果表明,ZSM-35沸石的比表面积为375m~2/g,微孔体积为0.158ml/g。     

高比表面活性碳微球分离H2中少量CO2

以实验数据为依据, 结合双Langmuir模型研究了用高比表面活性碳微球材料分离H2中少量CO2的行为. 在实验中, 用高精度的IGA-003重力吸附仪测定了温度为298、273 和268 K, 压力在0-1.8 MPa范围内CO2、H2及n(CO2):n(H2)=1:9混合物在活性碳微球中的吸附等温线. 比较不同吸附模型的计算结果与实验数据, 结果表明, 双Langmuir模型与实验结果拟合得较好; 而且通过结合理想吸附溶液理论, 该模型可以准确地计算不同的混合物体系(包括H2-CO2体系)的吸附量和吸附选择性. 利用该模型求解了不同温度下各组分的分吸附量, 得到了CO2的吸附选择性;在268 K和1.7 MPa下, CO2的吸附选择性可达到73.4, 表明活性碳微球是一种优秀的吸附H2中少量CO2的材料.     

应用Polanyi吸附势理论描述超高交联树脂对多环芳烃的吸附

研究了萘、苊、芴三种多环芳烃类化合物在超高交联吸附树脂HC-1上的静态吸附平衡行为,分别采用Langmuir、Freundlich和Poanyi-Dubinin-Manes模型方程对吸附平衡数据进行了拟合分析,并探讨了吸附机理。实验结果表明,基于微孔填充机理的Polanyi-Dubinin-Manes方程能较好地拟合吸附平衡数据,表明树脂的微孔区对吸附起着重要作用。实验结果也表明,吸附质分子尺寸是影响吸附效果的重要因素,吸附质分子越大则吸附量越小;采用吸附质分子尺寸对Polanyi-Dubinin-Manes方程中吸附势密度进行修正,以体积吸附量对修正后吸附势密度作图,可得到一条与吸附质无关的特性曲线,根据该曲线方程可有效预测二、三环的多环芳烃化合物在HC-1上的吸附性能。     

CXN天然沸石的研究Ⅱ.吸附性质

采用N2,NH3,CO2,乙烯,丙烯,水,甲醇,乙醇,丙醇等作为吸附剂,研究了由我国CXN天然沸石改性制得的H-STI和Na-STI沸石的吸附性质,H-STI和Na-STI沸石的BET表面积及微孔孔体积约为420m2/g和0.20m3/g.根据NH3和CO2在H-STI沸石上的吸附等温线计算得到它们的吸附热分别为44.8和26.5kJ/mol.乙烯,丙烯,甲醇,乙醇,丙醇等在Na-STI沸石上的吸附等温线表明该沸石对有机分子的吸附具有链长选择性.在低分压下水相对于甲醇的吸附量表明沸石具有一定的疏水性质.     

活性炭吸附CO2与其微孔体积的关系

对五种活性炭样品进行液氮温度下的N2吸附、碘吸附测定和冰点下的CO2吸附表征。结果表明,碘吸附值测定法和基于N2吸附等温线的BET方程、D-R方程,孔结构参数都不能正确反映活性炭对CO2的吸附特性;由CO2吸附等温线得到的D A模型参数也不适合分析活性炭吸附CO2特性;CO2吸附等温线的密度泛函理论（DFT）分析结果表明,CO2在活性炭上的吸附发生在极微孔内,DFT分析的微孔孔容与吸附等温线反映的吸附性能完全一致。因此,根据CO2吸附等温线的DFT模型是准确反映活性炭吸附CO2特性的表征分析方法。     

活性炭纤维的微孔结构水吸附

测定了两种活性炭纤维（ACF）的氮气、水吸附等温线和XPS,研究了ACF的微孔结构和表面性质,用αs图分析氮吸附等温线获得了ACF的比表面积、微孔容量和微孔径。XPS表明在ACF表面存在多种不同结合状态的氧。水在ACF上的吸附等温线呈V型,具有很大的脱附滞后环。水通过与ACF表面的氧形成氢键发生吸附。ACF表面的初始吸附点多,则在低、中压时的水吸附量就大。     

吸附树脂和活性炭对气体中苯的吸附研究

采用了动态吸附实验方法研究了吸附树脂NDA-201和椰壳型活性炭C1对苯蒸汽的吸附行为.对吸附平衡数据采用Dubinill-Astakov方程进行了拟合分析,并根据吸附剂孔结构特征探讨了吸附机理.实验结果表明,两种吸附剂的苯吸附等温线存在交叉现象,对高浓度苯蒸汽吸附治理可采用NDA-201树脂,低浓度则采用椰壳型活性炭C1;Dubinin-Astakov方程能用来对两种吸附剂的等温线进行拟合,表明吸附剂的微孔区域对吸附起着重要作用.微孔体积计算值的比较和特征曲线叠合的程度说明了.Polanyi吸附势理论更适合于描述椰壳型活性炭C1对苯的吸附,这可能是由于椰壳型活性炭C1的孔分布集中于微孔区,而NDA-201树脂除了微孔外还有一定量的中孔和大孔.     

Theory of volume filling of micropores applied to the description of methane adsorption on the microporous carbon adsorbent AUK

Methane adsorption on the microporous carbon adsorbent AUK was calculated on the basis of Dubinin’s theory of volume filling of micropores in the temperature range 177.7—393 K and at pressures from 1 Pa to 6 MPa. The calculated isotherms of absolute adsorption were compared with the isotherms of methane obtained experimentally. Good agreement between the calculated and experimentally measured amounts adsorbed is observed in the area of applicability of the theory at micropore ranging in coverage θ from 0.25 to 0.95. The adsorption isosters were calculated for the same pressure and temperature ranges. The adsorption isosters satisfactorily represent the temperature dependence of the amount of methane adsorbed obtained experimentally. The calculations gave for the thermal coefficient of limiting adsorption a value of 6h_calc = 1.64• 10^-3 K^-1., which exceeds the experimental value by ∼15%.     

氢原子在Ni(100), Ni(111)和Ni(110)面上吸附扩散势能面的结构

本文构造了氢-镍相互作用的5参数Morse势, 用经典的对势方法研究氢原子在Ni(100), Ni(111)和Ni(110)面上的吸附和扩散, 得到氢原子在三个表面上的吸附位、吸附几何、结合能及本征振动等数据, 和实验结果符合得很好。同时, 系统地研究了三个体系的吸附扩散势能面结构。     

比表面积和孔径分布测定与计算方法的改进

本文比较了BET多层吸附模型, Pickett有限层吸附模型以及Dubinin微孔填充模型, 并在此基础上, 假定多层吸附和微孔填充两种过程同时发生, 导出一个修正的吸附方程式, 并说明修正后的方程具有较大的适用性和准确性, 在孔径分布的测定中, 用H2替代He作为载气, 大大降低测定成本, 应用微机实现数据运算过程微机化和结果的图谱化, 大大缩短处理时间。     

Optimization of structural and energy characteristics of adsorbents for methane storage

Using numerical and analytical methods, a model for microporous carbon adsorbents with slit-shaped pores of different widths was developed. Such pores are formed during activation procedure by the removal of the hexagonal carbon layers burnt out in a graphite-like crystallites. Dubinin’s theory of volume filling of micropores was used to calculate methane adsorption equilibria on these model adsorbents. Isobaric dependences of methane adsorption on pore width, specific micropore volumes, and the specific surface were plotted in the range of pressures from 1 to 10 MPa. It was found that the isobaric adsorption curves had a maximum the position of which depends on both the structural-energy characteristics of the adsorbent and thermodynamic conditions chosen to operate the adsorption system. As pressure increased, the maximum of adsorption shifts to the porous systems with wider pores and larger micropore volume.     

AlPO4-11分子筛的吸附热力学性质

AlPO_4-n系列分子筛是八十年代初由美国联合碳化物公司开发的一类新型分子筛,据报导到目前为止已经合成出20种不同型号结构的AlPO_4分子筛。经X-射线多晶和单晶衍射结构分析,部分AlPO_4分子筛的结构已搞清楚,AlPO_4-11结构也已经测定,它具有十元环一维孔道,孔口大小为0.67nm×0.40nm的分子筛。     

Molecular dynamics study of hydrated faujasite-type zeolites

Molecular dynamics (MD) simulations of hydrated zeolite NaX (Si/Al = 1.0) and NaY (Si/Al = 2.0) were done at a temperature of 300 K. The calculation results show that the adsorption of water occurs via a three-step mechanism in zeolite NaX: (1) adsorption around Na, (2) formation of a monolayer on the walls, and (3) pore filling in the supercage during which adsorbed water molecules are localized around the 12-membered rings. Zeolite NaY adsorbs in a similar manner. However, at intermediate hydration states, cluster formation occurs around Na instead of monolayer formation. The calculated energy distribution functions suggest that in zeolite NaX, the water vapor adsorption can be expressed by using the Langmuir model with two adsorption sites, but in zeolite NaY, it is not Langmuir-type adsorption.     

甲醇与氧在银钯合金上的吸附和反应

本文运用UPS、超高真空程序升温反应谱(TPRS)研究了氧和甲醇在银钯合金上的吸附和反应。实验结果表明, 合金表面存在两种分别与Ag和Pd原子有关的活性位; 少量钯原子的存在, 一方面提供了甲醇分解反应的活性中心, 另一方面通过与银之间的电子相互作用, 削弱了氧与银的结合, 增强了表面吸附氧的反应活性, 从而改变了甲醇氧化反应的选择性。     

Adsorption and adsorption-induced deformation of NaX zeolite under high pressures of carbon dioxide

Isotherms of carbon dioxide adsorption and adsorption-induced deformation of pelletized crystalline NaX zeolite at pressures of 0.2--5.4 MPa and temperatures of 195--423 K are measured. The adsorption deformation is positive at low zeolite micropore filling (a < 1 mmol g^-1) at all temperatures, i.e., the zeolite suffers expansion. Further, as the amount of the adsorbed substance increases, the adsorption deformation curves pass first through a maximum and then through a minimum. In the range of high fillings (a > 7 mmol g^-1) the NaX zeolite shows dramatic expansion.     

On the applicability of the theory of ideal adsorption solutions to equilibria in the N2-O2-zeolite NaX system

Experimental data on the joint adsorption of a nitrogen-oxygen gas mixture on zeolite NaX were analyzed using the theory of ideal adsorption solutions. Acceptable accuracy was obtained in calculations of binary isotherms from the adsorption isotherms of the pure gas mixture components. The calculated binary isotherms can be used to determine the parameters of the mathematical models of binary adsorption, for instance, competitive adsorption models.