The present invention relates in general to the field of thermodynamic modeling, and more particularly, to a generalization of thermodynamic Langmuir isotherms for mixed-gas adsorption equilibria.
Without limiting the scope of the invention, its background is described in connection with Langmuir isotherm modeling.
The chemical process industry is among the most essential manufacturing sectors around the globe. The United States alone has a chemical product output of greater than $979 billion in 2019. [1] Over the years, the energy demands to operate these chemical processes grow rapidly due to an increase in chemical products demand. The separation of chemical products consumes nearly 45-55% of the industrial energy and 10-15% of the overall energy produced in the United States. [2, 3] To date, distillation, membrane-based separation, and adsorptive separation are among the widely used separation technologies. [4] However, after decades of optimization and improvements, distillation processes remain the dominant separation technologies and account for more than 50% of overall separation energy consumed due to low energy efficiency. [4, 5] Membrane-based separation is an emerging and energy-efficient technology but its industrial applications continue to be limited by low selectivity, low capacity, low stability, and elevated fouling tendency. [4, 6] In contrast, adsorptive separation is relatively established, energy-efficient, and heavily practiced in the air separation industry and others. [7]
In spite of the high industrial potential of adsorptive separation, lack of experimental measurement of mixed-gas adsorption equilibrium data hampers its wide application in industry. [8, 9] Therefore, it is imperative that robust and accurate thermodynamic models be developed and validated to reliably extrapolate and predict mixed-gas adsorption equilibria from pure component adsorption isotherms. [10] Among a wide range of models and theories proposed to estimate mixed-gas adsorption equilibria are Vacancy Solution Theory (VST) [11], Loading Ratio Correlation (LRC) [12], the extended Langmuir (eL) [13], Ideal Adsorbed Solution Theory (IAST) [14], etc. Although VST predicts azeotropic adsorption behavior, it is thermodynamically inconsistent and the model parameters lack physical significance. [7,15] The LRC model can reasonably predict mixed-gas adsorption equilibria for ideal systems. [16] However, its empiricism and failure to predict adsorption azeotrope diminish LRC's applicability to model and design adsorbers. [7, 17] Similarly, the widely practiced eL model is thermodynamically inconsistent and fails to address the pressure dependence as it presents a constant selectivity at all pressures for a given mixed-gas adsorption system. [7, 18, 19] The benchmark to predict mixed-gas adsorption equilibria from pure component adsorption isotherms and the only thermodynamically consistent model is IAST. However, IAST does not account for surface heterogeneity and it fails to predict nonideal mixed-gas adsorption equilibria. [10. 20] In short, the state-of-the-art adsorption isotherm models are either thermodynamically inconsistent or incapable of describing the nonideal behavior of mixed-gas adsorption equilibria.
Recently, for the first time, Kaur et al. [21] proposed an adsorption Nonrandom Two-Liquid (aNRTL) activity coefficient model to account for the adsorbent surface heterogeneity and its underlying adsorbate-adsorbent interactions in the adsorbate phase. Subsequently, substituting adsorbate and vacant site concentrations in the classical Langmuir (cL) adsorption rate formulation with activities using aNRTL model, Chang et al. [22] presented a thermodynamic Langmuir (tL) isotherm to capture the adsorbent surface heterogeneity for pure component adsorption and isosteric heat of adsorption. [23] Moreover, Tun and Chen [10] implemented IAST in combination with the aNRTL model and showed the feasibility to reliably correlate and predict binary and multicomponent gas adsorption equilibria from pure component isotherms at constant spreading pressure. However, the adsorbate phase activity coefficients in the IAST thermodynamic framework are functions of spreading pressure. [24] As spreading pressure is not a measurable property, it is believed that no theoretical investigations have adequately addressed the spreading pressure dependence [25] for the adsorbate phase activity coefficients.
What is needed is a new Langmuir model that allows an accurate account of both surface loading dependence and adsorbate phase composition dependence for mixed-gas adsorption equilibria.
A simple and yet thermodynamically consistent multicomponent adsorption isotherm expression to estimate mixed-gas adsorption equilibria from pure component adsorption isotherms is described herein. The generalized Langmuir (gL) adsorption isotherm treats the adsorbent as an integral part of the adsorption system, assumes competitive adsorption of multiple adsorbates on adsorbent surface, tracks the available adsorbent vacant site surface area, and computes adsorbate and vacant site activities with an area-based aNRTL activity coefficient model. Devoid of the needs to consider the system spreading pressure constraint and the spreading pressure dependence of the adsorbate phase activity coefficients as imposed by IAST, the gL model allows an accurate account of both surface loading dependence and adsorbate phase composition dependence for mixed-gas adsorption equilibria.
In one embodiment, a computerized method for estimating an adsorption equilibria for one or more gases from pure component adsorption isotherms include providing one or more processors, a memory communicably coupled to the one or more processors and an output device communicably coupled to the one or more processors, calculating, using the one or more processors, an adsorption of each gas on a constant monolayer adsorption surface and the generalized Langmuir isotherm equations:
where: θi is an adsorbate phase area fraction covered with the gas i,
The adsorption of each gas is provided to the output device, and a chemical process or product is developed using the adsorption of each gas. The method can be implemented by an apparatus, system, computer, or non-transitory computer readable medium encoded with a computer program for execution by a processor that performs the steps of the method.
In one aspect, the generalized Langmuir isotherm equations reduce to
when (1) the adsorbate and vacant site effective areas are the same A1=A2= . . . =Ai=Aϕ, or equivalently, the saturation loadings of adsorbates and phantom molecule are same n10=n20= . . . =n10=nϕ0, and (2) the adsorbate phase activity coefficients are unity γi=γϕ=1. In another aspect, the one or more gases comprise a mixed gas having two or more components. In another aspect, the constant monolayer adsorption surface comprises activated carbon, LiLSX or Zeolite H-mordenite. In another aspect, the gas i comprises CH4, C2H4, C2H6, C3H6, N2, O2, CO2, H2S, or C3H8. In another aspect, the one or more gasses comprise a mixed gas selected from CH4—C2H4, CH4—C2H6, C2H4—C2H6, C2H4—C3H6, and C2H6—C3H6. In another aspect, the one or more gasses comprise a mixed gas selected from N2 and O2. In another aspect, the one or more gasses comprise a mixed gas selected from H2S—CO2, C3H8—H2S, and C3H8—CO2.
In another embodiment, an apparatus, system or computer includes at least one input/output interface, a data storage, and one or more processors communicably coupled to the at least one input/output interface and the data storage. The one or more processors calculate an adsorption of each gas i on a constant monolayer adsorption surface Ao using generalized Langmuir isotherm equations:
where: θi is an adsorbate phase area fraction covered with the gas i,
In one aspect, the generalized Langmuir isotherm equations reduce to
when (1) the adsorbate and vacant site effective areas are the same A1=A2= . . . =Ai=Aϕ, or equivalently, the saturation loadings of adsorbates and phantom molecule are same n10=n20= . . . =ni0=nϕ0, and (2) the adsorbate phase activity coefficients are unity γi=γϕ=1. In another aspect, the one or more gases comprise a mixed gas having two or more components. In another aspect, the constant monolayer adsorption surface comprises activated carbon, LiLSX or Zeolite H-mordenite. In another aspect, the gas i comprises CH4, C2H4, C2H6, C3H6, N2, O2, CO2, H2S, or C3H8. In another aspect, the one or more gasses comprise a mixed gas selected from CH4—C2H4, CH4—C2H6, C2H4—C2H6, C2H4—C3H6, and C2H6—C2H6. In another aspect, the one or more gasses comprise a mixed gas selected from N2 and O2. In another aspect, the one or more gasses comprise a mixed gas selected from H2S—CO2, C3H8—H2S, and C3H8—CO2.
In another embodiment, a method of adsorbing one or more gases includes providing a vessel containing a constant monolayer adsorption surface, introducing one or more gases into the vessel, wherein the adsorption of each gas on the constant monolayer adsorption surface is determined by the generalized Langmuir isotherm equations:
where: θi is an adsorbate phase area fraction covered with the gas i,
The adsorption of each gas i is provided to the output device, and a chemical process or a product is developed using the adsorption of each gas i. A product can be produced in accordance with this method.
In one aspect, the generalized Langmuir isotherm equations reduce to
when (1) the adsorbate and vacant site effective areas are the same A1=A2= . . . =Ai=Aϕ, or equivalently, the saturation loadings of adsorbates and phantom molecule are same n10=n20= . . . =ni0=nϕ0, and (2) the adsorbate phase activity coefficients are unity γi=γϕ=1. In another aspect, the one or more gases comprise a mixed gas having two or more components. In another aspect, the constant monolayer adsorption surface comprises activated carbon, LiLSX or Zeolite H-mordenite. In another aspect, the gas i comprises CH4, C2H4, C2H6, C3H6, N2, O2, CO2, H2S, or C3H8. In another aspect, the one or more gasses comprise a mixed gas selected from CH4—C2H4, CH4—C2H6, C2H4—C2H6, C2H4—C3H6, and C2H6—C3H6. In another aspect, the one or more gasses comprise a mixed gas selected from N2 and O2. In another aspect, the one or more gasses comprise a mixed gas selected from H2S—CO2, C3H8—H2S, and C3H8—CO2.
For a more complete understanding of the features and advantages of the present invention, reference is now made to the detailed description of the invention along with the accompanying figures and in which:
While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention.
To facilitate the understanding of this invention, a number of terms are defined below. Terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention. Terms such as “a”, “an” and “the” are not intended to refer to only a singular entity but include the general class of which a specific example may be used for illustration. The terminology herein is used to describe specific embodiments of the invention, but their usage does not limit the invention, except as outlined in the claims.
A thermodynamically consistent model to predict mixed-gas adsorption equilibria from pure gas adsorption isotherms is described herein. A generalization of thermodynamic Langmuir isotherm for pure component adsorption, the model assumes competitive adsorption of multiple adsorbates on adsorbent surface and it applies an area-based adsorption Nonrandom Two-Liquid activity coefficient model in the activity coefficient calculations for the adsorbate phase. The resulting generalized Langmuir (gL) isotherm properly captures both surface loading dependence and adsorbate phase composition dependence for mixed-gas adsorption equilibria. The model is validated with accurate representations of gas adsorption equilibrium data for wide varieties of unary, binary, and ternary gas systems. The model results are further compared with those calculated from extended Langmuir isotherm and Ideal Adsorbed Solution Theory.
Starting from the fundamental adsorption and desorption reactions of pure adsorbate gas A on an adsorbent surface containing vacant sites S:
The adsorption reaction with rate constant ka results in occupied sites denoted with AS. In contrast, the desorption reaction having rate constant kd results in pure gas A and vacant sites S. Once the adsorption equilibrium has been achieved, the rates of adsorption and desorption become equal as shown in Eq. (2).
Here [S] and [AS] denote the classical Langmuir (cL) site concentrations of vacant sites and occupied sites, respectively. The occupied sites can be expressed in the amount adsorbed for adsorbate component 1, n1. The vacant sites can be represented as (n10−n1), where n10 is the saturation amount adsorbed for component 1. The apparent adsorption equilibrium constant K1 can be expressed as a function of the adsorbate phase site concentrations as:
where x1 is the ratio of n1 and n10. Simplification of Eq. (3) for x1 yields the classical Langmuir isotherm shown in Eq. (4):
The classical Langmuir isotherm disregards the adsorbent surface heterogeneity upon assuming the rates of adsorption and desorption are proportional to the site concentrations. Chang et al. [22] proposed the thermodynamic Langmuir isotherm to address the surface heterogeneity by substituting the site concentrations with the site activities expressed as the product of site concentration and site activity coefficient as shown in Eq. (5), leading to the thermodynamic Langmuir isotherm expressed as Eq. (6):
where K1o is the intrinsic adsorption equilibrium constant of adsorbate component 1, x1 is the ratio of n1 and n10, and xϕ, representing the vacant site fraction on the adsorbent surface, is calculated as (1−x1). y1 is the activity coefficient of component 1 on the occupied sites and γϕ is the activity coefficient of “phantom” molecule ϕ on the vacant sites. The reference state for adsorbate component 1 is the adsorbate phase fully occupied with component 1 while the reference state for the phantom molecule ϕ is the absorbate phase with vacant sites only.
In addition to addressing the surface heterogeneity, this work further proposes that there is a constant total adsorbent surface area, Ao, which is covered with adsorbate component 1 with the “effective” molecular area, A1. The adsorbate phase area fraction covered with component 1, θ1, is a function of Ao, A1, and n1, expressed as:
where nϕ and nϕ0 are the remaining amount and the maximum amount of vacant sites, respectively, Aϕ is the “effective” area of phantom molecule ϕ, with nitrogen chosen as the model molecule for ϕ. x1 is the ratio of n1 and nT referred as the adsorbate phase mole fraction of component 1, and xϕ is the ratio of nϕ and nT and referred as the adsorbate phase mole fraction of vacant sites. While Ao remains constant, the occupied site area fraction, θ1, and the vacant site area fraction, θϕ, change with respect to the loading of component 1. Upon considering both the site activities and the site area fractions, the generalized Langmuir isotherm is expressed in Eqs. (13)-(14) for adsorbate component 1 and vacant site area fractions:
Here, q1 is the ratio of effective area of component 1 and the effective area of phantom molecule ϕ and it should depend on the adsorbent surface characteristics, adsorption temperature, and the local minimal energy adsorbate molecular configuration on the adsorbent surface. [26] γ1 and γϕ are the activity coefficients of component 1 and phantom molecule, respectively, which are functions of x1, xϕ, A1, and Aϕ. Eq. (13) reduces to the thermodynamic Langmuir (tL) isotherm, Eq. (6), when the effective area of adsorbate is same as the effective area of phantom molecule. Eq. (13) further reduces to the classical Langmuir isotherm, Eq. (4), when both the effective area of adsorbate and the effective area of phantom molecule are same and the activity coefficients are unity.
The generalized Langmuir isotherm for pure component adsorption can be readily extended for mixed-gas adsorption. For a competitive adsorption of multiple adsorbates on a constant monolayer adsorption surface area, A°, the corresponding generalized Langmuir isotherm equations for mixed-gas adsorption equilibria can be expressed as:
where γi is the gas phase mole fraction of adsorbate component i, n is the number of adsorbates, nT is the sum of the total amount adsorbed of all adsorbates and the remaining amount of vacant sites. θi is the adsorbate phase area fraction covered with component i, and θϕ is the adsorbate phase vacant site area fraction. Eq. (16) defines the intrinsic adsorption equilibrium constant of component i while Eqs. (17)-(20) express the adsorbate phase mole fractions of component i and vacant sites and their relationships. Eqs. (21) and (22) track the adsorbate phase area fractions occupied by adsorbate component i and vacant sites, respectively. Eq. (23) shows, while the total adsorbent surface area, Ao, remains constant, the occupied area for component i, niAi and the are for vacant sites, nϕAϕ, vary with loading and adsorbate phase compositions.
Rearrangement of Eqs. (16)-(20) in combination with Eqs. (21)-(22) results in the generalized Langmuir isotherm equations for mixed-gas adsorption equilibria as presented in Eqs. (24) and (25).
Here, qi is the ratio of effective area of component i and effective area of phantom molecule, γi and γϕ represent the activity coefficients of component i and vacant sites, respectively, which are functions of xi's, xϕ, Ai's, and Aϕ. In summary, solving n number of Eq. (24) for n number of adsorbates coupled with Eq. (25) for nϕ along with an appropriate activity coefficient model results in the generalized Langmuir isotherm for mixed-gas adsorption equilibria. The generalized Langmuir isotherm reduces to the extended Langmuir isotherm, shown in Eq. (27), if the following two conditions are satisfied: 1) the adsorbate and vacant site effective areas are the same, i.e., A1=A2= . . . =Ai=Aϕ, or equivalently, the saturation loadings of adsorbates and phantom molecule are same, i.e., n10=n20= . . . =ni=n00, and 2) the adsorbate phase activity coefficients are unity. Devoid of the simplifying assumptions of the extended Langmuir isotherm, the generalized Langmuir isotherm provides a thermodynamically consistent generalization of the extended Langmuir expression.
Area-Based Multicomponent aNRTL Model
The original adsorption NRTL model derived from the two-fluid theory does not take into account the effective areas of adsorbates and phantom molecule on the adsorbate phase. [21] To make aNRTL model consistent with the generalized Langmuir model formulation, the aNRTL model formulation has been revisited to incorporate the adsorbate area fractions. The derivation of area-based aNRTL model is provided below.
Consider an adsorbent surface containing energetically non-interacting multiple adsorption sites where each site “0” is surrounded with the molecules of n number of adsorbates. To address the local composition of multicomponent adsorbate phase, Nonrandom two-liquid theory [36] has been implied while incorporating the size of adsorbates. So, the sum of local area fractions of n adsorbates around the adsorbent site “0” shall be unity, written as:
Here, θi0 is the local area fractions of ith adsorbate near the adsorbent site “0” that can be expressed in the form of area fraction and mole fraction as follow:
Here, gi indicates the interaction energy between the ith adsorbate and the adsorption site. α denotes the non-randomness factor and qi is the effective area of the ith adsorbate.
To derive the expression for molar excess Gibbs energy for area based aNRTL model, the multicomponent adsorbate system is treated with the two-liquid theory. [37] Starting from the sum of changes of residual Gibbs energy of the adsorbate phase:
Here g is the residual Gibbs energy. Now, using Eq. (29) and (32) results in:
Eq. (34) can be simplified to Eq. (35):
Simplification of Eq. (35) results in the final expression of Gibbs energy for multicomponent adsorbate systems, written as:
Afterwards, the activity coefficients are related to the partial molar excess Gibbs energy expressed as follow:
Rearranging Eq. (36) and then substituting in Eq. (37) results in:
Here, p=j=k=1, 2, 3, . . . , i, . . . , m. Now, taking the derivative of Eq. (39) with respect to ng at constant T, π, and nj≠i;
Upon simplification, Eq. (40) can be written as:
Now, taking the partial derivative of 2nd term as expressed in Eq. (41):
Upon simplification of Eq. (42), the resulting expressions are:
Now, combining Eq. (41) and (44) results in:
Simplification of Eq. (45) provides the final expression of activity coefficient of component i in the multicomponent gas adsorption equilibria system.
Here, qi=Ai/Aϕ is the ratio of effective adsorbate area of component i and that of the model molecule (nitrogen) for phantom molecule, and xi is the adsorbate phase mole fraction of component i.
It is worth noting that the gL isotherm treats the adsorbent as a part of the adsorption system. In other words, the adsorbate phase of a single component gas adsorption system is treated as a binary system of adsorbate component 1 and phantom molecule ϕ for adsorbent vacant sites with the composition of (x1, xϕ). Likewise, the adsorbate phase of a binary gas adsorption system is treated as a ternary system of two adsorbates and phantom molecule with the composition of (x1, x2, xϕ). For a mixed-gas adsorption system with n components, adsorbent vacant sites or phantom molecule ϕ included in the mixture, the excess Gibbs energy expression for the adsorbate phase is:
The corresponding activity coefficient expression is given in Eq. (50):
where α is the nonrandomness factor fixed at 0.3 and τij's are the adjustable binary interaction parameters for the i-j pair, with τij=−τji. In short, the area-based adsorption NRTL activity coefficients are functions of xi's, xϕ, Ai's, and Aϕ, and τij's.
Accurate representation of experimental pure component adsorption isotherm data is the first step towards successful modeling of mixed-gas adsorption equilibria. The classical Langmuir (cL), thermodynamic Langmuir (tL), and generalized Langmuir (gL) models are used herein to represent pure component adsorption isotherms. Requiring no activity coefficient calculations, cL makes use of two model parameters (Ki and ni0). In contrast, both tL and gL isotherms require three model parameters (τiϕ, Kio, and ni0). For internal consistency, the original aNRTL model [21] is used in the activity coefficient calculation for tL and the area-based aNRTL model presented above is used with gL. Note that, with literature reported values for Ao and Ai the ni0 parameter in gL can be calculated per Eq. (23) and leave gL with only two adjustable model parameters, i.e., τiϕ and Kio. The effective areas in gL, Ai's, are notably dependent on adsorbent, adsorption temperature, and the configuration of adsorbate molecule on the adsorbent surface. [26] The recommended effective areas of adsorbates and adsorbent surface areas are available in the literature. [26] To regress the adsorption isotherm parameters, a Maximum Likelihood Principle-based objective function is minimized, [27] given as follow:
where σ indicates the standard deviation of the experimental data set to 0.05 mol/kg while nicalc and niexpt denote the calculated and experimentally measured adsorption amounts. To evaluate the performance of isotherm fitting, Root Mean Square Error (RMSE) is used, and it is expressed as:
where N represents the total number of data points.
Nine pure component adsorption isotherm data sets are selected to support subsequent mixed-gas adsorption equilibria studies and they have been used to identify the model parameters of cL, tL, and gL pure component isotherms. These data include adsorption isotherms of CH4, C2H4, C2H6, and C3H6 on activated carbon at 323 K, [28] N2 and O2 on LiLSX at 303.15 K [29], and CO2, H2S, and C3H8 on zeolite H-mordenite at 303.15 K [30]. The graphical representation of these data sets and the model results are shown in the
The results show both tL and gL perform much better than cL. In addition, while tL and gL show very similar RMSE's in fitting the data, some of the values of tL isotherm parameter ni0 seem unreasonable. For example, the regressed tL ni0 value for CH4 adsorbed on activated carbon is exceedingly small and only a fraction (˜20%) of that of C2H4. In contrast, given a constant Ao for an adsorbent, the values of gL isotherm parameter ni0 are inversely proportional to the values of Ai. Note that the adsorbate saturation loadings, i.e., ni0's, on activated carbon shown in Table 3 are calculated from the reported adsorbent surface area of
and the corresponding adsorbate effective areas in the literature [32, 33]. For LiLSX, Ai is known for N2 [26], ni0 for N2 is fitted to the isotherm data, and Ao is then calculated to be
For zeolite H-mordenite, Ai is known for CO2 [26], ni0 for CO2 is fitted to the isotherm data, and Ao is then calculated to be
consistent with the literature value of
Ten binary mixed-gas adsorption systems have been investigated with eL, IAST, and gL. The regressed gL parameters and the corresponding RMSE's for all the binary mixed-gas adsorption systems with the three models are reported in Table 4. For internal model consistency, the cL model is used to calculate pure component adsorption isotherms in the eL calculations for mixed-gas adsorption equilibria. The tL model is used to calculate pure component adsorption isotherms and the corresponding spreading pressures in the IAST calculations. In contrast, the gL isotherm is used in both pure component adsorption isotherms and mixed-gas adsorption equilibria.
Five binary mixed-gas adsorption of hydrocarbons on activated carbon at 323 K and 0.1 bar [28] are investigated. gL estimations accurately match the experimental data and outperform eL predictions for the five binary systems of CH4—C2H4, CH4—C2H6, C2H4—C2H6, C2H4—C3H6, and C2H6—C3H6. RMSEs of IAST and gL are same for all five binary systems on activated carbon.
Estimate Surface Loading from Adsorption Equilibria
The unique feature of gL to consider adsorbent as a part of adsorption system makes the tracking of adsorbent surface loading possible. For the adsorption of N2—O2 binary on LiLSX at 1.013 bar and 6.08 bar and at 303.15 K [29],
For the two binary mixtures exhibiting azeotropic behavior, i.e., C3H8—H2S binary on zeolite H-mordenite at 0.081 bar and 303.15 K [30] and C3H8—CO2 binary on zeolite H-mordenite at 0.41 bar and 303.15 K [30],
The mixed-gas adsorption equilibria phase diagram analogous to P-xy phase diagram in vapor-liquid equilibria can be generated from gL.
Estimate Activity Coefficients from Adsorption Equilibria
Besides tracking the adsorbent surface loading, gL captures the adsorbent surface heterogeneity by tracking the adsorbate phase activity coefficients of adsorbates and vacant sites. As previously mentioned, full adsorbent surface coverage of pure adsorbate molecules is defined as the reference state for adsorbates. For the adsorption of N2—O2 binary on LiLSX at 1.013 (black lines denoted as 702) and 6.08 bar (red lines denoted as 704), and 303.15 K [29],
To examine the predictive capability of gL, the mixed-gas adsorption equilibria is predicted for CH4—C2H4—C2H6 ternary and C2H4—C2H6—C3H6 ternary on activated carbon at 323 K and 0.1 bar [28] and CO2— H2S—C3H8 ternary on zeolite H-mordenite at 303.15 K and 0.007-0.1342 bar [30]. The predictions with eL, IAST, and gL are based on the pure component adsorption isotherm parameters reported in Table 1, Table 2, and Table 3 and the regressed τij's reported in Table 4. The parity plots of above mentioned mixed-gas adsorption equilibria predictions for apparent adsorbate phase compositions are presented in
The average relative deviation (ARD %) results are reported in Table 5.
For mixed-gas adsorption equilibria for CH4—C2H4—C2H6 ternary and C2H4—C2H6-C3H6 ternary on activated carbon at 323 K and 0.1 bar [28], the eL predictions have the highest ARD's of 47% and 38%, respectively. IAST and gL provide very similar predictions for CH4—C2H4-C2H6 ternary and C2H4—C2H6—C3H6 ternary on activated carbon with ARD around 27% and 18%, respectively. In case of mixed-gas adsorption for CO2— H2S—C3H8 ternary on zeolite H-mordenite at 303.15 K and 0.007-0.1342 bar [30], the IAST predictions yield the highest ARD of nearly 49%, followed by the eL predictions with ARD of 27%. The gL predictions yield the best predictions with ARD of 19%.
Comparison of IAST-aNRTL and generalized Langmuir capabilities
In addition to the comparison with eL and IAST, the gL results have also been checked against our prior investigation for mixed-gas adsorption equilibria based a modified IAST and the original adsorption NRTL model [10]. Specifically, Table 6 reports the RMSEs for IAST-aNRTL and gL for five binary systems: N2—O2 binary at 1.013 bar and at 6.08 bar on LiLSX at 303.15 K [29], H2S—CO2 binary at 0.156 bar, C3H8—H2S binary at 0.081 bar, and C3H8—CO2 binary at 0.41 bar on zeolite H-mordenite at 303.15 K. [30] Overall, the gL results for the mixed-gas adsorption equilibria are slightly better than the IAST-aNRTL results. More importantly, the gL results are thermodynamically consistent while the IAST-aNRTL results are valid at constant spreading pressures even though the adsorption equilibria are at constant system pressures. Moreover, gL does not require the computationally expansive calculations on spreading pressures as required for IAST-aNRTL.
A simple, robust, and thermodynamically consistent adsorption model for pure component adsorption isotherms and mixed-gas adsorption equilibria has been described herein. Treating the adsorbent surface as an integral part of adsorption systems, the proposed generalized Langmuir isotherm accurately correlates and predicts mixed-gas adsorption equilibria without the need to compute “spreading pressure” as required for Ideal Adsorbed Solution Theory. Tested with mixed-gas adsorption equilibria data for ten binary and three ternary systems, the generalized Langmuir isotherm outperforms both extended Langmuir and Ideal Adsorbed Solution Theory in predicting mixed-gas adsorption equilibria. As the generalized Langmuir isotherm tracks the surface loading in terms of occupied and vacant sites surface area fractions and the surface heterogeneity in terms of the adsorbate phase activity coefficients, it is shown for the first-time complete phase diagrams for mixed-gas adsorption equilibria analogous to the TPxy phase diagrams for vapor-liquid equilibria. Additionally, the generalized Langmuir isotherm predictions for mixed-gas adsorption equilibria can be used to elucidate the spreading pressure dependence of adsorbate phase activity coefficients in the context of Ideal Adsorbed Solution Theory.
Some other embodiments of the present invention will now be described with respect to
The apparatus, system or computer 900 can be used to estimate an adsorption equilibria for one or more gases from pure component adsorption isotherms. The one or more processors calculate an adsorption of each gas i on a constant monolayer adsorption surface Ao using generalized Langmuir isotherm equations:
where: θi is an adsorbate phase area fraction covered with the gas i,
The adsorption of each gas i is provided to the output device 908, and a chemical process or a product is developed using the adsorption of each gas i.
In one aspect, the generalized Langmuir isotherm equations reduce to
when (1) the adsorbate and vacant site effective areas are the same A1=A2= . . . =Ai=Aϕ, or equivalently, the saturation loadings of adsorbates and phantom molecule are same n10=n20= . . . =ni0=nϕ0, and (2) the adsorbate phase activity coefficients are unity γi=γϕ=1. In another aspect, the one or more gases comprise a mixed gas having two or more components. In another aspect, the constant monolayer adsorption surface comprises activated carbon, LiLSX or Zeolite H-mordenite. In another aspect, the gas i comprises CH4, C2H4, C2H6, C3H6, N2, O2, CO2, H2S, or C3H8. In another aspect, the one or more gasses comprise a mixed gas selected from CH4—C2H4, CH4—C2H6, C2H4—C2H6, C2H4—C2H6, and C2H6—C3H6. In another aspect, the one or more gasses comprise a mixed gas selected from N2 and O2. In another aspect, the one or more gasses comprise a mixed gas selected from H2S—CO2, C3H8—H2S, and C3H8—CO2.
where: θi is an adsorbate phase area fraction covered with the gas i,
The adsorption of each gas is provided to the output device in block 1006, and a chemical process or product is developed using the adsorption of each gas in block 1008. The method 1000 can be implemented by the apparatus 900 or by a non-transitory computer readable medium encoded with a computer program for execution by a processor that performs the steps of the method 1000.
In one aspect, the generalized Langmuir isotherm equations reduce to
when (1) the adsorbate and vacant site effective areas are the same A1=A2= . . . =Ai=Aϕ, or equivalently, the saturation loadings of adsorbates and phantom molecule are same n10=n20= . . . =ni0?=nϕ0, and (2) the adsorbate phase activity coefficients are unity γi=γϕ=1. In another aspect, the one or more gases comprise a mixed gas having two or more components. In another aspect, the constant monolayer adsorption surface comprises activated carbon, LiLSX or Zeolite H-mordenite. In another aspect, the gas i comprises CH4, C2H4, C2H4, C2H6, N2, O2, CO2, H2S, or C3H8. In another aspect, the one or more gasses comprise a mixed gas selected from CH4—C2H4, CH4—C2H6, C2H4—C2H6, C2H4—C3H6, and C2H6—C3H6. In another aspect, the one or more gasses comprise a mixed gas selected from N2 and O2. In another aspect, the one or more gasses comprise a mixed gas selected from H2S—CO2, C3H8—H2S, and C3H8—CO2.
where: θi is an adsorbate phase area fraction covered with the gas i,
In one aspect, the generalized Langmuir isotherm equations reduce to
when (1) the adsorbate and vacant site effective areas are the same A1=A2= . . . =Ai=Aϕ, or equivalently, the saturation loadings of adsorbates and phantom molecule are same n10=n20= . . . =ni0=nϕ0, and (2) the adsorbate phase activity coefficients are unity γi=γϕ=1. In another aspect, the one or more gases comprise a mixed gas having two or more components. In another aspect, the constant monolayer adsorption surface comprises activated carbon, LiLSX or Zeolite H-mordenite. In another aspect, the gas i comprises CH4, C2H4, C2H6, C3H6, N2, O2, CO2, H2S, or C3H8. In another aspect, the one or more gasses comprise a mixed gas selected from CH4—C2H4, CH4—C2H6, C2H4—C2H6, C2H4—C3H6, and C2H6—C3H6. In another aspect, the one or more gasses comprise a mixed gas selected from N2 and O2. In another aspect, the one or more gasses comprise a mixed gas selected from H2S—CO2, C3H6—H2S, and C3H8—CO2.
It will be understood that particular embodiments described herein are shown by way of illustration and not as limitations of the invention. The principal features of this invention can be employed in various embodiments without departing from the scope of the invention. Those skilled in the art will recognize or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims.
All publications and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.
The use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” The use of the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and/or.” Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects.
As used in this specification and claim(s), the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited features, elements, components, groups, integers, and/or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers and/or steps. In embodiments of any of the compositions and methods provided herein, “comprising” may be replaced with “consisting essentially of” or “consisting of”. As used herein, the term “consisting” is used to indicate the presence of the recited integer (e.g., a feature, an element, a characteristic, a property, a method/process step or a limitation) or group of integers (e.g., feature(s), element(s), characteristic(s), property(ies), method/process steps or limitation(s)) only. As used herein, the phrase “consisting essentially of” requires the specified features, elements, components, groups, integers, and/or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers and/or steps as well as those that do not materially affect the basic and novel characteristic(s) and/or function of the claimed invention.
The term “or combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context.
As used herein, words of approximation such as, without limitation, “about”, “substantial” or “substantially” refers to a condition that when so modified is understood to not necessarily be absolute or perfect but would be considered close enough to those of ordinary skill in the art to warrant designating the condition as being present. The extent to which the description may vary will depend on how great a change can be instituted and still have one of ordinary skill in the art recognize the modified feature as still having the required characteristics and capabilities of the unmodified feature. In general, but subject to the preceding discussion, a numerical value herein that is modified by a word of approximation such as “about” may vary from the stated value by at least ±1, 2, 3, 4, 5, 6, 7, 10, 12 or 15%.
All of the compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.
To aid the Patent Office, and any readers of any patent issued on this application in interpreting the claims appended hereto, applicants wish to note that they do not intend any of the appended claims to invoke paragraph 6 of 35 U.S.C. § 112, U.S.C. § 112 paragraph (f), or equivalent, as it exists on the date of filing hereof unless the words “means for” or “step for” are explicitly used in the particular claim.
For each of the claims, each dependent claim can depend both from the independent claim and from each of the prior dependent claims for each and every claim so long as the prior claim provides a proper antecedent basis for a claim term or element.
This application claims priority to U.S. Provisional Application Ser. No. 63/226,303, filed Jul. 28, 2021, the entire contents of which are incorporated herein by reference. This application is related to PCT Application Serial No. PCT/US20/45586, filed Aug. 10, 2020, which claims priority to U.S. Provisional Application Ser. No. 62/860,319, filed Jun. 12, 2019. The entire contents of the foregoing applications are incorporated herein by reference.
This invention was made with government support under DE-EE0007888 awarded by the U.S. Department of Energy. The government has certain rights in the invention.
Filing Document | Filing Date | Country | Kind |
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PCT/US2022/037972 | 7/22/2022 | WO |
Number | Date | Country | |
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63226303 | Jul 2021 | US |