Synthesis of Zn(NH3) (CO3) inorganic helical framework and its use for selective separation of carbon dioxide

Abstract

A novel one-pot solvothermal reaction based on urea hydrolysis to synthesize single crystals of the Zn(NH.sub.3)(CO.sub.3) inorganic helical framework and its applications in selective CO.sub.2 separation.

Claims

1. A method for capturing CO.sub.2 in a fixed bed column comprising: adsorbing CO.sub.2 from a gas mixture stream in a column comprising Zn(NH.sub.3)(CO.sub.3) sorbent at room temperature and at an adsorption pressure P.sub.ads; and regenerating the column adsorbing the CO.sub.2, after its saturation breakthrough, by desorption at room temperature and at a desorption pressure P.sub.des, wherein P.sub.des is less than P.sub.ads.

2. The method of claim 1 wherein the gas mixture is a CO.sub.2/O.sub.2 mixture.

3. The method of claim 2 wherein the capture is for an oxy-fuel CO.sub.2 process by pressure swing adsorption.

4. The method of claim 3 wherein the P.sub.ads/P.sub.des is about 5 atm/1 atm.

5. The method of claim 1 wherein the gas mixture is CO.sub.2/CH.sub.4.

6. The method of claim 5 wherein the capture is for a landfill gas process under pressure swing adsorption.

7. The method of claim 5 wherein the P.sub.ads/P.sub.des is about 5 atm/1 atm.

8. The method of claim 5 wherein the capture is for a landfill gas process under pressure swing adsorption.

9. The method of claim 8 wherein the P.sub.ads/P.sub.des is about 1 atm/vacuum pressure of 0.1 atm.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

(1) The accompanying drawings, which are incorporated into and form a part of the specification, illustrate one or more embodiments of the present invention and, together with the description, serve to explain the principles of the invention. The drawings are only for the purpose of illustrating one or more embodiments of the invention and are not to be construed as limiting the invention. In the drawings:

(2) FIG. 1 is a photograph of Zn(NH.sub.3)(CO.sub.3) single crystals;

(3) FIG. 2 shows powder x ray diffraction (PXRD) pattern of as-synthesized product as well as simulated pattern of Zn(NH.sub.3)(CO.sub.3);

(4) FIG. 3 shows adsorption isotherm for N.sub.2 uptake at 293, 273, 263, and 253 K;

(5) FIG. 4 shows adsorption isotherm for H.sub.2 uptake at 293, 273, 263, and 253 K;

(6) FIG. 5 shows adsorption isotherm for CO.sub.2 uptake at 313, 293, 273, 263, and 253 K;

(7) FIG. 6 shows adsorption isotherm for CH.sub.4 uptake at 293, 273, 263, and 253 K;

(8) FIG. 7A shows adsorption isotherm for O.sub.2 uptake at 293, 273, 263, and 253 K;

(9) FIG. 7B shows the Performance of Zn(NH.sub.3)(CO.sub.3) and other selected adsorbents in PSA-based oxy-fuel CO.sub.2 purification. The highest value of each parameter is bolded;

(10) FIG. 8 shows the adsorption branches of the isotherms of CO.sub.2, O.sub.2, H.sub.2, CH.sub.4, and N.sub.2 isotherms at 293 K for comparison;

(11) FIG. 9 shows the variation of composition of adsorbed phase and separation selectivity by Zn(NH.sub.3)(CO.sub.3), with pressure calculated by IAST method for binary mixture of CO.sub.2/CH.sub.4 (10/90) at 273 and 293 K;

(12) FIG. 10 shows the variation of composition of adsorbed phase and separation selectivity by Zn(NH.sub.3)(CO.sub.3), with pressure calculated by IAST method for binary mixture of CO.sub.2/CH.sub.4 (50/50) at 273 and 293 K;

(13) FIG. 11 show the variation of composition of adsorbed phase and separation selectivity by Zn(NH.sub.3)(CO.sub.3), with pressure calculated by IAST method for binary mixture of CO.sub.2/H.sub.2 (40/60) at 273 K and 293 K;

(14) FIG. 12 shows the variation of composition of adsorbed phase and separation selectivity by Zn(NH.sub.3)(CO.sub.3), with pressure calculated by IAST method for binary mixture of CO.sub.2/N.sub.2 (10/90) at 273 K and 293 K;

(15) FIG. 13 shows the variation of composition of adsorbed phase and separation selectivity by Zn(NH.sub.3)(CO.sub.3), with pressure calculated by IAST method for binary mixture of CO.sub.2/O.sub.2 (90/10) at 273 K and 293 K;

(16) FIG. 14 shows the variation of composition of adsorbed phase and separation selectivity by Zn(NH.sub.3)(CO.sub.3), with pressure calculated by IAST method for binary mixture of H.sub.2/N.sub.2 (50/50) at 273 K and 293 K;

(17) FIG. 15 shows the Polynomial fittings of CO.sub.2 (P,q) isotherm data;

(18) FIG. 16 shows sample isosteres of CO.sub.2 and temperature windows of diffusion- and adsorption-controlled domains;

(19) FIG. 17 shows sample isosteres of N.sub.2 and temperature windows of diffusion- and adsorption-controlled domains;

(20) FIG. 18 shows sample isosteres of H.sub.2 and temperature windows of diffusion- and adsorption-controlled domains;

(21) FIG. 19 shows sample isosteres of O.sub.2 and temperature windows of diffusion- and adsorption-controlled domains;

(22) FIG. 20 shows sample isosteres of CH.sub.4 and temperature windows of diffusion- and adsorption-controlled domains;

(23) FIG. 21 shows Isosteric heat of adsorption of CO.sub.2 calculated for diffusion-controlled (diamond) and adsorption-controlled domains (square);

(24) FIG. 22 shows Isosteric heat of adsorption of N.sub.2 calculated for diffusion-controlled (diamond) and adsorption-controlled domains (square);

(25) FIG. 23 shows Isosteric heat of adsorption of H.sub.2 calculated for diffusion-controlled (diamond) and adsorption-controlled domains (square);

(26) FIG. 24 shows Isosteric heat of adsorption of O.sub.2 calculated for diffusion-controlled (diamond) and adsorption-controlled domains (square);

(27) FIG. 25 shows Isosteric heat of adsorption of CH.sub.4 calculated for diffusion-controlled (diamond) and adsorption-controlled domains (square);

(28) FIG. 26 shows Isosteric heats of adsorption of CO.sub.2, N.sub.2, H.sub.2, O.sub.2, and CH.sub.4 at diffusion-controlled domain;

(29) FIG. 27 shows Isosteric heats of adsorption of CO.sub.2, N.sub.2, H.sub.2, O.sub.2, and CH.sub.4 at adsorption-controlled domain;

(30) FIG. 28 shows N.sub.2 adsorption isotherm at 77 K by Zn(NH.sub.3)(CO.sub.3), used to calculate BET surface area. Filled and open symbols represent adsorption and desorption data, respectively;

(31) FIG. 29A shows the crystalline structure of Zn(NH.sub.3)(CO.sub.3). CO.sub.3 trigonal planars and ZnO.sub.3N tetrahedra are shown in gray and green, respectively. The circular arrows show the spiral directions of the folded helices. The (ZnOCO).sub.2 and (ZnOCO).sub.4 helices are visualized in orange and blue, respectively. The border of the helices is shown in yellow;

(32) FIG. 29B shows the folded helices are shown in detail. Ammine ligands are eliminated for better visualization in this schematic; and

(33) FIG. 29C shows the projection of crystalline structure in the b direction. The two types of microchannels with 8 and 16 components in the Zn(NH.sub.3)(CO.sub.3) helical framework are shown in yellow and cyan, respectively. (Legend: (Green: Zn; Gray: C; Red: O; Cyan: N; Magenta: H)).

DETAILED DESCRIPTION OF THE INVENTION

(34) In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the invention. However, it will be understood by one of ordinary skill in the art that the embodiments may be practiced without these specific details. For instance, well known operation or techniques may not be shown in detail. Technical and scientific terms used in this description have the same meaning as commonly understood to one or ordinary skill in the art to which this subject matter belongs.

(35) In one embodiment, Zn(NH.sub.3)(CO.sub.3) is synthesized through a single-pot approach based on urea hydrolysis and solvothermal aging. In this embodiment, zinc acetate and urea solutions in the mixture of N,N-Dimethylformamide (DMF) and water are preferably used to construct a ZnNH.sub.3CO.sub.3.sup.2 system that upon heating at between approximately 80 C. and approximately 100 C., more preferably between approximately 85 C. and approximately 95 C., and most preferably between approximately 88 C. and approximately 92 C., and afterwards solvothermal aging at between approximately 120 C. and approximately 160 C., more preferably between approximately 130 C. and approximately 150 C., and most preferably between approximately 135 C. and approximately 142 C., leads to the growth of large single crystals of Zn(NH.sub.3)(CO.sub.3). In one embodiment DMF is substituted for another solvent with a high boiling point, for example, N-Methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), hexamethylphosphoramide (HMPA), pyridine (Py), and gamma-Butyrolactone (GBL).

(36) Thermodynamic calculations show that zinc ammine is the dominant stable specie in ZnNH.sub.3CO.sub.3.sup.2 system at pH of 10 when concentration of total zinc and carbonate ions are below 0.1M respectively. As the concentration of the zinc or carbonate ions increase, the zinc ammine fraction exponentially decreases and Zn.sub.5(OH).sub.6(CO.sub.3).sub.2 precipitates. Therefore, as long as synthesis of Zn(NH.sub.3)(CO.sub.3) is taking place, the concentration of zinc and carbonate sources in the reaction mixture should preferably not exceed about 0.1M.

(37) In addition to the zinc and carbonate sources concentration, the concentration of ammonia in the reaction mixture is preferably low enough to control the pH between 8 and 11 to crystalize Zn(NH.sub.3)(CO.sub.3) rather than production of soluble zinc ammine complexes. For example, low introduction of ammonia to the reaction medium is optionally used to prevent production of soluble zinc ammine complexes, which is preferably achieved by a urea hydrolysis system. Upon heating above approximately 90 C., the aqueous solution of urea decomposes to cyanate and ammonium ions resulting in a series of acid/base reactions. The overall effect of those reactions is slow release of ammonia to the reaction medium:
OC(NH.sub.2).sub.2NCO.sup.+NH.sub.4.sup.+(2)
NCO.sup.+2H.sub.2O.fwdarw.NH.sub.3+HCO.sub.3.sup.(3)

(38) The urea hydrolysis reactions and associated acid/base equilibria when the aqueous urea solution is heated at approximately 90 C. are as follows:
OC(NH.sub.2).sub.2NCO.sup.+NH.sub.4.sup.+(4)
NCO.sup.+2H.sub.2O.fwdarw.NH.sub.3+HCO.sub.3.sup.(5)
NCO.sup.+2H.sub.2O+HCO.sub.3.sup..fwdarw.NH.sub.3+2HCO.sub.3.sup.(6)
NCO.sup.+2H.sub.2O+NH.sub.3.fwdarw.2NH.sub.3+HCO.sub.3.sup.(7)
HNCO+H.sub.2O+H.sup.+.fwdarw.NH.sub.4.sup.++CO.sub.2(8)
HNCO+H.sub.2O.fwdarw.NH.sub.3+CO.sub.2(9)
H.sub.2OH.sup.++OH.sup.(10)
NH.sub.4.sup.+NH.sub.3+H.sup.+(11)
CO.sub.2+H.sub.2OHCO.sub.3.sup.+H.sup.+(12)
HCO.sub.3.sup.CO.sub.3.sup.2+H.sup.+(13)
HNCONCO.sup.+H.sup.+(14)

(39) Reactions 4 to 9 are independent reactions of decomposition of the urea to ammonia and cyanate and later decomposition of cyanate to ammonia and carbonic acid. CO.sub.2 in Equations 8 and 9 denotes gaseous and aqueous carbon dioxide and carbonic acid. Equations 10 to 14 are acid/base equilibria associated with the dissociations of urea products including cyanic acid, carbonic acid, and ammonium ion. The overall acid/base dissociation leads to a slow release of ammonia in the solution.

(40) The products of the second reaction (equation 3) preferably supply the ammonia and carbonate to the Zn(NH.sub.3)(CO.sub.3) structure and the ammonium ion from the first reaction (equation 2) serves as buffer to maintain the pH in the range of 8 to 11. The overall reaction of crystal formation follows:
Zn.sup.2++OC(NH.sub.2).sub.2+3H.sub.2O.fwdarw.Zn(NH.sub.3)(C.sub.3)+NH.sub.4OH+2H.sup.+(15)

(41) Another function of slow release of NH.sub.3 to reaction medium is preferably balancing the nucleation vs. growth reactions of crystallization in favor of growth reaction that preferably leads to the formation of large single crystals.

INDUSTRIAL APPLICABILITY

(42) The invention is further illustrated by the following non-limiting example.

Example 1

(43) A mixture of 19 mL DMF and 1 mL water was prepared. 439.0 mg (0.2 mmol) zinc acetate and 132 mg (2.2 mmol) urea were gently mixed in 210 mL of the solvent mixture to dissolve. Then, zinc acetate solution was gradually added to the urea solution and gently mixed to make a uniform solution. The solution of reactants was then capped and heated to 90 C. The heating resulted in precipitation. The mixture was heated for 2 hr. Next, the reaction mixture was placed into the Teflon liner of a hydrothermal reactor and the mixture was heated at 140 C. for 4 days. The process led to the formation of large single crystals of the product that were washed with DMF and dispersed into 10 mL of fresh chloroform for 4 days. The chloroform was exchanged every day. Finally, the crystals were activated by heating at 110 C. under vacuum to be prepared for adsorption analysis.

Example 2

(44) Urea (60 mg, 1 mmole) was dissolved in DMF (5 mL) in a 20-mL vial. Then, deionized water (1 mL) was slowly dripped into the urea solution in DMF and the vial was capped. The obtained solution was heated at 90-95 C. for 6 h. Afterwards, zinc acetate (329.3 mg, 1.5 mmole) was dissolved in DMF (10 mL) and dripped into the urea solution. The mixture started to precipitate, and it was heated at 90 C. for 1 h until precipitation was completed. Next, the uncapped vial of the mixture was placed into the Teflon liner of a hydrothermal reactor and heated at 150 C. for 4 days. Finally, the produced crystals were washed 3 times with DMF (10 mL) and then soaked in chloroform (10 mL) for 3 days. Every day, the used chloroform was replaced with a fresh solvent.

(45) FIG. 1 is a photograph of Zn(NH.sub.3)(CO.sub.3) single crystals.

(46) Referring now to FIG. 2, the pattern of powder x ray diffraction (PXRD) analysis performed on an as-synthesized sample and the simulated pattern of a phase pure product are shown. The pattern of the product repeated the simulated pattern. Therefore, the product was phase pure Zn(NH.sub.3)(CO.sub.3).

(47) The structure of Zn(NH.sub.3)(CO.sub.3) is represented in FIG. 29a-c. As revealed by SC-XRD from ICSD #41113, Zn(NH.sub.3)(CO.sub.3) has a helical crystalline framework, which is reproduced in FIG. 29a. The structure consists of CO.sub.3 trigonal planars, each of which is isolated from the others by three ZnO.sub.3N tetrahedra that share oxygens in the corners, whereas each ZnO.sub.3N tetrahedron keeps the N corner unshared. Regardless of polar-polar interactions between O and H and between N and H of the adjacent tetrahedra, the tetrahedra are also isolated from each other. With this configuration of isolated tetrahedra and trigonal planars, Zn, C, and O create two types of folded helices that develop in the b direction (shown in orange and blue in FIG. 29a, b): 1) a small helix of (ZnOCO).sub.2, and 2) a big helix of (ZnOCO).sub.4 with two ammines pendant from every other zinc toward the axis of the big helix, whose nitrogens are 4.018 away from each other. The helices share the ZnOC piece of their backbones (shown in yellow in FIG. 29a, b) and the pitches of both helices are 5.498 , which is equal to the b dimension of the Zn(NH.sub.3)(CO.sub.3) unit cell. The spiral direction of the helices in the c direction stays the same, but helices are packed with a right-handed/left-handed pattern in the a direction. The projection of the structure in the b direction visualizes two types of microchannels with 8 and 16 components, which are shown in yellow and cyan, respectively, in FIG. 29c.

(48) Adsorption Isotherms

(49) As can be seen from FIG. 29, the pendant ammines in the (ZnOCO).sub.4 helix have enough distance between them to accommodate small gas molecules such as H.sub.2, CO.sub.2, O.sub.2, N.sub.2, and CH.sub.4, whose kinetic diameters range from 2.9 to 3.8 . The configuration of the (ZnOCO) in helices with a pitch of 5.498 could make the volume of the (ZnOCO).sub.2 helix accessible from the a and c directions for the molecules that can primarily diffuse to the (ZnOCO).sub.4 helix. Based upon these speculations, an adsorption property for this structure could be hypothesized. The adsorptives used for adsorption analysis in this study were CO.sub.2, N.sub.2, H.sub.2, O.sub.2, and CH.sub.4. The physical properties of the adsorptives are tabulated in Table 3.1. The kinetic diameter is a critical property of the adsorptives that is effective in specifying the mechanism of adsorption. Polarizability is also influential on the strength of interaction between adsorbate and adsorbent in thermodynamic mechanism. Additionally, dipole moment is a significant measure for determining the strength of the interaction between adsorbate and adsorbent. Since the adsorptives of this study are all nonpolar, their dipole moments are zero.

(50) TABLE-US-00001 TABLE 0.1 Physical properties of adsorptives. Molecular Boiling Kinetic Polarizability Adsorptive weight (amu) point (K) diameter () 10.sup.25 (cm.sup.3) H.sub.2 2.016 20.27 2.89 8.042 N.sub.2 28.013 77.35 3.80 17.403 O.sub.2 31.999 90.17 3.46 15.812 CO.sub.2 44.01 216.55 3.3 29.11 CH.sub.4 16.034 111.66 3.76 25.93

(51) Referring to FIGS. 3-7, the isotherms of CO.sub.2 uptake at 253, 263, 273, 293, and 313 K and 0 to 4500 mmHg and N.sub.2, H.sub.2, CH.sub.4, and O.sub.2 uptake at 253, 263, 273, and 293 K and 0 to 4500 mmHg are shown. FIG. 8 shows the adsorption branches of all of these isotherms to allow better comparison of the adsorption behavior. The adsorption branches of the N.sub.2, H.sub.2, CH.sub.4, and O.sub.2 isotherms were convex toward the pressure axis, indicating poor interaction between these nonpolar adsorbates and the microchannels of the adsorbent. The isotherm of CO.sub.2 uptake, in contrast, was concave to the pressure axis at lower pressures and deflects toward the uptake axis at approximately 1800 mmHg, indicating favorable adsorbate-adsorbent interaction at lower pressures. While CO.sub.2 had a kinetic diameter of 3.3 , which was larger than the diameter of H.sub.2 (2.9 ) and smaller than N.sub.2 (3.6 ), the hydrogen-bond-type interaction between oxygens of CO.sub.2 and hydrogens of pendant NH.sub.3 gave rise to the shape of the adsorption branch of the isotherm as well as the uptake, 0.56 mmol/g, which was an order of magnitude higher than that of H.sub.2, O.sub.2, CH.sub.4 and N.sub.2.

(52) Henry's Constants and Selectivities

(53) Henry's constant, K.sub.H, which is the ratio of uptake to pressure at equilibrium and at a concentration of the adsorbate that is sufficiently low to ignore adsorbate-adsorbate interaction (Equation 1.37),

(54) $\begin{array}{cc}q=\frac{{K^{}\left(T\right)}_{H}p}{\mathrm{RT}}={K_H\left(T\right)}_p={K^{}\left(T\right)}_{H}C& \mathrm{Eq}.0.1\end{array}$
provides a quantitative measure for assessing the interaction of an adsorbate with an adsorbent and evaluating the selectivity of the synthesized material (Equation 1.67).

(55) $\begin{array}{cc}{}_{\mathrm{Hij}}=\frac{K_{\mathrm{Hi}}}{K_{\mathrm{Hj}}}& \mathrm{Eq}.0.2\end{array}$
Henry's constant can be calculated by fitting the isotherm data in a virial equation, expressed in Equation 1.51.

(56) $\begin{array}{cc}\frac{p}{q}=\frac{1}{K_H}.Math.\exp \left(C_{1}q+C_2{q}^2+\mathrm{.Math.}\right)& \mathrm{Eq}.0.3\end{array}$
For low pressures and/or small uptakes, second and higher orders of q in Equation 1.51 are small enough to be ignored. Therefore, Equation 1.51 can be modified as follows:

(57) $\begin{array}{cc}\mathrm{Ln}\left(\frac{P}{q}\right)=C_{1}q-\ln K_H& \mathrm{Eq}.0.4\end{array}$

(58) By performing linear regression of Ln(P/q) versus q and by extrapolating the fitted line to calculate the intercept, K.sub.H can be obtained. The calculated Henry's constants are shown in Table 3.4.

(59) Henry's constant, derived from the adsorption isotherm of pure gas, is an asset for assessing the separation behavior of the material when it is exposed to a gas mixture. Table 3.5 shows the equilibrium separation selectivities of the material when it is exposed to the binary mixtures of CO.sub.2, N.sub.2, H.sub.2, O.sub.2, and CH.sub.4 based on the ratio of Henry's constants (Equation 1.67).

(60) Since adsorption at low temperatures is diffusion controlled the adsorbent does not offer significant equilibrium selectivity at 253 K. Rather, separation at this temperature should be based on adsorption kinetic. At 263 K, where adsorptions on CO.sub.2, N.sub.2, and H.sub.2 are controlled by both diffusion and adsorption, the equilibrium selectivities of those binary mixtures increase.

(61) TABLE-US-00002 TABLE 0.2 Henry's constants of CO.sub.2, N.sub.2, H.sub.2, O.sub.2, and CH.sub.4 adsorption, calculated from virial isotherm. K.sub.H (mmole/kPa .Math. g) 10.sup.4 293 273 263 253 Adsorptive (K) (K) (K) (K) CO.sub.2 5.700 5.939 5.710 28.342 N.sub.2 0.091 0.036 0.166 15.742 H.sub.2 0.184 0.079 1.361 15.663 O.sub.2 0.506 0.634 12.717 27.832 CH.sub.4 0.158 0.036 12.804 15.361

(62) TABLE-US-00003 TABLE 0.3 Estimated selectivities for binary mixtures of CO.sub.2, N.sub.2, H.sub.2, O.sub.2, and CH.sub.4 by Zn(NH.sub.3)(CO.sub.3) at 293, 273, 263, and 253 K. Gas .sub.Hij Mixture 293 (K) 273 (K) 263 (K) 253 (K) CO.sub.2/CH.sub.4 36.0 166.6 0.4 1.8 CO.sub.2/H.sub.2 31.1 75.1 4.2 1.8 CO.sub.2/N.sub.2 62.9 166.0 34.3 1.8 CO.sub.2/O.sub.2 11.3 9.4 0.4 1.0 H.sub.2/N.sub.2 2.0 2.2 8.2 1.0 O.sub.2/N.sub.2 5.6 17.7 76.5 1.8

(63) The maximum selectivity for air separation (N.sub.2/O.sub.2 mixture) can be achieved at 263 K, where O.sub.2 adsorption is still in diffusion-controlled domain, but where N.sub.2 has entered the dual-controlled mode. Separation of CO.sub.2 from O.sub.2 and CH.sub.4 at this temperature is not advantageous because of CO.sub.2 adsorption being in dual-controlled mode. The largest equilibrium selectivities for CO.sub.2 separation are exhibited at 273 K, where adsorptions of all gases are in the dual-controlled domain. Selectivities of CO.sub.2 separation from N.sub.2, H.sub.2, and CH.sub.4 at 293 K have decreased compared to 273 K because uptakes of those gases have increased at 293 K in comparison to 273 K (see the inset of FIG. 7.5).

(64) Selectivity Based on IAST

(65) As explained in Subsection 1.6.8.2, IAST is capable of predicting the composition of the adsorbed phase for a given binary mixture of adsorptives with known q=f(p) isotherm data of pure components of the mixture. Once the composition of adsorptive and adsorbate phases is known, selectivity (.sub.Iij) can be calculated. This section calculates .sub.Iij for selected binary mixtures with potential industrial significance (Table 3.6) at varied pressures (0 to 4600 mmHg) and temperatures (293 and 273 K) to evaluate the functionality of the selectivity with pressure and temperature.

(66) To find q=f(p), isotherm data were fitted into polynomial equations, and the equations were plugged into Equation 1.71.

(67) $\begin{array}{cc}{}_{t=0}^{P\frac{y_1}{x_1}}{q}_1\left(t\right)\frac{\mathrm{dt}}{t}={}_{t=0}^{P\frac{y_2}{x_2}}{q}_2\left(t\right)\frac{\mathrm{dt}}{t}& \mathrm{Eq}.0.5\end{array}$

(68) The integrals of Equation 1.71 can be solved for a sample polynomial q=f(p) with n=3 as follows:

(69) $\begin{array}{cc}{}_{t=0}^{P\frac{y_1}{x_1}}\left({\mathrm{at}}^3+{\mathrm{bt}}^2+\mathrm{ct}\right)\frac{\mathrm{dt}}{t}=\frac{a}{3}{\left(P\frac{y_1}{x_1}\right)}^3+\frac{b}{2}{\left(P\frac{y_1}{x_1}\right)}^2+c\left(P\frac{y_1}{x_1}\right)& \mathrm{Eq}.0.6\end{array}$
Equation 1.71, with the solution in the form of Equation 3.21, can be solved by trial and error for a given P to calculate equivalent x.sub.1 (and thus x.sub.2).

(70) TABLE-US-00004 TABLE 0.4 Binary mixtures of CO.sub.2, N.sub.2, H.sub.2, O.sub.2, and CH.sub.4 and their potential industrial significance considered for calculation of .sub.Iij. Composition Gas Mixture (%/%) Significance CO.sub.2/CH.sub.4 10/90 Natural gas purification CO.sub.2/CH.sub.4 50/50 Landfill gas separation CO.sub.2/H.sub.2 40/60 Syngas separation CO.sub.2/N.sub.2 10/90 Flue gas separation CO.sub.2/O.sub.2 90/10 Oxy-fuel gas separation H.sub.2/N.sub.2 50/50

(71) FIG. 9 shows the varied compositions of the adsorbed phase and the separation selectivities by Zn(NH.sub.3)(CO.sub.3) with pressure at 273 K and 293 K for a binary mixture of CO.sub.2/CH.sub.4 (10/90), FIG. 10 shows the same for CO.sub.2/CH.sub.4 (50/50), FIG. 11 for CO.sub.2/H.sub.2 (40/60), FIG. 12 for CO.sub.2/N.sub.2 (10/90), FIG. 13 for CO.sub.2/O.sub.2 (90/10), and FIG. 14 for H.sub.2/N.sub.2 (50/50).

(72) The common feature of all separations is an exponential decrease of selectivity and therefore, the composition of more adsorbed adsorptive as pressurei.e., uptakeincreases. This behavior can be attributed to the effect of adsorbate-adsorbate interaction in the selectivity of adsorbent as uptake increases.

(73) Selectivity, as a ratio of Henry's constants of the separation mixture, (.sub.Hij), is a measure of the adsorbent's behavior at low pressures. The values of .sub.Hij for separation by Zn(NH.sub.3)(CO.sub.3) were calculated and tabulated in Table 3.5. To compare the selectivity based on Henry's constant and IAST, .sub.Iij at 10 mmHg and .sub.Hij at 293 K and 273 K are compared in Table 3.7.

(74) The values of .sub.Iij and .sub.Hij at 293 K and 273 K for separation of CO.sub.2/CH.sub.4 (10/90) are far different. On the other hand, .sub.Iij and .sub.Hij have the same order of magnitude at 293 K and 273 K for the separation of the same components but different concentrations: CO.sub.2/CH.sub.4 (50/50). This discrepancy of selectivities for the separation of 10/90 mixture is related to the inaccuracy of IAST method for predicting the composition of the adsorbed phase of the mixture with high concentrations of the less-adsorbed component (here, CH.sub.4 with concentration of 90%). A similar discrepancy can be observed between .sub.Iij and .sub.Hij for the separation of CO.sub.2/N.sub.2 (10/90). The agreement between .sub.Iij and .sub.Hij increased as the concentration of the less-adsorbed component decreased, and the highest agreement was observed for CO.sub.2/O.sub.2 (90/10), where at 293 K, .sub.Iij and .sub.Hij are 11.3 and 13.8, respectively, and 9.4 and 9.2, respectively, at 273 K.

(75) At low pressures, IAST predicts that the concentration of adsorbed CO.sub.2 and consequently the selectivity for the separation of CO.sub.2/H.sub.2 (40/60) and CO.sub.2/N.sub.2 (10/90) at 273 K are smaller than at 293 K (see FIGS. 11 and 12). However, the trends reverse as pressure increases (approximately 700 mmHg for CO.sub.2/H.sub.2 (40/60) and 150 mmHg for CO.sub.2/N.sub.2 (10/90)). Such changes in selectivity and the concentration of the adsorbed phase are congruent with H.sub.2 and N.sub.2 isotherms at 293 K and 273 K (see FIGS. 4 and 3). The values of .sub.Hij at 293 K and 273 K agree with the IAST trend at higher pressure (.sub.Hij at 273 is larger than .sub.Hij at 293 K). That is because the uptakes at larger pressures were used to calculate .sub.Hij.

(76) As FIG. 13 shows, IAST predicts the concentration of adsorbed CO.sub.2 and the selectivity of CO.sub.2/O.sub.2 (90/10) separation at 293 K to be larger than those at 273 K. This trend agrees with the trend of .sub.Hij at 293 K and 273 K represented in Table 3.5.

(77) TABLE-US-00005 TABLE 0.5 Comparison of .sub.Hij and .sub.Iij at 293 K and 273 K for different binary mixtures. Gas Mixture 293 (K) 273 (K) (%/%) .sub.Hij .sub.Iij .sup.a .sub.Hij .sub.Iij .sup.a CO.sub.2/CH.sub.4 (10/90) 36.0 1491.0 166.6 1583.9 CO.sub.2/CH.sub.4 (50/50) 36.0 44.5 166.6 351.1 CO.sub.2/H.sub.2 (40/60) 31.1 22.7 75.1 19.1 CO.sub.2/N.sub.2 (10/90) 62.9 520.4 166.0 152.1 CO.sub.2/O.sub.2 (90/10) 11.3 13.8 9.4 9.2 H.sub.2/N.sub.2 (50/50) 2.0 6.3 2.2 9.4 .sup.a Calculated at 10 mmHg
BET Analysis and Structural Stability

(78) To calculate the BET surface area, N.sub.2 adsorption analysis by Zn(NH.sub.3)(CO.sub.3) was performed at 77 K. FIG. 28 shows the adsorption isotherm of the material. 5.3 mmole/g of N.sub.2 was adsorbed at the relative pressure (P/P.sub.s) of 0.995. The adsorption branch of the isotherm is almost linear, and hysteresis at lower pressure could still be observed.

(79) The equivalent BET surface area calculated for the Zn(NH.sub.3)(CO.sub.3) framework is 207 m.sup.2/g. The C-value and correlation coefficient were calculated as 2.44 and 0.9973, respectively. The C-value, a parameter used for fitting the BET equation, is exponentially related to the enthalpy of adsorption in the first layer of adsorbed gas, and it is a qualitative measure for adsorbate-adsorbent interaction. The obtained BET surface area is in the range of the values reported for other ultramicroporous materials.

(80) To assess if the material is sufficiently structurally robust to withstand the recurring cycles of adsorption and desorption that commonly occur in separation processes, a comparison was performed between the CO.sub.2 adsorption isotherms of a sample of fresh Zn(NH.sub.3)(CO.sub.3) and Zn(NH.sub.3)(CO.sub.3) subjected to 80 cycles of adsorption and desorption. The maximum uptake at 4500 mmHg for the used sample was only 0.8% less than the uptake of the fresh sample, indicating that the material structure is stable under the cyclical adsorption-desorption process.

(81) In addition to structural stability, as the adsorption analysis procedure implies, Zn(NH.sub.3)(CO.sub.3) is thermally stable at 110 C. To check the chemical stability in water, the crystals were mixed in water for weeks, a procedure that was found not to affect Zn(NH.sub.3)(CO.sub.3) structure.

(82) Potential Industrial Applications

(83) As previously discussed there are CO.sub.2 separation processes associated with power generation, in which CO.sub.2/N.sub.2, CO.sub.2/H.sub.2, and CO.sub.2/O.sub.2 are good constituents of post-combustion, pre-combustion, and oxy-fuel CO.sub.2 capture, respectively. In addition to power generation sector, the natural gas industry is another sector facing the challenge of CO.sub.2 separation. An important component of natural gas is CH.sub.4 (80-95%), and it also includes impurities composed of N.sub.2, CO.sub.2, H.sub.2, other hydrocarbons heavier than CH.sub.4, and traces of other materials such as water and sulphur. Landfill gas (LFG) is another source of CH.sub.4. LFG comprises 45-60% CH.sub.4 and 40-60% CO.sub.2. CO.sub.2 separation from CH.sub.4 is necessary to upgrade the natural gas and prevent pipeline corrosion.

(84) As explained above, Zn(NH.sub.3)(CO.sub.3) is thermally, chemically, and structurally robust enough to withstand the operating conditions of CO.sub.2 separation processes. In the present subsection, the adsorption selection criteria are calculated for Zn(NH.sub.3)(CO.sub.3) for the above-mentioned CO.sub.2 separation processes by Pressure swing adsorption (PSA) or Vacuum swing adsorption (VSA), and the values are compared with those of other adsorbents. For each process, a binary mixture with an average composition is selected, and adsorption pressure (P.sub.ads) and desorption pressure (P.sub.des) are set close to the conditions of upstream industrial operations. The criteria used to evaluate the adsorbents' performances are uptake capacity (q), working capacity (q), working selectivity (.sub.qij), regenerability (R), and adsorbent selection parameter (S). Out of this analysis and comparison, the suitability of the adsorbent for a specific application can be assessed.

(85) Natural Gas Purification Using PSA

(86) Typical operating conditions for natural gas purification using PSA are as follows: CO.sub.2/CH.sub.4 composition: 10/90 P.sub.ads/P.sub.des: 5 atm/1 atm T: Room temperature (RT)

(87) Table 3.9 tabulates the calculated values of the selection parameters for Zn(NH.sub.3)(CO.sub.3) and other prominent adsorbents. Zn(NH.sub.3)(CO.sub.3) exhibits the highest R, which is the result of the type of isotherm. However, since the partial pressure of the CO.sub.2 in the mixture is low, q and q of the adsorbent are lower than other adsorbents. Moreover, other adsorbents are better candidates with respect to the working selectivity and S. All in all, Zn(NH.sub.3)(CO.sub.3) is not the best candidate for PSA-based natural gas purification.

(88) TABLE-US-00006 TABLE 0.6 Performance of Zn(NH.sub.3)(CO.sub.3) and other selected adsorbents in PSA-based natural gas purification. The highest value of each parameter is bolded. T q q R Adsorbent (K) (mmole/g) (mmole/g) (%) .sub.qij S Zn(NH.sub.3)(CO.sub.3) 293 0.027 0.022 80.9 7.2 1.4 POP1.sup.a 298 1.39 0.86 62.2 9.7 7.5 MOF1.sup.b 303 0.89 0.62 69.7 16.7 18.7 HKUST-1 298 2.07 1.70 63.0 10.0 9.6 MOF Zeolite-13X 298 3.97 1.48 37.3 18.9 9.0 .sup.aDiimide porous organic polymer (POP) .sup.bAmine-Al-MIL-53
LFG Separation Using PSA

(89) Typical operating conditions for this process are as follows:

(90) CO.sub.2/CH.sub.4 composition: 50/50

(91) P.sub.ads/P.sub.des: 5 atm/1 atm T: RT

(92) Table 3.10 tabulates the calculated values of the selection parameters for Zn(NH.sub.3)(CO.sub.3) and other prominent adsorbents. Regardless of q and q, Zn(NH.sub.3)(CO.sub.3) provides higher R, .sub.qij, and S values than other known candidates. Therefore, Zn(NH.sub.3)(CO.sub.3) can be an appropriate adsorbent for LFG separation by PSA.

(93) TABLE-US-00007 TABLE 0.7 Performance of Zn(NH.sub.3)(CO.sub.3) and other selected adsorbents in PSA-based LFG separation. The highest value of each parameter is bolded. T q q R Adsorbent (K) (mmole/g) (mmole/g) (%) .sub.qij S Zn(NH.sub.3)(CO.sub.3) 293 0.158 0.131 82.9 13.5 50.7 HKUST-1 298 8.01 5.34 66.7 4.9 21.0 MOF MIL-101c 303 6.70 3.20 47.8 5.0 9.5 MOF MOF1.sup.a 298 0.94 0.66 70.6 3.3 8.3 Zeolite-13X 298 5.37 1.40 26.1 4.2 2.0 POP1.sup.b 298 2.93 1.44 49.2 3.6 11.5 .sup.a[Zn.sub.3(OH)(p-cdc).sub.2.5(DMF).sub.4] where p-CDC is deprotonated form of 1,12-dihydroxydicarbonyl-1,12-dicarba-closo-dode-caborane .sup.b35% Li-reduced diimide-POP
LFG Separation Using VSA

(94) Typical operating conditions for this process are as follows: CO.sub.2/CH.sub.4 composition: 50/50 P.sub.ads/P.sub.des: 1 atm/0.1 atm T: RT

(95) Table 3.11 displays the calculated values of the selection parameters for Zn(NH.sub.3)(CO.sub.3) and other prominent adsorbents. Regardless of q and q, Zn(NH.sub.3)(CO.sub.3) provides higher R, .sub.qij, and S values than other known candidates. The superior performance of Zn(NH.sub.3)(CO.sub.3) for this process originates from the fact that CH.sub.4 adsorption at the conditions of this process can practically be considered as zero. Therefore, Zn(NH.sub.3)(CO.sub.3) can be an appropriate adsorbent for LFG separation by VSA.

(96) TABLE-US-00008 TABLE 0.8 Performance of Zn(NH.sub.3)(CO.sub.3) and other selected adsorbents in VSA-based LFG separation. The highest value of each parameter is bolded. T q q R Adsorbent (K) (mmole/g) (mmole/g) (%) .sub.qij S Zn(NH.sub.3)(CO.sub.3) 293 0.027 0.024 90.5 42.8 272.7 HKUST-1 298 2.81 1.90 67.5 5.5 19.8 MOF MIL-101c 303 6.70 3.20 47.8 5.0 9.5 MOF Mg-MOF-74 298 7.23 2.32 32.1 12.5 23.5 ZIF-82 298 1.42 1.20 84.9 5.6 20.5 Zeolite-13X 298 3.97 1.97 49.6 13.2 19.1
Post-Combustion Flue Gas Separation Using VSA

(97) Typical operating conditions for this process are as follows: CO.sub.2/N.sub.2 composition: 10/90 P.sub.ads/P.sub.des: 1 atm/0.1 atm T: RT

(98) Regarding the low partial pressure of CO.sub.2, the CO.sub.2 uptake is not considerable under the conditions of this process. In addition, adsorbents like zeolite 13-x, Co-carborane MOF-4b, and ZIF-78 show higher R, .sub.qij, and S values than Zn(NH.sub.3)(CO.sub.3). Therefore, Zn(NH.sub.3)(CO.sub.3) is not a good candidate for VSA-based post-combustion flue gas separation.

(99) Pre-Combustion Hydrogen Separation Using PSA

(100) Typical operational conditions for this process are as follows: CO.sub.2/H.sub.2 composition: 40/60 P.sub.ads/P.sub.des: 5 atm/1 atm T: RT

(101) Table 3.12 shows the calculated values of the selection parameters for Zn(NH.sub.3)(CO.sub.3) and other prominent adsorbents. Zn(NH.sub.3)(CO.sub.3) exhibits the highest R, which is result of the type of isotherm. However, since the partial pressure of the CO.sub.2 in the mixture is low, q and q of the adsorbent are lower than other adsorbents. Moreover, other adsorbents are better candidates with respect to the working selectivity and S. All in all, Zn(NH.sub.3)(CO.sub.3) is not a good candidate for PSA-based natural gas purification.

(102) TABLE-US-00009 TABLE 0.9 Performance of Zn(NH.sub.3)(CO.sub.3) and other selected adsorbents in PSA-based precombustion hydrogen separation. The highest value of each parameter is bolded T q q R Adsorbent (K) (mmole/g) (mmole/g) (%) .sub.qij S Zn(NH.sub.3)(CO.sub.3) 293 0.122 0.101 82.5 7.3 10.9 Carbon active 303 3.33 1.88 56.5 58.7 639.6 Zeolite NaX 303 5.02 1.22 24.4 4.04 2.6 Zeolite 303 3.93 1.96 49.8 98.3 1960.3
Oxy-Fuel CO.sub.2 Purification Using PSA

(103) Typical operating conditions for this process are as follows: CO.sub.2/O.sub.2 composition: 90/10 P.sub.ads/P.sub.des: 5 atm/1 atm T: RT

(104) Table 3.13 tabulates the calculated values of the selection parameters for Zn(NH.sub.3)(CO.sub.3) and other prominent adsorbents. Regardless of q and q, Zn(NH.sub.3)(CO.sub.3) provides higher R, .sub.qij, and S values than other known candidates. The superior performance of the adsorbent for this process originates from the high partial pressure of CO.sub.2 and low O.sub.2 uptake at RT. Therefore, Zn(NH.sub.3)(CO.sub.3) can be an appropriate adsorbent for Oxy-fuel CO.sub.2 Purification by PSA.

(105) TABLE-US-00010 TABLE 0.10 Performance of Zn(NH.sub.3)(CO.sub.3) and other selected adsorbents in PSA-based oxy-fuel CO.sub.2 purification. The highest value of each parameter is bolded. T q q R Adsorbent (K) (mmole/g) (mmole/g) (%) .sub.qij S Zn(NH.sub.3)(CO.sub.3) 293 0.338 0.288 85.1 17.3 844.8 Cu-BTC MOF 298 10.207 5.760 56.4 4.1 6.6 Zeolite NaX 303 5.548 1.281 23.1 9.4 85.5

(106) Regarding the ultramicroporous structure, Zn(NH.sub.3)(CO.sub.3) does not exhibit large gas uptake compared to other adsorbents. However, this deficiency is offset by considerable selectivity, regenerability, and adsorbent selection parameterespecially for processes in which partial pressure of CO.sub.2 and/or adsorption pressure is large. The origin of this behavior is the Type II isotherm of CO.sub.2 adsorption and the Type II isotherm of adsorption of other gases at room temperature. Since all selection criteria are considered for industrial adsorbent selection, Zn(NH.sub.3)(CO.sub.3) is capable of being adopted for processes such as LFG and CO.sub.2/O.sub.2 separations. It should be noted that chemical, structural, and thermal stabilities were not assessed for all the candidate adsorbents referenced in Tables 3.9 to 3.13. If these conditions were considered in the selection criteria, some adsorbents would be recognized as unsuitable for industrial use. For instance, MOF-74's superior CO.sub.2 capacity is due to the exposed cations, which make MOF-74 water- and air-sensitive and thus inapplicable for LFG (see Table 3.11) and flue gas separation.

(107) N.sub.2 and O.sub.2 needed in industries are acquired from air by air separation processes, and the most common air separation process utilized in industry is cryogenic distillation. Since the critical temperature and pressure of air are 140.7 C. (132.5 K) and 37.7 bar, respectively, air separation should be performed at temperatures below 140.7 C. (132.5 K). For instance, to separate air at atmospheric pressure, the temperature must be decreased to 192 C. (81.5 K) to have vapor-liquid equilibrium. To increase this temperature to 172 C. (101 K), air should be compressed to 6 bar. Therefore, air separation by this process is extremely energy-intensive. On the other hand, air separation by the adsorption process is limited to small-scale separation by zeolites under the kinetic mechanism. The O.sub.2 and N.sub.2 separated by this process are not pure and usually are used in hospitals. As Table 3.5 implies, Zn(NH.sub.3)(CO.sub.3) shows considerable selectivity to separate O.sub.2 from N.sub.2 at 263 K (.sub.Hij=76.5). Although this temperature is still sub-atmospheric, it is much higher than temperatures at which cryogenic distillation is operated. Therefore, adsorption-based air separation by Zn(NH.sub.3)(CO.sub.3) can be proposed, for which the operating conditions are as follows: O.sub.2/N.sub.2 composition: 20/80 P.sub.ads/P.sub.des: 5 atm/1 atm T: 263 K

(108) Table 1.4 tabulates the calculated values of the selection parameters for Zn(NH.sub.3)(CO.sub.3). Based upon these selection criteria, it can be expected that air separation by this process is less energy-intensive than cryogenic distillation. To validate the proposed process, energy assessment analysis is required to measure the energy penalty associated with this process and compare it with that of cryogenic distillation. Such analysis was out of scope of this study.

(109) TABLE-US-00011 TABLE 0.11 Performance of Zn(NH.sub.3)(CO.sub.3) in a PSA based air separation. q q R (mmole/g) (mmole/g) (%) .sub.qij S 0.150 0.121 80.8 19.2 49.5

(110) The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or parameters of this invention for those used in the preceding examples.

(111) Note that in the specification and claims, about or approximately means within twenty percent (20%) of the numerical amount cited. Although the invention has been described in detail with particular reference to these embodiments, other embodiments can achieve the same results. Variations and modifications of the present invention will be obvious to those skilled in the art and it is intended to cover in the appended claims all such modifications and equivalents. The entire disclosures of all references, applications, patents, and publications cited above are hereby incorporated by reference.